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Nanomaterials 2021, 11(12), 3369
Heat-Up Colloidal Synthesis of Shape-Controlled Cu-Se-S Nanostructures—Role of Precursor and Surfactant Reactivity and Performance in N2 Electroreduction
Copper selenide-sulfide nanostructures were synthesized using metal-organic chemical routes in the presence of Cu- and Se-precursors as well as S-containing compounds. Our goal was first to examine if the initial Cu/Se 1:1 molar proportion in the starting reagents would always lead to equiatomic composition in the final product, depending on other synthesis parameters which affect the reagents reactivity. Such reaction conditions were the types of precursors, surfactants and other reagents, as well as the synthesis temperature. The use of ‘hot-injection’ processes was avoided, focusing on ‘non-injection’ ones; that is, only heat-up protocols were employed, which have the advantage of simple operation and scalability. All reagents were mixed at room temperature followed by further heating to a selected high temperature. It was found that for samples with particles of bigger size and anisotropic shape the CuSe composition was favored, whereas particles with smaller size and spherical shape possessed a Cu2−xSe phase, especially when no sulfur was present. Apart from elemental Se, Al2Se3 was used as an efficient selenium source for the first time for the acquisition of copper selenide nanostructures. The use of dodecanethiol in the presence of trioctylphosphine and elemental Se promoted the incorporation of sulfur in the materials crystal lattice, leading to Cu-Se-S compositions. A variety of techniques were used to characterize the formed nanomaterials such as XRD, TEM, HRTEM, STEM-EDX, AFM and UV-Vis-NIR. Promising results, especially for thin anisotropic nanoplates for use as electrocatalysts in nitrogen reduction reaction (NRR), were obtained.
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Eur. Phys. J. D 75, 304 (2021)
Effects of static and dynamic femtosecond laser modifications of Ti/Zr multilayer thin films
The experimental study of the static and dynamic femtosecond laser ablation of the multilayer 15x(Ti/Zr)/Si system is reported. The layer-by-layer selective laser ablation mechanism was studied by analysis of the surface morphology and elemental composition in static single pulse irradiation in a range of pulse energy from 10 to 17 μJ. The selective ablations, as number of concentric circles in modified spots are increased with the pulse energy. The boundary between the circles was shown a change in the depth, comparable to the thickness of the individual layers. Changes in the elemental composition at the edges are associated with the removal of the layer by layer. The dynamic multipulse irradiation was observed via the production of lines with laser-induced periodic surface structures (LIPSS) at different laser parameters (scan velocities and laser polarization). The spatial periodicity of the formed LIPSS depends on changes in the effective number of pulses and laser polarization, as well as the nature of the material. For better interpretation of the experimental results, simulations have been conducted to explore the thermal response of the multiple layered structure 15x(Ti/Zr) after static single pulse irradiation.
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Small 2021, 2104204
Block-Copolymers Enable Direct Reduction and Structuration of Noble Metal-Based Films
Noble metal nanostructured films are of great interest for various applications including electronics, photonics, catalysis, and photocatalysis. Yet, structuring and patterning noble metals, especially those of the platinum group, is challenging by conventional nanofabrication. Herein, an approach based on solution processing to obtain metal-based films (rhodium, ruthenium (Ru) or iridium in the presence of residual organic species) with nanostructuration at the 20 nm-scale is introduced. Compared to existing approaches, the dual functionality of block-copolymers acting both as structuring and as reducing agent under inert atmosphere is exploited. A set of in situ techniques has allowed for the capturing of the carbothermal reduction mechanism occurring at the hybrid organic/inorganic interface. Differently from previous literature, a two-step reduction mechanism is unveiled with the formation of a carbonyl intermediate. From a technological point of view, the materials can be solution-processed on a large scale by dip-coating as polymers and simultaneously structured and reduced into metals without requiring expensive equipment or treatments in reducing atmosphere. Importantly, the metal-based films can be patterned directly by block-copolymer lithography or by soft-nanoimprint lithography on various substrates. As proof-of-concept of application, the authors demonstrate that nanostructured Ru films can be used as efficient catalysts for H2 generation into microfluidic reactors.
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Small 2021, 2103561
Critical Role of Phosphorus in Hollow Structures Cobalt-Based Phosphides as Bifunctional Catalysts for Water Splitting
Cobalt phosphides electrocatalysts have great potential for water splitting, but the unclear active sides hinder the further development of cobalt phosphides. Wherein, three different cobalt phosphides with the same hollow structure morphology (CoP-HS, CoP2-HS, CoP3-HS) based on the same sacrificial template of ZIF-67 are prepared. Surprisingly, these cobalt phosphides exhibit similar OER performances but quite different HER performances. The identical OER performance of these CoPx-HS in alkaline solution is attributed to the similar surface reconstruction to CoOOH. CoP-HS exhibits the best catalytic activity for HER among these CoPx-HS in both acidic and alkaline media, originating from the adjusted electronic density of phosphorus to affect absorption–desorption process on H. Moreover, the calculated ΔGH* based on P-sites of CoP-HS follows a quite similar trend with the normalized overpotential and Tafel slope, indicating the important role of P-sites for the HER process. Moreover, CoP-HS displays good performance (cell voltage of 1.67 V at a current density of 50 mA cm−2) and high stability in 1 M KOH. For the first time, this work detailly presents the critical role of phosphorus in cobalt-based phosphides for water splitting, which provides the guidance for future investigations on transition metal phosphides from material design to mechanism understanding.
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J. Synchrotron Rad. (2021). 28, 1978-1984
Tomography of a seeded free-electron laser focal spot: qualitative and quantitative comparison of two reconstruction methods for spot size characterization
Performing experiments at free-electron lasers (FELs) requires an exhaustive knowledge of the pulse temporal and spectral profile, as well as the focal spot shape and size. Operating FELs in the extreme ultraviolet (EUV) and soft X-ray (SXR) spectral regions calls for designing ad-hoc optical layouts to transport and characterize the EUV/SXR beam, as well as tailoring its spatial dimensions at the focal plane down to sizes in the few micrometers range. At the FERMI FEL (Trieste, Italy) this task is carried out by the Photon Analysis Delivery and Reduction System (PADReS). In particular, to meet the different experimental requests on the focal spot shape and size, a proper tuning of the optical systems is required, and this should be monitored by means of dedicated techniques. Here, we present and compare two reconstruction methods for spot characterization: single-shot imprints captured via ablation on a poly(methyl methacrylate) sample (PMMA) and pulse profiles retrieved by means of a Hartmann wavefront sensor (WFS). By recording complementary datasets at and nearby the focal plane, we exploit the tomography of the pulse profile along the beam propagation axis, as well as a qualitative and quantitative comparison between these two reconstruction methods. (C) 2021 Optical Society of America under the terms of the OSA Open Access Publishing Agreement
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Optics Express Vol. 28, Issue 18, pp. 27000-27012 (2020)
Computational proximity lithography with extreme ultraviolet radiation
The potential of extreme ultraviolet (EUV) computational proximity lithography for fabrication of arbitrary nanoscale patterns is investigated. We propose to use a holographic mask (attenuating phase shifting mask) consisting of structures of two phase levels. This approach allows printing of arbitrary, non-periodic structures without using high-resolution imaging optics. The holographic mask is designed for a wavelength of 13.5 nm with a conventional high-resolution electron beam resist as the phase shifting medium (pixel size 50 nm). The imaging performance is evaluated by using EUV radiation with different degrees of spatial coherence. Therefore exposures on identical masks are carried out with both undulator radiation at a synchrotron facility and plasma-based radiation at a laboratory setup.
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Phys. Rev. B 101, 075207
Modeling ultrafast out-of-equilibrium carrier dynamics and relaxation processes upon irradiation of hexagonal silicon carbide with femtosecond laser pulses
We present a theoretical investigation of the yet unexplored dynamics of the produced excited carriers upon irradiation of hexagonal silicon carbide (6H-SiC) with femtosecond laser pulses. To describe the ultrafast behavior of laser-induced out-of-equilibrium carriers, a real-time simulation based on density-functional theory methodology is used to compute both the hot-carrier dynamics and transient change of the optical properties. A two-temperature model (TTM) is also employed to derive the relaxation processes (i.e., thermal equilibration between carrier and lattice through carrier-phonon coupling) for laser pulses of wavelength 401 nm, duration 50 fs at normal incidence irradiation which indicate that surface damage on the material occurs for fluence ∼1.88 J cm−2. This approach of linking real-time calculations, transient optical properties, and TTM modeling, has strong implications for understanding both the ultrafast dynamics and processes of energy relaxation between carrier and phonon subsystems and providing a precise investigation of the impact of hot-carrier population in surface damage mechanisms in solids.
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ECS J. Solid State Sci. Technol. 9 015006
Correlation of Threading Dislocations with the Electron Concentration and Mobility in InN Heteroepitaxial Layers Grown by MBE
The quantitative interdependencies of growth conditions, crystal defects and electrical/electronic properties of InN thin films, grown by plasma-assisted molecular beam epitaxy on GaN (0001) buffer layers have been investigated. InN epilayers with thickness near 700 nm, grown under different substrate temperature and/or growth rate, have been analyzed. Bulk electron concentration (Nbulk) and mobility values were extracted for each InN film using the inverted version of the multilayer Petritz model, subtracting the conductivity of a corresponding 120 nm InN film. The results indicate a significant reduction of the threading dislocation density by enhancing the diffusion length of indium adatoms during InN growth, through increase of substrate temperature and reduction of growth rate. The electrical characteristics deteriorate with increasing threading dislocation density. Assuming threading dislocations as exclusive sources of donors in InN, their charge state could be between +1 and +2 per c lattice constant length of dislocation line for Nbulk ≈ 4.0–5.7×1017 cm−3, and approximately +2 or larger for Nbulk ≈ 1.5–1.8×1018 cm−3. The scattering effect of threading dislocations is significantly weaker compared to reported theoretical calculations, i.e. it would correspond to an order of magnitude lower threading dislocation density than the experimentally observed density in the range of 1010 cm−2.
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J. Chem. Theory Comput. 2019, 15, 6, 3710–3720
Koopmans Meets Bethe–Salpeter: Excitonic Optical Spectra without GW
The Bethe–Salpeter equation (BSE) can be applied to compute from first-principles optical spectra that include the effects of screened electron–hole interactions. As input, BSE calculations require single-particle states, quasiparticle energy levels, and the screened Coulomb interaction, which are typically obtained with many-body perturbation theory, whose cost limits the scope of possible applications. This work tries to address this practical limitation, instead deriving spectral energies from Koopmans-compliant functionals and introducing a new methodology for handling the screened Coulomb interaction. The explicit calculation of the W matrix is bypassed via a direct minimization scheme applied on top of a maximally localized Wannier function basis. We validate and benchmark this approach by computing the low-lying excited states of the molecules in Thiel’s set and the optical absorption spectrum of a C60 fullerene. The results show the same trends as quantum chemical methods and are in excellent agreement with previous simulations carried out at the time-dependent density functional theory or G0W0-BSE level. Conveniently, the new framework reduces the parameter space controlling the accuracy of the calculation, thereby simplifying the simulation of charge-neutral excitations, offering the potential to expand the applicability of first-principles spectroscopies to larger systems of applied interest.
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Opt. Express 29, 36086-36099 (2021)
Tomography of a seeded free-electron laser focal spot: qualitative and quantitative comparison of two reconstruction methods for spot size characterization
Performing experiments at free-electron lasers (FELs) requires an exhaustive knowledge of the pulse temporal and spectral profile, as well as the focal spot shape and size. Operating FELs in the extreme ultraviolet (EUV) and soft X-ray (SXR) spectral regions calls for designing ad-hoc optical layouts to transport and characterize the EUV/SXR beam, as well as tailoring its spatial dimensions at the focal plane down to sizes in the few micrometers range. At the FERMI FEL (Trieste, Italy) this task is carried out by the Photon Analysis Delivery and Reduction System (PADReS). In particular, to meet the different experimental requests on the focal spot shape and size, a proper tuning of the optical systems is required, and this should be monitored by means of dedicated techniques. Here, we present and compare two reconstruction methods for spot characterization: single-shot imprints captured via ablation on a poly(methyl methacrylate) sample (PMMA) and pulse profiles retrieved by means of a Hartmann wavefront sensor (WFS). By recording complementary datasets at and nearby the focal plane, we exploit the tomography of the pulse profile along the beam propagation axis, as well as a qualitative and quantitative comparison between these two reconstruction methods.
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Polymers 2021, 13(20), 3453
Polylactide, Processed by a Foaming Method Using Compressed Freon R134a, for Tissue Engineering
Fabricating polymeric scaffolds using cost-effective manufacturing processes is still challenging. Gas foaming techniques using supercritical carbon dioxide (scCO2) have attracted attention for producing synthetic polymer matrices; however, the high-pressure requirements are often a technological barrier for its widespread use. Compressed 1,1,1,2-tetrafluoroethane, known as Freon R134a, offers advantages over CO2 in manufacturing processes in terms of lower pressure and temperature conditions and the use of low-cost equipment. Here, we report for the first time the use of Freon R134a for generating porous polymer matrices, specifically polylactide (PLA). PLA scaffolds processed with Freon R134a exhibited larger pore sizes, and total porosity, and appropriate mechanical properties compared with those achieved by scCO2 processing. PLGA scaffolds processed with Freon R134a were highly porous and showed a relatively fragile structure. Human mesenchymal stem cells (MSCs) attached to PLA scaffolds processed with Freon R134a, and their metabolic activity increased during culturing. In addition, MSCs displayed spread morphology on the PLA scaffolds processed with Freon R134a, with a well-organized actin cytoskeleton and a dense matrix of fibronectin fibrils. Functionalization of Freon R134a-processed PLA scaffolds with protein nanoparticles, used as bioactive factors, enhanced the scaffolds’ cytocompatibility. These findings indicate that gas foaming using compressed Freon R134a could represent a cost-effective and environmentally friendly fabrication technology to produce polymeric scaffolds for tissue engineering approaches.
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Sci Rep 11, 19981 (2021)
Revealing the effect of electrocatalytic performance boost during hydrogen evolution reaction on free-standing SWCNT film electrode
Large-scale sustainable hydrogen production by water electrolysis requires a highly active yet low-cost hydrogen evolution reaction (HER) electrocatalyst. Conductive carbon nanomaterials with high surface areas are promising candidates for this purpose. In this contribution, single-walled carbon nanotubes (SWCNTs) are assembled into free-standing films and directly used as HER electrodes. During the initial 20 h of electrocatalytic performance in galvanostatic conditions, the films undergo activation, which results in a gradual overpotential decrease to the value of 225 mV. Transient physicochemical properties of the films at various activation stages are characterized to reveal the material features responsible for the activity boost. Results indicate that partial oxidation of iron nanoparticles encapsulated in SWCNTs is the major contributor to the activity enhancement. Furthermore, besides high activity, the material, composed of only earth-abundant elements, possesses exceptional performance stability, with no activity loss for 200 h of galvanostatic performance at − 10 mA cm−2. In conclusion, the work presents the strategy of engineering a highly active HER electrode composed of widely available elements and provides new insights into the origins of electrocatalytic performance of SWCNT-based materials in alkaline HER.
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Science Advances, 7, 40 (2021)
Single alloy nanoparticle x-ray imaging during a catalytic reaction
The imaging of active nanoparticles represents a milestone in decoding heterogeneous catalysts’ dynamics. We report the facet-resolved, surface strain state of a single PtRh alloy nanoparticle on SrTiO3 determined by coherent x-ray diffraction imaging under catalytic reaction conditions. Density functional theory calculations allow us to correlate the facet surface strain state to its reaction environment–dependent chemical composition. We find that the initially Pt-terminated nanoparticle surface gets Rh-enriched under CO oxidation reaction conditions. The local composition is facet orientation dependent, and the Rh enrichment is nonreversible under subsequent CO reduction. Tracking facet-resolved strain and composition under operando conditions is crucial for a rational design of more efficient heterogeneous catalysts with tailored activity, selectivity, and lifetime.
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ACS Catal. 2021, 11, 19, 12324–12335
Detection of Spontaneous FeOOH Formation at the Hematite/Ni(Fe)OOH Interface During Photoelectrochemical Water Splitting by Operando X-ray Absorption Spectroscopy
The role that the α-Fe2O3/NiFeOOH interface plays in dictating the oxygen evolution reaction (OER) mechanism on hematite has been a source of intense debate for decades, but the chemical characteristics of this interface and its function are still ambiguous and subject to speculation. In this study, we employed operando X-ray absorption spectroscopy to investigate the interfacial dynamics at the α-Fe2O3/NiFeOOH interface. We uncovered the spontaneous formation of a FeOOH interfacial layer under (photo)electrochemical conditions. This FeOOH interfacial layer plays a role in the surface passivation of hematite and in accumulating the (photo)generated holes upon external potential application. This hole-accumulation process leads to the extraction of more (photo)generated holes from hematite before releasing them to NiFeOOH to carry out the water-splitting reaction, and it also explains the reason for the delay in the nickel oxidation process. Based on these observations, we propose a model where NiFeOOH acts mainly as an OER catalyst and a facilitator of holes extraction from hematite, while the interfacial FeOOH layer acts as a surface passivation and hole-accumulation overlayer.
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Phys. Rev. Lett. 127, 126404
Ab Initio Electron-Phonon Interactions in Correlated Electron Systems
Electron-phonon (e-ph) interactions are pervasive in condensed matter, governing phenomena such as transport, superconductivity, charge-density waves, polarons, and metal-insulator transitions. Firstprinciples approaches enable accurate calculations of e-ph interactions in a wide range of solids. However, they remain an open challenge in correlated electron systems (CES), where density functional theory often fails to describe the ground state. Therefore reliable e-ph calculations remain out of reach for many transition metal oxides, high-temperature superconductors, Mott insulators, planetary materials, and multiferroics. Here we show first-principles calculations of e-ph interactions in CES, using the framework of Hubbard-corrected density functional theory (DFT þ U) and its linear response extension (DFPT þ U), which can describe the electronic structure and lattice dynamics of many CES. We showcase the accuracy of this approach for a prototypical Mott system, CoO, carrying out a detailed investigation of its e-ph interactions and electron spectral functions. While standard DFPT gives unphysically divergent and shortranged e-ph interactions, DFPT þ U is shown to remove the divergences and properly account for the longrange Fröhlich interaction, allowing us to model polaron effects in a Mott insulator. Our work establishes a broadly applicable and affordable approach for quantitative studies of e-ph interactions in CES, a novel theoretical tool to interpret experiments in this broad class of materials.
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Journal of Microelectronics, Electronic Components and Materials Vol. 51, No. 3(2021), 157 – 167
Charge Configuration Memory (CCM) device - a novel approach to memory
Computer technologies have advanced unimaginably over the last 70 years, mainly due to scaling of electrical components down to the nanometre regime and their consequential increase in density, speed and performance. Decrease in dimensions also brings about many unwanted side effects, such as increased leakage, heat dissipation and increased cost of production [1], [2]. However, it seems that one of the biggest factors limiting further progress in high-performance computing is the increasing difference in performance between processors and memory units, a so called processor-memory gap [3]. To increase the efficiency of memory devices, emerging alternative non-volatile memory (NVM) technologies could be introduced, promising high operational speed, low power consumption and high density [4]. This review focuses on a conceptually unique non-volatile Charge Configuration Memory (CCM) device, which is based on resistive switching between different electronic states in a 1T-TaS2 crystal [5]. CCM demonstrates ultrafast switching speed <16 ps, very low switching energy (2.2 fJ/bit), very good endurance [6] and a straightforward design. It operates at cryogenic temperatures, which makes it ideal for integration into emerging cryo-computing [7] and other high-performance computing systems such as superconducting quantum computers.
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Phys. Rev. Materials 5, 083803
Excitons and carriers in transient absorption and time-resolved ARPES spectroscopy: An ab initio approach
I present a fully ab initio scheme to model transient spectroscopy signals in the presence of strongly bound excitons. Using LiF as a prototype material, I show that the scheme is able to capture the exciton signature both in time-resolved angle-resolved photoemission spectroscopy and transient absorption experiments. The approach is completely general and can become the reference scheme for modeling pump and probe experiment in a wide range of materials.
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Scientific Data volume 8, Article number: 217 (2021)
OPTIMADE, an API for exchanging materials data
The Open Databases Integration for Materials Design (OPTIMADE) consortium has designed a universal application programming interface (API) to make materials databases accessible and interoperable. We outline the first stable release of the specification, v1.0, which is already supported by many leading databases and several software packages. We illustrate the advantages of the OPTIMADE API through worked examples on each of the public materials databases that support the full API specification.
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Journal of Physics and Chemistry of Solids, 160, 110309 (2022)
Studying the heterogeneity of the CrxTi1-xCh2 (Ch = S, Se) single crystals using X-ray scanning photoemission microscopy
The morphology of the heterogeneous CrxTi1-xSe2 and CrxTi1-xS2 single crystals has been studied using X-ray scanning photoemission microscopy (SPEM) and angular resolved photoemission spectroscopy (ARPES). A direct method of SPEM provided us the insight into the origin of the blurred ARPES images for Cr0.78Ti0.36Se2 single crystal. Using SPEM, we confirmed the formation of the CrSe2-based structural fragments inside the CrxTi1-xSe2 single crystals with x ≥ 0.75. The chemical composition of the forming structural fragments depends on the chalcogen (S, Se) forming the crystal lattice.
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Front. Mater., 05 August 2021
Structural Study of the Hydration of Lipid Membranes Upon Interaction With Mesoporous Supports Prepared by Standard Methods and/or X‐Ray Irradiation
Mesoporous materials feature ordered tailored structures with uniform pore sizes and highly accessible surface areas, making them an ideal host for functional organic molecules or nanoparticles for analytical and sensing applications. Moreover, as their porosity could be employed to deliver fluids, they could be suitable materials for nanofluidic devices. As a first step in this direction, we present a study of the hydration of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) model lipid membranes on solid mesoporous support. POPC was selected as it changes the structure upon hydration at room temperature. Mesoporous films were prepared using two different templating agents, Pluronic P123 (PEO–PPO–PEO triblock copolymer where PEO is polyethylene oxide and PPO is polypropylene oxide) and Brij 58 (C16H33(EO)20OH where EO is ethylene oxide), both following the conventional route and by X-ray irradiation via deep X-ray lithography technique and subsequent development. The same samples were additionally functionalized with a self-assembly monolayer (SAM) of (3-aminopropyl)triethoxysilane. For every film, the contact angle was measured. A time resolved structural study was conducted using in situ grazing incidence small-angle X-ray scattering while increasing the external humidity (RH), from 15 to 75% in a specially designed chamber. The measurements evidenced that the lipid membrane hydration on mesoporous films occurs at a lower humidity value with respect to POPC deposited on silicon substrates, demonstrating the possibility of using porosity to convey water from below. A different level of hydration was reached by using the mesoporous thin film prepared with conventional methods or the irradiated ones, or by functionalizing the film using the SAM strategy, meaning that the hydration can be partially selectively tuned. Therefore, mesoporous films can be employed as “interactive” sample holders with specimens deposited on them. Moreover, thanks to the possibility of patterning the films using deep X-ray lithography, devices for biological studies of increasing complexity by selectively functionalizing the mesopores with biofunctional SAMs could be designed and fabricated.
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Energies 2021, 14(14), 4354
The Influence of Microstructured Charcoal Additive on ANFO’s Properties
The verification of the blasting parameters of Ammonium Nitrate Fuel Oil (ANFO) with the addition of microstructured charcoal (MC) produced by destructive wood distillation was performed. Additional investigation of specific surface and pore distribution by the nitrogen adsorption of the two granulations of MC was also carried out. High-resolution scanning electron microscopy was used for morphology evaluation and revealed smoothening of the initially developed external surface of carbon with intensive milling. In addition, the analysis of the thermal properties of the studied samples (TG/DSC) indicated that the size of the microstructured charcoal additives influenced the decomposition temperature of the prepared materials. The explosives containing microstructured charcoal grains of −90 μm underwent decomposition at lower temperatures in comparison with those containing higher sizes of microstructure charcoal grains (−1.18 mm), for which the decomposition temperature reached 292 °C. The obtained results of blasting parameters compared to the results derived from thermodynamic simulation showed the non-ideal character of the explosives (much lower values of blasting parameters than in established thermodynamic models). It was indicated that higher velocities of detonations (VOD) were obtained for non-ideal explosives where finer MC grains were added. Blasting tests confirmed that the studied type of MC can be applied as an additive to the ANFO.
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Nanomaterials 2021, 11(7), 1796
Hydrotalcite-Embedded Magnetite Nanoparticles for Hyperthermia-Triggered Chemotherapy
A magnetic nanocomposite, consisting of Fe3O4 nanoparticles embedded into a Mg/Al layered double hydroxide (LDH) matrix, was developed for cancer multimodal therapy, based on the combination of local magnetic hyperthermia and thermally induced drug delivery. The synthesis procedure involves the sequential hydrolysis of iron salts (Fe2+, Fe3+) and Mg2+/Al3+ nitrates in a carbonate-rich mild alkaline environment followed by the loading of 5-fluorouracil, an anionic anticancer drug, in the interlayer LDH space. Magnetite nanoparticles with a diameter around 30 nm, dispersed in water, constitute the hyperthermia-active phase able to generate a specific loss of power of around 500 W/g-Fe in an alternating current (AC) magnetic field of 24 kA/m and 300 kHz as determined by AC magnetometry and calorimetric measurements. Heat transfer was found to trigger a very rapid release of drug which reached 80% of the loaded mass within 10 min exposure to the applied field. The potential of the Fe3O4/LDH nanocomposites as cancer treatment agents with minimum side-effects, owing to the exclusive presence of inorganic phases, was validated by cell internalization and toxicity assays.
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iScience. 2021 Jul 23; 24(7): 102818
Resolving physical interactions between bacteria and nanotopographies with focused ion beam scanning electron microscopy
To robustly assess the antibacterial mechanisms of nanotopographies, it is critical to analyze the bacteria-nanotopography adhesion interface. Here, we utilize focused ion beam milling combined with scanning electron microscopy to generate three-dimensional reconstructions of Staphylococcus aureus or Escherichia coli interacting with nanotopographies. For the first time, 3D morphometric analysis has been exploited to quantify the intrinsic contact area between each nanostructure and the bacterial envelope, providing an objective framework from which to derive the possible antibacterial mechanisms of synthetic nanotopographies. Surfaces with nanostructure densities between 36 and 58 per μm2 and tip diameters between 27 and 50 nm mediated envelope deformation and penetration, while surfaces with higher nanostructure densities (137 per μm2) induced envelope penetration and mechanical rupture, leading to marked reductions in cell volume due to cytosolic leakage. On nanotopographies with densities of 8 per μm2 and tip diameters greater than 100 nm, bacteria predominantly adhered between nanostructures, resulting in cell impedance.
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Journal of Applied Physics 130, 015301 (2021)
Influence of swift heavy ion irradiations on temperature dependent phononic behavior of epitaxial LaNiO3 thin film
The effects of Ag15+ (200 MeV) swift heavy ion irradiations on the structural and phononic properties of epitaxial LaNiO3 (LNO) thin film have been investigated using high resolution x-ray diffraction and Raman spectroscopy. After irradiation, the decrease in the out-of-plane lattice parameter of LNO toward its bulk value indicates the relaxation of epitaxial strain. The temperature dependency of phononic response for different ion irradiation doses was studied by performing the Raman measurements in a temperature range of 80−300 K. For pristine as well as irradiated samples of LNO, the observed phononic modes A1g and Eg shows softening with an increment in the temperature. The temperature coefficient of both modes varies with ion fluence. For the A1g mode, temperature coefficient increases from −0.087 cm−1 K−1 for pristine to −0.092 cm−1 K−1 for a maximum ion fluence of 1012 ions/cm2, while for the Eg mode, it decreases from −0.022 cm−1 K−1 for pristine to −0.015 cm−1 K−1 for 1012 ions/cm2. Raman frequency shift for both the modes shows non-linear behavior with temperature. This temperature dependent behavior was quantitatively analyzed by using a model which suggests that Raman shifts of the A1g mode emerged predominantly due to four phonon processes whereas, for the Eg mode, major contribution came from the thermal expansion effect. Ion irradiation did not change the dominating mechanism resulting in these temperature dependent Raman shifts, although the relative contribution of different processes was altered with ion fluence.
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Journal of Colloid and Interface Science, 604, 2021, 91-103 (2021)
Insights into complex nanopillar-bacteria interactions: Roles of nanotopography and bacterial surface proteins
Nanopillared surfaces have emerged as a promising strategy to combat bacterial infections on medical devices. However, the mechanisms that underpin nanopillar-induced rupture of the bacterial cell membrane remain speculative. In this study, we have tested three medically relevant poly(ethylene terephthalate) (PET) nanopillared-surfaces with well-defined nanotopographies against both Gram-negative and Gram-positive bacteria. Focused ion beam scanning electron microscopy (FIB-SEM) and contact mechanics analysis were utilised to understand the nanobiophysical response of the bacterial cell envelope to a single nanopillar. Given their importance to bacterial adhesion, the contribution of bacterial surface proteins to nanotopography-mediated cell envelope damage was also investigated. We found that, whilst cell envelope deformation was affected by the nanopillar tip diameter, the nanopillar density affected bacterial metabolic activities. Moreover, three different types of bacterial cell envelope deformation were observed upon contact of bacteria with the nanopillared surfaces. These were attributed to bacterial responses to cell wall stresses resulting from the high intrinsic pressure caused by the engagement of nanopillars by bacterial surface proteins. Such influences of bacterial surface proteins on the antibacterial action of nanopillars have not been previously reported. Our findings will be valuable to the improved design and fabrication of effective antibacterial surfaces.
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Small 2021, 17, 2100307
Virus pH-Dependent Interactions with Cationically Modified Cellulose and Their Application in Water Filtration
Norovirus and Rotavirus are among the pathogens causing a large number of disease outbreaks due to contaminated water. These viruses are nanoscale particles that are difficult to remove by common filtration approaches which are based on physical size exclusion, and require adsorption-based filtration methods. This study reports the pH-responsive interactions of viruses with cationic-modified nanocellulose and demonstrates a filter material that adsorbs nanoscale viruses and can be regenerated by changing the solution's pH. The bacteria viruses Qbeta and MS2, with diameters below 30 nm but different surface properties, are used to evaluate the pH-dependency of the interactions and the filtration process. Small angle X-ray scattering, cryogenic transmission electron microscopy, and ζ-potential measurements are used to study the interactions and analyze changes in their nanostructure and surface properties of the virus upon adsorption. The virus removal capacity of the cationic cellulose-based aerogel filter is 99.9% for MS2 and 93.6% for Qbeta, at pH = 7.0; and desorption of mostly intact viruses occurs at pH = 3.0. The results contribute to the fundamental understanding of pH-triggered virus-nanocellulose self-assembly and can guide the design of sustainable and environmentally friendly adsorption-based virus filter materials as well as phage and virus-based materials.
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Biomedicines 2021, 9, 603
Perspectives of Microscopy Methods for Morphology Characterisation of Extracellular Vesicles from Human Biofluids
Extracellular vesicles (EVs) are nanometric membranous structures secreted from almost every cell and present in biofluids. Because EV composition reflects the state of its parental tissue, EVs possess an enormous diagnostic/prognostic potential to reveal pathophysiological conditions. However, a prerequisite for such usage of EVs is their detailed characterisation, including visualisation which is mainly achieved by atomic force microscopy (AFM) and electron microscopy (EM). Here we summarise the EV preparation protocols for AFM and EM bringing out the main challenges in the imaging of EVs, both in their natural environment as biofluid constituents and in a saline solution after EV isolation. In addition, we discuss approaches for EV imaging and identify the potential benefits and disadvantages when different AFM and EM methods are applied, including numerous factors that influence the morphological characterisation, standardisation, or formation of artefacts. We also demonstrate the effects of some of these factors by using cerebrospinal fluid as an example of human biofluid with a simpler composition. Here presented comparison of approaches to EV imaging should help to estimate the current state in morphology research of EVs from human biofluids and to identify the most efficient pathways towards the standardisation of sample preparation and microscopy modes.
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Materials Science and Engineering B, 270, 115218 (2021)
The crystal structure, chemical bonding, and magnetic properties of the intercalation compounds CrxZrTe2 (x = 0–0.3)
New intercalation compounds CrxZrTe2 were synthesized in the Cr concentration range of x = 0–0.3. A thorough study of the crystal and electronic structure has been performed. It was found that there is competition in the distribution of the Cr atoms over the octa- and tetrahedral sites in the van der Waals gap, depending on the Cr content. The ordering of the Cr atoms was found at x ≥ 0.25; at the same time, the lattice symmetry decreases from trigonal P-3m1 to monoclinic F2/m. This ordering stabilizes the octahedral coordination of the Cr atoms by Te atoms. The analysis of the experimental data on the electronic structure and DOS calculations showed that the Cr 3d states are spin-split. However, these Cr states are still overlapped by non-spin-split Zr and Te states.
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Cells 2021, 10(3), 552
Biomechanics of Ex Vivo-Generated Red Blood Cells Investigated by Optical Tweezers and Digital Holographic Microscopy
Ex vivo-generated red blood cells are a promising resource for future safe blood products, manufactured independently of voluntary blood donations. The physiological process of terminal maturation from spheroid reticulocytes to biconcave erythrocytes has not been accomplished yet. A better biomechanical characterization of cultured red blood cells (cRBCs) will be of utmost interest for manufacturer approval and therapeutic application. Here, we introduce a novel optical tweezer (OT) approach to measure the deformation and elasticity of single cells trapped away from the coverslip. To investigate membrane properties dependent on membrane lipid content, two culture conditions of cRBCs were investigated, cRBCPlasma with plasma and cRBCHPL supplemented with human platelet lysate. Biomechanical characterization of cells under optical forces proves the similar features of native RBCs and cRBCHPL, and different characteristics for cRBCPlasma. To confirm these results, we also applied a second technique, digital holographic microscopy (DHM), for cells laid on the surface. OT and DHM provided related results in terms of cell deformation and membrane fluctuations, allowing a reliable discrimination between cultured and native red blood cells. The two techniques are compared and discussed in terms of application and complementarity.
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Phys. Rev. B 103, 045141
Self-consistent Hubbard parameters from density-functional perturbation theory in the ultrasoft and projector-augmented wave formulations
The self-consistent evaluation of Hubbard parameters using linear-response theory is crucial for quantitatively predictive calculations based on Hubbard-corrected density-functional theory. Here, we extend a recently-introduced approach based on density-functional perturbation theory (DFPT) for the calculation of the on-site Hubbard U to also compute the inter-site Hubbard V . DFPT allows us to reduce significantly computational costs, improve numerical accuracy, and fully automate the calculation of the Hubbard parameters by recasting the linear response of a localized perturbation into an array of monochromatic perturbations that can be calculated in the primitive cell. In addition, here we generalize the entire formalism from norm-conserving to ultrasoft and projectoraugmented wave formulations, and to metallic ground states. After benchmarking DFPT against the conventional real-space Hubbard linear response in a supercell, we demonstrate the effectiveness of the present extended Hubbard formulation in determining the equilibrium crystal structure of LixMnPO4 (x=0,1) and the subtle energetics of Li intercalation.
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Review of Scientific Instruments 92, 015115 (2021)
Soft x-ray spectroscopies in liquids and at solid–liquid interface at BACH beamline at Elettra
The beamline for advanced dichroism of the Istituto Officina dei Materiali-Consiglio Nazionale delle Ricerche, operating at the Elettra synchrotron in Trieste (Italy), works in the extreme ultraviolet–soft x-ray photon energy range with selectable light polarization, high energy resolution, brilliance, and time resolution. The beamline offers a multi-technique approach for the investigation of the electronic, chemical, structural, magnetic, and dynamical properties of materials. Recently, one of the three end stations has been dedicated to experiments based on electron transfer processes at the solid/liquid interfaces and during photocatalytic or electrochemical reactions. Suitable cells to perform soft x-ray spectroscopy in the presence of liquids and reagent gases at ambient pressure were developed. Here, we present two types of static cells working in transmission or in fluorescence yield and an electrochemical flow cell that allows us to carry out cyclic voltammetry in situ and electrodeposition on a working electrode and to study chemical reactions under operando conditions. Examples of x-ray absorption spectroscopy measurements performed under ambient conditions and during electrochemical experiments in liquids are presented.
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J. Mater. Chem. C, 2021,9, 1657-1670
Electronic and crystal structure of bi-intercalated titanium diselenide CuxNiyTiSe2
A comprehensive study of the crystal and electronic structure of TiSe2 intercalated with two 3d metals, Cu and Ni, is presented. It is found that the intercalation of Cu into NixTiSe2 at room temperature leads to the displacement of the Ni atoms from the octahedral to tetrahedral sites with respect to the Se sublattice. This effect is explained by the charge transfer from Cu to the TiSe2-derived conduction band, which makes the chemical bond of Ni with the lattice more stable. This is because the hybridization between Ni 3d and Se 4p, 4s states is stronger than that between Ni 3d and Ti 3d in mono-intercalated NixTiSe2. Therefore, it is possible to control the type of the coordination of the intercalated transition metal atom by changing the concentration of doped electrons.
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npj 2D Materials and Applications, 5, 6 (2021)
Probing valley population imbalance in transition metal dichalcogenides via temperature-dependent second harmonic generation imaging
Degenerate minima in momentum space—valleys—provide an additional degree of freedom that can be used for information transport and storage. Notably, such minima naturally exist in the band structure of transition metal dichalcogenides (TMDs). When these atomically thin crystals interact with intense laser light, the second harmonic generated (SHG) field inherits special characteristics that reflect not only the broken inversion symmetry in real space but also the valley anisotropy in reciprocal space. The latter is present whenever there exists a valley population imbalance (VPI) between the two valleys and affects the polarization state of the detected SHG. In this work, it is shown that the temperature-induced change of the SHG intensity dependence on the excitation field polarization is a fingerprint of VPI in TMDs. In particular, pixel-by-pixel VPI mapping based on polarization-resolved raster-scanning imaging microscopy was performed inside a cryostat to generate the SHG contrast in the presence of VPI from every point of a TMD flake. The generated contrast is marked by rotation of the SHG intensity polar diagrams at low temperatures and is attributed to the VPI-induced SHG.
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Appl. Sci. 2021, 11(1), 325
Time-Resolved XUV Absorption Spectroscopy and Magnetic Circular Dichroism at the Ni M2,3-Edges
Ultrashort optical pulses can trigger a variety of non-equilibrium processes in magnetic thin films affecting electrons and spins on femtosecond timescales. In order to probe the charge and magnetic degrees of freedom simultaneously, we developed an X-ray streaking technique that has the advantage of providing a jitter-free picture of absorption cross-section changes. In this paper, we present an experiment based on this approach, which we performed using five photon probing energies at the Ni M2,3-edges. This allowed us to retrieve the absorption and magnetic circular dichroism time traces, yielding detailed information on transient modifications of electron and spin populations close to the Fermi level. Our findings suggest that the observed absorption and magnetic circular dichroism dynamics both depend on the extreme ultraviolet (XUV) probing wavelength, and can be described, at least qualitatively, by assuming ultrafast energy shifts of the electronic and magnetic elemental absorption resonances, as reported in recent work. However, our analysis also hints at more complex changes, highlighting the need for further experimental and theoretical studies in order to gain a thorough understanding of the interplay of electronic and spin degrees of freedom in optically excited magnetic thin films.
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Phys. Rev. B 103, 045141
Pulay forces in density-functional theory with extended Hubbard functionals: From nonorthogonalized to orthogonalized manifolds
We present a derivation of the exact expression for Pulay forces in density-functional theory calculations augmented with extended Hubbard functionals and arising from the use of orthogonalized atomic orbitals as projectors for the Hubbard manifold. The derivative of the inverse square root of the orbital overlap matrix is obtained as a closed-form solution of the associated Lyapunov (Sylvester) equation. The expression for the resulting contribution to the forces is presented in the framework of ultrasoft pseudopotentials and the projector-augmented-wave method and using a plane-wave basis set. We have benchmarked the present implementation with respect to finite differences of total energies for the case of NiO, finding excellent agreement. Owing to the accuracy of Hubbard-corrected density-functional theory calculations—provided the Hubbard parameters are computed for the manifold under consideration—the present work paves the way for systematic studies of solid-state and molecular transition-metal and rare-earth compounds.
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Appl. Sci. 2020, 10(24), 8811
The Role of Crystalline Orientation in the Formation of Surface Patterns on Solids Irradiated with Femtosecond Laser Double Pulses
A theoretical investigation of the underlying ultrafast processes upon irradiation of rutile TiO2 of (001) and (100) surface orientation with femtosecond (fs) double pulsed lasers was performed in ablation conditions, for which, apart from mass removal, phase transformation and surface modification of the heated solid were induced. A parametric study was followed to correlate the transient carrier density and the produced lattice temperature with the laser fluence, pulse separation and the induced damage. The simulations showed that both temporal separation and crystal orientation influence the surface pattern, while both the carrier density and temperature drop gradually to a minimum value at temporal separation equal to twice the pulse separation that remain constant at long delays. Carrier dynamics, interference of the laser beam with the excited surface waves, thermal response and fluid transport at various pulse delays explained the formation of either subwavelength or suprawavelength structures. The significant role of the crystalline anisotropy is illustrated through the presentation of representative experimental results correlated with the theoretical predictions.
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Optica Vol. 7, Issue 11, pp. 1602-1608 (2020)
Soft x-ray microscopy with 7 nm resolution
The availability of intense soft x-ray beams with tunable energy and polarization has pushed the development of highly sensitive, element-specific, and noninvasive microscopy techniques to investigate condensed matter with high spatial and temporal resolution. The short wavelengths of soft x-rays promise to reach spatial resolutions in the deep single-digit nanometer regime, providing unprecedented access to magnetic phenomena at fundamental length scales. Despite considerable efforts in soft x-ray microscopy techniques, a two-dimensional resolution of 10 nm has not yet been surpassed in direct imaging. Here, we report on a significant step beyond this long-standing limit by combining newly developed soft x-ray Fresnel zone plate lenses with advanced precision in scanning control and careful optical design. With this approach, we achieve an image resolution of 7 nm. By combining this highly precise microscopy technique with the x-ray magnetic circular dichroism effect, we reveal dimensionality effects in an ensemble of interacting magnetic nanoparticles. Such effects are topical in current nanomagnetism research and highlight the opportunities of high-resolution soft x-ray microscopy in magnetism research and beyond.
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Nature Materials volume 20, pages93–99 (2021)
Direct X-ray and electron-beam lithography of halogenated zeolitic imidazolate frameworks
Metal–organic frameworks (MOFs) offer disruptive potential in micro- and optoelectronics because of the unique properties of these microporous materials. Nanoscale patterning is a fundamental step in the implementation of MOFs in miniaturized solid-state devices. Conventional MOF patterning methods suffer from low resolution and poorly defined pattern edges. Here, we demonstrate the resist-free, direct X-ray and electron-beam lithography of MOFs. This process avoids etching damage and contamination and leaves the porosity and crystallinity of the patterned MOFs intact. The resulting high-quality patterns have excellent sub-50-nm resolution, and approach the mesopore regime. The compatibility of X-ray and electron-beam lithography with existing micro- and nanofabrication processes will facilitate the integration of MOFs in miniaturized devices.
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Carbon ,172, 296-301 (2021)
Strain release at the graphene-Ni(100) interface investigated by in-situ and operando scanning tunnelling microscopy
Interface strain can significantly influence the mechanical, electronic and magnetic properties of low-dimensional materials. Here we investigated by scanning tunneling microscopy how the stress introduced by a mismatched interface affects the structure of a growing graphene (Gr) layer on a Ni(100) surface in real time during the process. Strain release appears to be the main factor governing morphology, with the interplay of two simultaneous driving forces: on the one side the need to obtain two-dimensional best registry with the substrate, via formation of moiré patterns, on the other side the requirement of optimal one-dimensional in-plane matching with the transforming nickel carbide layer, achieved by local rotation of the growing Gr flake. Our work suggests the possibility of tuning the local properties of two-dimensional films at the nanoscale through exploitation of strain at a one-dimensional interface.
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Small 2020, 16, 2002290
Anisotropic Etching of Pyramidal Silica Reliefs with Metal Masks and Hydrofluoric Acid
This work describes the fabrication of anisotropically etched, faceted pyramidal structures in amorphous layers of silicon dioxide or glass. Anisotropic and crystal-oriented etching of silicon is well known. Anisotropic etching behavior in completely amorphous layers of silicon dioxide in combination with purely isotropic hydrofluoric acid as etchant is an unexpected phenomenon. The work presents practical exploitations of this new process for self-perfecting pyramidal structures. It can be used for textured silica or glass surfaces. The reason for the observed anisotropy, leading to enhanced lateral etch rates, is the presence of thin metal layers. The lateral etch rate under the metal significantly exceeds the vertical etch rate of the non-metallized area by a factor of about 6–43 for liquid and 59 for vapor-based processes. The ratio between lateral and vertical etch rate, thus the sidewall inclination, can be controlled by etchant concentration and selected metal. The described process allows for direct fabrication of shallow angle pyramids, which for example can enhance the coupling efficiency of light emitting diodes or solar cells, can be exploited for producing dedicated silicon dioxide atomic force microscopy tips with a radius in the 50 nm range, or can potentially be used for surface plasmonics.
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Data Intelligence (2020) 2 (4): 513–528.
Deep Learning, Feature Learning, and Clustering Analysis for SEM Image Classification
In this paper, we report upon our recent work aimed at improving and adapting machine learning algorithms to automatically classify nanoscience images acquired by the Scanning Electron Microscope (SEM). This is done by coupling supervised and unsupervised learning approaches. We first investigate supervised learning on a ten-category data set of images and compare the performance of the different models in terms of training accuracy. Then, we reduce the dimensionality of the features through autoencoders to perform unsupervised learning on a subset of images in a selected range of scales (from 1 μm to 2 μm). Finally, we compare different clustering methods to uncover intrinsic structures in the images.
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Applied Surface Science Volume 538, 147936 (2021)
High carrier mobility epitaxially aligned PtSe2 films grown by one-zone selenization
Few-layer PtSe2 films are promising candidates for applications in high-speed electronics, spintronics and photodetectors. Reproducible fabrication of large-area highly crystalline films is, however, still a challenge. Here, we report the fabrication of epitaxially aligned PtSe2 films using one-zone selenization of pre-sputtered platinum layers. We have studied the influence of the growth conditions on the structural and electrical properties of the films prepared from Pt layers with different initial thickness. The best results were obtained for PtSe2 layers grown at elevated temperatures (600 °C). The films exhibit signatures for a long-range in-plane ordering resembling an epitaxial growth. Charge carrier mobility determined by Hall-effect measurements is up to 24 cm2/V.s in these films.
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Structural Dynamics 7, 054302 (2020)
Simultaneous two-color snapshot view on ultrafast charge and spin dynamics in a Fe-Cu-Ni tri-layer
Ultrafast phenomena on a femtosecond timescale are commonly examined by pump-probe experiments. This implies multiple measurements, where the sample under investigation is pumped with a short light pulse and then probed with a second pulse at various time delays to follow its dynamics. Recently, the principle of streaking extreme ultraviolet (XUV) pulses in the temporal domain has enabled recording the dynamics of a system within a single pulse. However, separate pump-probe experiments at different absorption edges still lack a unified timing, when comparing the dynamics in complex systems. Here, we report on an experiment using a dedicated optical element and the two-color emission of the FERMI XUV free-electron laser to follow the charge and spin dynamics in composite materials at two distinct absorption edges, simultaneously. The sample, consisting of ferromagnetic Fe and Ni layers, separated by a Cu layer, is pumped by an infrared laser and probed by a two-color XUV pulse with photon energies tuned to the M-shell resonances of these two transition metals. The experimental geometry intrinsically avoids any timing uncertainty between the two elements and unambiguously reveals an approximately 100 fs delay of the magnetic response with respect to the electronic excitation for both Fe and Ni. This delay shows that the electronic and spin degrees of freedom are decoupled during the demagnetization process. We furthermore observe that the electronic dynamics of Ni and Fe show pronounced differences when probed at their resonance, while the demagnetization dynamics are similar. These observations underline the importance of simultaneous investigation of the temporal response of both charge and spin in multi-component materials. In a more general scenario, the experimental approach can be extended to continuous energy ranges, promising the development of jitter-free transient absorption spectroscopy in the XUV and soft X-ray regimes.
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Scientific Data volume 7, 299 (2020)
Materials Cloud, a platform for open computational science
Materials Cloud is a platform designed to enable open and seamless sharing of resources for computational science, driven by applications in materials modelling. It hosts (1) archival and dissemination services for raw and curated data, together with their provenance graph, (2) modelling services and virtual machines, (3) tools for data analytics, and pre-/post-processing, and (4) educational materials. Data is citable and archived persistently, providing a comprehensive embodiment of entire simulation pipelines (calculations performed, codes used, data generated) in the form of graphs that allow retracing and reproducing any computed result. When an AiiDA database is shared on Materials Cloud, peers can browse the interconnected record of simulations, download individual files or the full database, and start their research from the results of the original authors. The infrastructure is agnostic to the specific simulation codes used and can support diverse applications in computational science that transcend its initial materials domain.
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Scientific Data, 7, 300 (2020)
AiiDA 1.0, a scalable computational infrastructure for automated reproducible workflows and data provenance
The ever-growing availability of computing power and the sustained development of advanced computational methods have contributed much to recent scientific progress. These developments present new challenges driven by the sheer amount of calculations and data to manage. Next-generation exascale supercomputers will harden these challenges, such that automated and scalable solutions become crucial. In recent years, we have been developing AiiDA (aiida.net), a robust open-source high-throughput infrastructure addressing the challenges arising from the needs of automated workflow management and data provenance recording. Here, we introduce developments and capabilities required to reach sustained performance, with AiiDA supporting throughputs of tens of thousands processes/hour, while automatically preserving and storing the full data provenance in a relational database making it queryable and traversable, thus enabling high-performance data analytics. AiiDA’s workflow language provides advanced automation, error handling features and a flexible plugin model to allow interfacing with external simulation software. The associated plugin registry enables seamless sharing of extensions, empowering a vibrant user community dedicated to making simulations more robust, user-friendly and reproducible.
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Phys. Rev. B 102, 104437
Real-time modeling of optical orientation in GaAs: Generation and decay of the degree of spin polarization
We present a real-time ab initio description of optical orientation in bulk GaAs due to the coupling with an ultrashort circularly polarized laser source. The injection of spin-polarized electrons in the conduction band is correctly reproduced, and a nonvanishing spin polarization P parallel to the direction of propagation of the laser (z) emerges. A detailed analysis of the generation and the evolution of P(t) is given. The single k-point dynamics is a motion of precession around a fixed axis with constant |P| and fixed frequency. Instead, the k-integrated signal shows only a time-dependent Pz(t) and decays a few picoseconds after the end of the laser pump due to decoherence. Decoherence emerges since the individual contributions activated by the pump give rise to destructive interference. We interpret the results in terms of the free induction decay mechanism proposed some years ago [M. W. Wu and C. Z. Ning, Eur. Phys. J. B 18, 373 (2000)]. We are able to reproduce such an effect in a full ab initio fashion, giving a quantitative estimate of the associated decay time. Our result also shows a possible explanation for the time decay of spin magnetization observed in many real-time ab initio simulations.
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Phys. Rev. Lett. 125, 096401
Observation of an Excitonic Mott Transition through Ultrafast Core-cum-Conduction Photoemission Spectroscopy
Time-resolved soft-X-ray photoemission spectroscopy is used to simultaneously measure the ultrafast dynamics of core-level spectral functions and excited states upon excitation of excitons in WSe$_2$. We present a many-body approximation for the Green's function, which excellently describes the transient core-hole spectral function. The relative dynamics of excited-state signal and core levels reveals a delayed core-hole renormalization due to screening by excited quasi-free carriers, revealing an excitonic Mott transition. These findings establish time-resolved core-level photoelectron spectroscopy as a sensitive probe of subtle electronic many-body interactions and an ultrafast electronic phase transition.
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Phys. Rev. Research 2, 033265
Electronic structure of pristine and Ni-substituted LaFeO3 from near edge x-ray absorption fine structure experiments and first-principles simulations
We present a joint theoretical and experimental study of the oxygen K-edge spectra for LaFeO3 and homovalent Ni-substituted LaFeO3 (LaFe0.75Ni0.25O3), using first-principles simulations based on density-functional theory with extended Hubbard functionals and x-ray absorption near edge structure (XANES) measurements. Ground-state and excited-state XANES calculations employ Hubbard on-site U and inter-site V parameters determined from first principles and the Lanczos recursive method to obtain absorption cross sections, which allows for a reliable description of XANES spectra in transition-metal compounds in a very broad energy range, with an accuracy comparable to that of hybrid functionals but at a substantially lower cost. We show that standard gradient-corrected exchange-correlation functionals fail in capturing accurately the electronic properties of both materials. In particular, for LaFe0.75Ni0.25O3 they do not reproduce its semiconducting behaviour and provide a poor description of the pre-edge features at the O K edge. The inclusion of Hubbard interactions leads to a drastic improvement, accounting for the semiconducting ground state of LaFe0.75Ni0.25O3 and for a good agreement between calculated and measured XANES spectra. We show that the partial substitution of Fe for Ni affects the conduction-band bottom by generating a strongly hybridized O(2p)-Ni(3d) minority-spin empty electronic state. The present work, based on a consistent correction of self-interaction errors, outlines the crucial role of extended Hubbard functionals to describe the electronic structure of complex transition-metal oxides such as LaFeO3 and LaFe0.75Ni0.25O3 and paves the way to future studies on similar systems.
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Optica Vol. 7, Issue 8, pp. 1007-1014 (2020)
Observation of an Excitonic Mott Transition through Ultrafast Core-cum-Conduction Photoemission Spectroscopy
X-ray free-electron lasers (XFELs) are paving the way towards new experiments in many scientific fields, such as ultrafast science, nonlinear spectroscopy, and coherent imaging. However, the strong intensity fluctuations inherent to the lasing process in these sources often lead to problems in signal normalization. In order to address this challenge, we designed, fabricated, and characterized diffractive x-ray optics that combine the focusing properties of a Fresnel zone plate with the beam-splitting capability of a grating in a single diffractive optical element. The possibility to split the incident beam into identical copies allows for direct shot-to-shot normalization of the sample signal, thereby greatly enhancing the signal-to-noise ratio in experiments with XFEL radiation. Here we propose two schemes for the design of such diffractive x-ray optical elements for splitting and focusing an incoming beam into up to three foci by merging a grating with a focusing zone plate. By varying the duty cycle of the grating or the relative shift of the Fresnel zone plate structure, we are able to tune the relative intensities of the different diffraction orders to achieve the desired splitting ratios. Experimental confirmation of the design is provided with soft x-ray light (540 eV) and shows a good agreement with calculations, confirming the suitability of this approach for XFEL experiments.
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Beilstein J. Nanotechnol. 2020, 11, 1198–1206
3D superconducting hollow nanowires with tailored diameters grown by focused He+ beam direct writing
Currently, the patterning of innovative three-dimensional (3D) nano-objects is required for the development of future advanced electronic components. Helium ion microscopy in combination with a precursor gas can be used for direct writing of three-dimensional nanostructures with a precise control of their geometry, and a significantly higher aspect ratio than other additive manufacturing technologies. We report here on the deposition of 3D hollow tungsten carbide nanowires with tailored diameters by tuning two key growth parameters, namely current and dose of the ion beam. Our results show the control of geometry in 3D hollow nanowires, with outer and inner diameters ranging from 36 to 142 nm and from 5 to 28 nm, respectively; and lengths from 0.5 to 8.9 µm. Transmission electron microscopy experiments indicate that the nanowires have a microstructure of large grains with a crystalline structure compatible with the face-centered cubic WC1−x phase. In addition, 3D electron tomographic reconstructions show that the hollow center of the nanowires is present along the whole nanowire length. Moreover, these nanowires become superconducting at 6.8 K and show high values of critical magnetic field and critical current density. Consequently, these 3D nano-objects could be implemented as components in the next generation of electronics, such as nano-antennas and sensors, based on 3D superconducting architectures.
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Nanomaterials 2020, 10(8), 1568
Iron Oxide Nanoparticles as an Alternative to Antibiotics Additive on Extended Boar Semen
This study examined the effect of Fe3O4 nanoparticles on boar semen. Beltsville thawing solution without antibiotics was used to extend ejaculates from 5 boars (4 ejaculates/boar). Semen samples of control group (C) and group with Fe3O4 (Fe; 0.192 mg/mL semen) were incubated under routine boar semen storage temperature (17 °C) for 0.5 h and nanoparticles were removed by a magnetic field. Before and after treatment, aliquots of all groups were cultured using standard microbiological methods. The samples after treatment were stored (17 °C) for 48 h and sperm parameters (computer-assisted sperm analyzer (CASA) variables; morphology; viability; hypo-osmotic swelling test (HOST); DNA integrity) were evaluated at storage times 0, 24, 48 h. Semen data were analyzed by a repeated measures mixed model and microbial data with Student’s t-test for paired samples. Regarding CASA parameters, Fe group did not differ from C at any time point. In group C, total motility after 24 h and progressive motility after 48 h of storage decreased significantly compared to 0 h. In group Fe, linearity (LIN) after 48 h and head abnormalities after 24 h of storage increased significantly compared to 0 h. The microbiological results revealed a significant reduction of the bacterial load in group Fe compared to control at both 24 and 48 h. In conclusion, the use of Fe3O4 nanoparticles during semen processing provided a slight anti-microbiological effect with no adverse effects on sperm characteristics.
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J. Mater. Chem. C, 2020, Advance Article
A cryogenic solid-state reaction at the interface between Ti and the Bi2Se3 topological insulator
Understanding the chemical processes at the interface between a metal and topological insulator (TI) is important when it comes to designing devices that exploit the peculiar topological surface states or studying the properties of TI heterostructures. In this paper we show that the interface between Ti and Bi2Se3 is unstable at RT and results in the formation of interfacial phases of titanium selenides and metallic Bi. The reaction has shown significant kinetics already at cryogenic temperatures, which is very surprising for a solid-state redox reaction. This can be explained with the possibility of electrons in the topological surface states playing a role in enhancing the Bi2Se3 surface reactivity due to the electron-bath effect. For the Ti coverage above 40 nm, the interfacial processes cause compressive stress that triggers the morphological change (buckling) of the deposited film. The observed interface reaction, with all of its consequences, has to be considered not only in the design of devices, where the Ti adhesion layer is often used for contacts, but also for possible engineering of 2D TI heterostructures.
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Applied Nanoscience volume 10, pages5053–5061 (2020)
Pulsed laser deposition of the LaVO4:Eu, Ca nanoparticles on glass and silicon substrates
Thin films from the LaVO4:Eu, Ca nanoparticles were successfully grown by pulsed laser deposition method on glass and silicon substrates for the first time. Morphology and thickness of the films depend on the type of substrate and number of pulses. The films are of 27–220 nm thickness and formed by very small particles (up to 20 nm) and also can contain single nanoparticles with dimensions of 40–60 nm and sometimes agglomerates of nanoparticles. Spectral properties of the samples have been investigated and discussed. The vanadate films deposited on the silicon substrates lead to appearance of antireflection properties in the visible range. Luminescence spectra of the investigated films consist of narrow lines caused by f–f transitions in the Eu3+ ions. For the samples on glass substrates the wide bands of glass emission also contributed to the spectra. The optimal experimental conditions which allowed to obtain films with promising applications as luminescent converters are considered.
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Corrosion Science, 174, 108841 (2020)
Lateral variation of the native passive film on super duplex stainless steel resolved by synchrotron hard X-ray photoelectron emission microscopy
A native passive film on 25Cr-7Ni super duplex stainless steel was analyzed using synchrotron hard X-ray photoemission electron microscopy, focusing on variations between individual grains of ferrite and austenite phases. The film consists of an oxide inner layer and an oxyhydroxide outer layer, in total 2.3 nm thick. The Cr content is higher in the outer than the inner layer, ca. 80 % on average. The Cr content is higher on ferrite than austenite, whereas the thickness is rather uniform. The grain orientation has a small but detectable influence, ferrite (111) grains have a lower Cr content than other ferrite grains.
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Nano Lett. 2020, 20, 8, 5893–5899
Control of Spin–Orbit Torques by Interface Engineering in Topological Insulator Heterostructures
(Bi1–xSbx)2Te3 topological insulators (TIs) are gathering increasing attention owing to their large charge-to-spin conversion efficiency and the ensuing spin–orbit torques (SOTs) that can be used to manipulate the magnetization of a ferromagnet (FM). The origin of the torques, however, remains elusive, while the implications of hybridized states and the strong material intermixing at the TI/FM interface are essentially unexplored. By combining interface chemical analysis and spin-transfer ferromagnetic resonance (ST-FMR) measurements, we demonstrate that intermixing plays a critical role in the generation of SOTs. By inserting a suitable normal metal spacer, material intermixing is reduced and the TI properties at the interface are largely improved, resulting in strong variations in the nature of the SOTs. A dramatic enhancement of a field-like torque, opposing and surpassing the Oersted-field torque, is observed, which can be attributed to the non-equilibrium spin density in Rashba-split surface bands and to the suppression of spin memory loss. These phenomena can play a relevant role at other interfaces, such as those comprising transition metal dichalcogenides.
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Front. Chem., 8, 520 (2020)
Supported porous nanostructures developed by plasma processing of metal phthalocyanines and porphyrins
The large area scalable fabrication of supported porous metal and metal oxide nanomaterials is acknowledged as one of the greatest challenges for their eventual implementation in on-device applications. In this work, we will present a comprehensive revision and the latest results regarding the pioneering use of commercially available metal phthalocyanines and porphyrins as solid precursors for the plasma-assisted deposition of porous metal and metal oxide films and three-dimensional nanostructures (hierarchical nanowires and nanotubes). The most advanced features of this method relay on its ample general character from the point of view of the porous material composition and microstructure, mild deposition and processing temperature and energy constrictions and, finally, its straightforward compatibility with the direct deposition of the porous nanomaterials on processable substrates and device-architectures. Thus, taking advantage of the variety in the composition of commercially available metal porphyrins and phthalocyanines, we present the development of metal and metal oxides layers including Pt, CuO, Fe2O3, TiO2, and ZnO with morphologies ranging from nanoparticles to nanocolumnar films. In addition, we combine this method with the fabrication by low-pressure vapor transport of single-crystalline organic nanowires for the formation of hierarchical hybrid organic@metal/metal-oxide and @metal/metal-oxide nanotubes. We carry out a thorough characterization of the films and nanowires using SEM, TEM, FIB 3D, and electron tomography. The latest two techniques are revealed as critical for the elucidation of the inner porosity of the layers.
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J. Chem. Phys. 152, 214117 (2020)
Modern quantum chemistry with [Open]Molcas
MOLCAS/OpenMolcas is an ab initio electronic structure program providing a large set of computational methods from Hartree–Fock and density functional theory to various implementations of multiconfigurational theory. This article provides a comprehensive overview of the main features of the code, specifically reviewing the use of the code in previously reported chemical applications as well as more recent applications including the calculation of magnetic properties from optimized density matrix renormalization group wave functions.
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J. Mater. Chem. C, ,8, 8876-8886 (2020)
Molecular anchoring stabilizes low valence Ni(I)TPP on copper against thermally induced chemical changes
Many applications of molecular layers deposited on metal surfaces, ranging from single-atom catalysis to on-surface magnetochemistry and biosensing, rely on the use of thermal cycles to regenerate the pristine properties of the system. Thus, understanding the microscopic origin behind the thermal stability of organic/metal interfaces is fundamental for engineering reliable organic-based devices. Here, we study nickel porphyrin molecules on a copper surface as an archetypal system containing a metal center whose oxidation state can be controlled through the interaction with the metal substrate. We demonstrate that the strong molecule–surface interaction, followed by charge transfer at the interface, plays a fundamental role in the thermal stability of the layer by rigidly anchoring the porphyrin to the substrate. Upon thermal treatment, the molecules undergo an irreversible transition at 420 K, which is associated with an increase of the charge transfer from the substrate, mostly localized on the phenyl substituents, and a downward tilting of the latters without any chemical modification.
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Nanoscale, 2020,12, 13697-13707
Highly luminescent and ultrastable cesium lead bromide perovskite patterns generated in phosphate glass matrices
Owing to their exceptional optoelectronic properties, all-inorganic lead halide perovskites offer enormous potential for next generation photonic, light-emitting, and optoelectronic devices. However, their usage is significantly limited by their poor stability upon moisture exposure and lead toxicity issues. Moreover, many of the aforementioned applications rely on the development of confined perovskite patterns of various shapes and periodicities. Here we report a simple and low-temperature method enabling the controlled incorporation of photoluminescent all-inorganic metal halide PNCs into a silver phosphate glass (AgPO3) matrix which is transparent in most of the visible range. The developed fabrication protocol is based on a simple melting encapsulation process in which pre-synthesized perovskite crystals are inserted in the glass matrix, following the initial glass quenching. Using this novel approach, two types of composite perovskite glasses are prepared, one that hosts perovskite isles and the second in which a thin perovskite layer is embedded beneath the glass surface. Both types of composite glasses exhibit remarkable photoluminescence stability when compared to the ambient air-exposed perovskite crystals. More importantly, by means of a simple and fast cw-laser processing technique, we demonstrate the development of encapsulated dotted perovskite micropatterns within the composite perovskite glass. The ability of the proposed system to resolve stability and lead toxicity issues, coupled with the facile formation of highly luminescent perovskite patterns pave the way towards the broad exploitation of perovskite crystals in photonic applications.
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Nanotechnology, 31, 32 (2020)
Feature size control using surface reconstruction temperature in block copolymer lithography for InAs nanowire growth
Here we present a method to control the size of the openings in hexagonally organized BCP thin films of poly(styrene)-block-poly(4-vinylpyridine) (PS-b-P4VP) by using surface reconstruction. The surface reconstruction is based on selective swelling of the P4VP block in ethanol, and its extraction to the surface of the film, resulting in pores upon drying. We found that the BCP pore diameter increases with ethanol immersion temperature. In our case, the temperature range 18 to 60 °C allowed fine-tuning of the pore size between 14 and 22 nm. A conclusion is that even though the molecular weight of the respective polymer blocks is fixed, the PS-b-P4VP pore diameter can be tuned by controlling temperature during surface reconstruction. These results can be used for BCP-based nanofabrication in general, and for vertical nanowire growth in particular, where high pattern density and diameter control are of importance. Finally, we demonstrate successful growth of indium arsenide InAs vertical nanowires by selective-area metal-organic vapor phase epitaxy (MOVPE), using a silicon nitride mask patterned by the proposed PS-b-P4VP surface reconstruction lithography method.
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Scientific Reports, 10, 8675 (2020)
Ionisation processes and laser induced periodic surface structures in dielectrics with mid-infrared femtosecond laser pulses
Irradiation of solids with ultrashort pulses and laser processing in the mid-Infrared (mid-IR) spectral region is a yet predominantly unexplored field with a large potential for a wide range of applications. In this work, laser driven physical phenomena associated with processes following irradiation of fused silica (SiO2) with ultrashort laser pulses in the mid-IR region are investigated in detail. A multiscale modelling approach is performed that correlates conditions for formation of perpendicular or parallel to the laser polarisation low spatial frequency periodic surface structures for low and high intensity mid-IR pulses (not previously explored in dielectrics at those wavelengths), respectively. Results demonstrate a remarkable domination of tunneling effects in the photoionisation rate and a strong influence of impact ionisation for long laser wavelengths. The methodology presented in this work is aimed to shed light on the fundamental mechanisms in a previously unexplored spectral area and allow a systematic novel surface engineering with strong mid-IR fields for advanced industrial laser applications.
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Appl. Phys. Lett. 116, 203102 (2020)
Prominent room temperature valley polarization in WS2/graphene heterostructures grown by chemical vapor deposition
We examine different cases of heterostructures consisting of WS2 monolayers grown by chemical vapor deposition (CVD) as the optically active material. We show that the degree of valley polarization of WS2 is considerably influenced by the material type used to form the heterostructure. Our results suggest the interaction between WS2 and graphene (WS2/Gr) has a strong effect on the temperature dependent depolarization (i.e. decrease of polarization with increasing temperature), with polarization degrees reaching 24% at room temperature under near-resonant excitation. This contrasts to hBN- encapsulated WS2, which exhibits a room temperature polarization degree of only 11%. The observed low depolarization rate in WS2/Gr heterostructure is attributed to the nearly temperature independent scattering rate due to phonons and fast charge and energy transfer processes from WS2 to graphene. Significant variations in the degree of polarization are also observed at 4K between the different heterostructure configurations. Intervalley hole scattering in the valence band proximity between the K and {\Gamma} points of WS2 is sensitive to the immediate environment, leading to the observed variations.
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ACS Catal. 10, 11, 6223–6230 (2020)
In Situ X-ray Microscopy Reveals Particle Dynamics in a NiCo Dry Methane Reforming Catalyst under Operating Conditions
Herein, we report the synthesis of a γ-Al2O3-supported NiCo catalyst for dry methane reforming (DMR) and study the catalyst using in situ scanning transmission X-ray microscopy (STXM) during the reduction (activation step) and under reaction conditions. During the reduction process, the NiCo alloy particles undergo elemental segregation with Co migrating toward the center of the catalyst particles and Ni migrating to the outer surfaces. Under DMR conditions, the segregated structure is maintained, thus hinting at the importance of this structure to optimal catalytic functions. Finally, the formation of Ni-rich branches on the surface of the particles is observed during DMR, suggesting that the loss of Ni from the outer shell may play a role in the reduced stability and hence catalyst deactivation. These findings provide insights into the morphological and electronic structural changes that occur in a NiCo-based catalyst during DMR. Further, this study emphasizes the need to study catalysts under operating conditions in order to elucidate material dynamics during the reaction.
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J. Mater. Chem. B, 2020,8, 5080-5088
Stable anchoring of bacteria-based protein nanoparticles for surface enhanced cell guidance
In tissue engineering, biological, physical, and chemical inputs have to be combined to properly mimic cellular environments and successfully build artificial tissues which can be designed to fulfill different biomedical needs such as the shortage of organ donors or the development of in vitro disease models for drug testing. Inclusion body-like protein nanoparticles (pNPs) can simultaneously provide such physical and biochemical stimuli to cells when attached to surfaces. However, this attachment has only been made by physisorption. To provide a stable anchoring, a covalent binding of lactic acid bacteria (LAB) produced pNPs, which lack the innate pyrogenic impurities of Gram-negative bacteria like Escherichia coli, is presented. The reported micropatterns feature a robust nanoscale topography with an unprecedented mechanical stability. In addition, they are denser and more capable of influencing cell morphology and orientation. The increased stability and the absence of pyrogenic impurities represent a step forward towards the translation of this material to a clinical setting.
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Applied Surface Science, 520, 146307 (2020)
Deep UV laser induced periodic surface structures on silicon formed by self-organization of nanoparticles
The Sm-activated orthvanadate nanoparticles were synthesized by co-precipitation and sol-gel methods. XRD study has shown that synthesized samples are characterized by monoclinic or tetragonal structure as well as their mixture dependently on Sm concentration and methods of synthesis. Influence of method of synthesis on morphology of nanoparticles, their absorption, diffuse reflectance and emission spectra was observed and studied.
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Materials 2020, 13(7), 1762
Improvement of Manganese Feroxyhyte’s Surface Charge with Exchangeable Ca Ions to Maximize Cd and Pb Uptake from Water
The surface configuration of tetravalent manganese feroxyhyte (TMFx) was appropriately modified to achieve higher negative surface charge density and, hence, to improve its efficiency for the removal of dissolved Cd and Pb mostly cationic species from water at pH values commonly found in surface or ground waters. This was succeeded by the favorable engagement of Ca2+ cations onto the surface of a mixed Mn-Fe oxy-hydroxide adsorbent during the preparation step, imitating an ion-exchange mechanism between H+ and Ca2+; therefore, the number of available negatively-charged adsorption sites was increased. Particularly, the calcium coverage can increase the deprotonated surface oxygen atoms, which can act as adsorption centers, as well as maintain them during the subsequent drying procedure. The developed Ca-modified adsorbent (denoted as TMFx-Ca) showed around 10% increase of negative surface charge density, reaching 2.0 mmol [H+]/g and enabling higher adsorption capacities for both Cd and Pb aquatic species, as was proved also by carrying out specific rapid small-scale column tests, and it complied with the corresponding strict drinking water regulation limits. The adsorption capacity values were found 6.8 μg·Cd/mg and 35.0 μg·Pb/mg, when the restructured TMFx-Ca adsorbent was used, i.e., higher than those recorded for the unmodified material.
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Results in Materials, 6,2020, 100088 (2020)
Controlling electrical and optical properties of zinc oxide thin films grown by thermal atomic layer deposition with oxygen gas
The preparation of ZnO thin films with controlled electrical resistivity and optical properties is often challenged by the presence of defects, such as oxygen vacancies or interstitial zinc. Here, we investigate the material properties of ZnO polycrystalline thin films prepared by thermal Atomic Layer Deposition (ALD) with the presence of molecular oxygen pulsing during the growth. By means of structural, electrical and optical characterizations, we identify key growth parameters of this unusual ALD process. Unexpectedly, the influence of oxygen molecules on the crystallography, microstructure and morphology of ZnO films is significant from hundred-nanometers to micrometer thick film. The electrical resistivity of the films grown with oxygen gas shows a dramatic increase from 3 to 4 orders of magnitude. Additionally, photoluminescence measurements reveal that deep-level emissions caused by defects located deep in the band gap can be reduced by applying an adequate pulsing of oxygen gas during the process. Finally, we conclude with a discussion about the degree of consistency between the chemical composition, the inner strain and the optical and electrical properties of the films obtained with the different thermodynamic parameters of growth. Several hypotheses are discussed in order to understand the dominance of (002) orientation in the presence of oxygen during the ALD growth process.
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ACS Nano 2020, 14, 5, 5700–5710
Strongly Coupled Coherent Phonons in Single-Layer MoS2
We present a transient absorption setup combining broadband detection over the visible–UV range with high temporal resolution (∼20 fs) which is ideally suited to trigger and detect vibrational coherences in different classes of materials. We generate and detect coherent phonons (CPs) in single-layer (1L)-MoS2, as a representative semiconducting 1L-transition metal dichalcogenide (TMD), where the confined dynamical interaction between excitons and phonons is unexplored. The coherent oscillatory motion of the out-of-plane A′1 phonons, triggered by the ultrashort laser pulses, dynamically modulates the excitonic resonances on a time scale of few tens of fs. We observe an enhancement by almost 2 orders of magnitude of the CP amplitude when detected in resonance with the C exciton peak, combined with a resonant enhancement of CP generation efficiency. Ab initio calculations of the change in the 1L-MoS2 band structure induced by the A′1 phonon displacement confirm a strong coupling with the C exciton. The resonant behavior of the CP amplitude follows the same spectral profile of the calculated Raman susceptibility tensor. These results explain the CP generation process in 1L-TMDs and demonstrate that CP excitation in 1L-MoS2 can be described as a Raman-like scattering process.
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Phys. Chem. Chem. Phys., 2020,22, 8336-8343
Order–disorder phase transition of the subsurface cation vacancy reconstruction on Fe3O4 (001)
We present surface X-ray diffraction and fast scanning tunneling microscopy results to elucidate the nature of the surface phase transition on magnetite (001) from (sqrt2 x sqrt2) R45° reconstructed to a non-reconstructed surface around 720 K. In situ surface X-ray diffraction at a temperature above the phase transition, at which long-range order is lost, gives evidence that the subsurface cation vacancy reconstruction still exists as a local structural motif, in line with the characteristics of a 2D second-order phase transition. Fast scanning tunneling microscopy results across the phase transition underpin the hypothesis that the reconstruction lifting is initiated by surplus Fe ions occupying subsurface octahedral vacancies. The reversible near-surface iron enrichment and reduction of the surface to stoichiometric composition is further confirmed by in situ low-energy ion scattering, as well as ultraviolet and X-ray photoemission results.
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Applied Surface Science, Volume 514, 1 June 2020, 145923
Single-layer graphene on epitaxial FeRh thin films
Graphene is a 2D material that displays excellent electronic transport properties with prospective applications in many fields. Inducing and controlling magnetism in the graphene layer, for instance by proximity of magnetic materials, may enable its utilization in spintronic devices. This paper presents fabrication and detailed characterization of single-layer graphene formed on the surface of epitaxial FeRh thin films. The magnetic state of the FeRh surface can be controlled by temperature, magnetic field or strain due to interconnected order parameters. Characterization of graphene layers by X-ray Photoemission and X-ray Absorption Spectroscopy, Low-Energy Ion Scattering, Scanning Tunneling Microscopy, and Low-Energy Electron Microscopy shows that graphene is single-layer, polycrystalline and covers more than 97% of the substrate. Graphene displays several preferential orientations on the FeRh(0 0 1) surface with unit vectors of graphene rotated by 30°, 15°, 11°, and 19° with respect to FeRh substrate unit vectors. In addition, the graphene layer is capable to protect the films from oxidation when exposed to air for several months. Therefore, it can be also used as a protective layer during fabrication of magnetic elements or as an atomically thin spacer, which enables incorporation of switchable magnetic layers within stacks of 2D materials in advanced devices.
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CrystEngComm, 2020,22, 2483-2490
Synthesis of Na2Ti3O7 nanorods by a V-assisted route and investigation of their battery performance
We report the V-assisted synthesis of Na2Ti3O7 nanorods via a conventional solid state reaction technique. Energy dispersive X-ray spectroscopy (EDS) mapping showed that V-ions are not incorporated into the main structure of the nanorods but rather V behaves as a flux agent during the growth of the nanorods. The cyclic voltammetry (CV) analysis of the samples shows changes in the redox peaks as a function of V content. Our detailed ex situ X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray absorption spectroscopy (XAS) analyses after 1000 cycles show that the degradation mechanism is the formation of various titanium oxide impurity phases which inhibits the Na-ion diffusion.
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Nature Communications, 11, 428 (2020)
Diameter-independent skyrmion Hall angle observed in chiral magnetic multilayers
Magnetic skyrmions are topologically non-trivial nanoscale objects. Their topology, which originates in their chiral domain wall winding, governs their unique response to a motion-inducing force. When subjected to an electrical current, the chiral winding of the spin texture leads to a deflection of the skyrmion trajectory, characterised by an angle with respect to the applied force direction. This skyrmion Hall angle is predicted to be skyrmion diameter-dependent. In contrast, our experimental study finds that the skyrmion Hall angle is diameter-independent for skyrmions with diameters ranging from 35 to 825 nm. At an average velocity of 6 ± 1 ms−1, the average skyrmion Hall angle was measured to be 9° ± 2°. In fact, the skyrmion dynamics is dominated by the local energy landscape such as materials defects and the local magnetic configuration.
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Carbon Volume 161, May 2020, Pages 528-534
Operando atomic-scale study of graphene CVD growth at steps of polycrystalline nickel
An operando investigation of graphene growth on (100) grains of polycrystalline nickel (Ni) surfaces was performed by means of variable-temperature scanning tunneling microscopy complemented by density functional theory simulations. A clear description of the atomistic mechanisms ruling the graphene expansion process at the stepped regions of the substrate is provided, showing that different routes can be followed, depending on the height of the steps to be crossed. When a growing graphene flake reaches a monoatomic step, it extends jointly with the underlying Ni layer; for higher Ni edges, a different process, involving step retraction and graphene landing, becomes active. At step bunches, the latter mechanism leads to a peculiar ‘staircase formation’ behavior, where terraces of equal width form under the overgrowing graphene, driven by a balance in the energy cost between C–Ni bond formation and stress accumulation in the carbon layer. Our results represent a step towards bridging the material gap in searching new strategies and methods for the optimization of chemical vapor deposition graphene production on polycrystalline metal surfaces.
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Phys. Rev. A 101, 013820 (2020)
Ghost imaging at an XUV free-electron laser
Here we present the results of a classical ghost imaging experiment accomplished at an XUV free-electron laser (FEL). To perform such experiment at an FEL source each x-ray pulse was transmitted through a moving diffuser, which created a noncorrelated speckled beam. This beam was then split in two identical branches by introducing a beam splitter in the form of a transmission grating. In one of these branches the sample was positioned. We demonstrate the possibility of image formation, a double bar in our case, in the beam that has never interacted with the sample. With this experiment we extend the quantum optics methodology to the FEL community.
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Materials & Design, 189, April 2020, 108505
Gas tungsten arc welding of as-rolled CrMnFeCoNi high entropy alloy
High entropy alloys have emerged as novel engineering alloys with remarkable mechanical properties in a wide range of temperatures. Among the several high entropy alloys that were already described, the equiatomic CrMnFeCoNi alloy is the most studied one. In this work, gas tungsten arc welding of as-rolled CrMnFeCoNi high entropy alloy sheets was performed. The microstructural characterization encompassed the use of electron microscopy, including electron backscattered diffraction, synchrotron X-ray diffraction analysis, microhardness testing and mechanical evaluation. A comprehensive description of the microstructural evolution, including texture and microstrain determination, of the joint is presented and discussed. Upon mechanical testing, the joints systematically failed in the fusion zone due. The large grain size and low hardness of this region justifies the failure location. The joints' mechanical behaviour is correlated with the material microstructure.
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Phys. Rev. B 101, 045414
Surface susceptibility and conductivity of MoS2 and WSe2 monolayers: A first-principles and ellipsometry characterization
We employ a recent formulation for the optical properties of two-dimensional crystals from first principles [L. Matthes et al., New J. Phys. 16, 105007 (2014); L. Matthes et al., Phys. Rev. B 94, 205408 (2016)] to compute the surface susceptibility and surface conductivity of MoS2 and WSe2 monolayers [G. Jayaswal et al., Opt. Lett. 43, 703 (2018)]. As electron-hole interactions are known to be crucial for the description of the absorption spectrum of monolayer transition metal dichalcogenides, the excitonic dielectric function is computed at the Bethe-Salpeter equation level, including spin-orbit interactions. For both of these examples, excellent agreement with experimental ellipsometry measurements is obtained. Driven by the emergence of additional features in our theoretical results, we applied a second-derivative analysis in order to identify excited exciton peaks in the ellipsometric spectra.
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Applied Surface Science, 509, 145263 (2020)
Influence of pulsed laser ablation temperature on structure, morphology and electrocatalytic properties of cobalt-based films deposited on carbon cloth
Cobalt-based electrocatalytic films on electrochemically activated carbon cloth (EACC) were prepared by pulsed laser deposition (PLD) technique at different substrate temperatures. The composition, nanostructure and morphology of the films were thoroughly characterized and their electrocatalytic activities towards hydrogen and oxygen evolution in alkaline solutions were assessed. The electrochemical performances were correlated with material characteristics. The cobalt-based film morphology and structure changed significantly with increasing growth temperature, from nanocrystalline dense film, through uniform monocrystalline nanopillar structure, up to coarser irregular grains. Also, the film composition has clearly changed in the series of electrodes. The films prepared at lower temperatures were predominantly composed of CoCO3, while at higher temperatures their primary component was Co3O4. For prepared electrodes, the influence of material morphology on hydrogen evolution activity is shown to be pivotal, while no effect of material composition on performance is confirmed. Careful control over deposition parameters enabled formation of the film with optimal electrocatalytic performance towards both HER and OER, characterized with nanopillar morphology topped with pyramid-shape caps, providing high electrochemically active surface area for electrochemical reactions. The optimized electrode requires the overpotentials of 270 and 400 mV to deliver the current density of 10 mA cm−2 for HER and OER respectively.
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Nanomaterials 2020, 10(1), 103
Grain-Boundary-Induced Alignment of Block Copolymer Thin Films
We present and discuss the capability of grain boundaries to induce order in block copolymer thin films between horizontally and vertically assembled block copolymer grains. The system we use as a proof of principle is a thermally annealed 23.4 nm full-pitch lamellar Polystyrene-block-polymethylmetacrylate (PS-b-PMMA) di-block copolymer. In this paper, grain-boundary-induced alignment is achieved by the mechanical removal of the neutral brush layer via atomic force microscopy (AFM). The concept is also confirmed by a mask-less e-beam direct writing process. An elongated grain of vertically aligned lamellae is trapped between two grains of horizontally aligned lamellae. This configuration leads to the formation of 90° twist grain boundaries. The features maintain their orientation on a characteristic length scale, which is described by the material’s correlation length ξ. As a result of an energy minimization process, the block copolymer domains in the vertically aligned grain orient perpendicularly to the grain boundary. The energy-minimizing feature is the grain boundary itself. The width of the manipulated area (e.g., the horizontally aligned grain) does not represent a critical process parameter.
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J. Synchrotron Rad. (2020). 27, 51-59
Picosecond pump–probe X-ray scattering at the Elettra SAXS beamline
A new setup for picosecond pump–probe X-ray scattering at the Austrian SAXS beamline at Elettra-Sincrotrone Trieste is presented. A high-power/high-repetion-rate laser has been installed on-site, delivering UV/VIS/IR femto­second-pulses in-sync with the storage ring. Data acquisition is achieved by gating a multi-panel detector, capable of discriminating the single X-ray pulse in the dark-gap of the Elettra hybrid filling mode. Specific aspects of laser- and detection-synchronization, on-line beam steering as well protocols for spatial and temporal overlap of laser and X-ray beam are also described. The capabilities of the setup are demonstrated by studying transient heat-transfer in an In/Al/GaAs superlattice structure and results are confirmed by theoretical calculations.
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Coatings 2019, 9(12), 854
Laser-Assisted Surface Texturing of Ti/Zr Multilayers for Mesenchymal Stem Cell Response
The formation of an ordered surface texture with micro and nanometer features on Ti/Zr multilayers is studied for better understanding and improvement of cell integration. Nanocomposite in form 30×(Ti/Zr)/Si thin films was deposited by ion sputtering on Si substrate for biocompatibility investigation. Surface texturing by femtosecond laser processing made it possible to form the laser-induced periodic surface structure (LIPSS) in each laser-written line. At fluence slightly above the ablation threshold, beside the formation of low spatial frequency-LIPSS (LSFL) oriented perpendicular to the direction of the laser polarization, the laser-induced surface oxidation was achieved on the irradiated area. Intermixing between the Ti and Zr layers with the formation of alloy in the sub-surface region was attained during the laser processing. The surface of the Ti/Zr multilayer system with changed composition and topography was used to observe the effect of topography on the survival, adhesion and proliferation of the murine mesenchymal stem cells (MSCs). Confocal and SEM microscopy images showed that cell adhesion and their growth improve on these modified surfaces, with tendency of the cell orientation along of LIPSS in laser-written lines.
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Phys. Rev. A 100, 061404(R)
Quantum path interferences in high-order harmonic generation from aligned diatomic molecules
Electron quantum path interferences in strongly laser-driven aligned molecules and their dependence on the molecular alignment is an essential open problem in strong-field molecular physics. Here, we demonstrate an approach which provides direct access to the observation of these interference processes. The approach is based on the combination of the time-gated-ion-microscopy technique with a pump-probe arrangement used to align the molecules and generate high-order harmonics. By spatially resolving the interference pattern produced by the spatiotemporal overlap of the harmonics emitted by the short and long electron quantum paths, we have succeeded in measuring in situ their phase difference and disclose their dependence on molecular alignment. The findings constitute a vital step towards an understanding of strong-field molecular physics and the development of attosecond spectroscopy approaches without the use of auxiliary atomic references.
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Nanoscale, 2020,12, 815-824
GaAs nanoscale membranes: prospects for seamless integration of III–Vs on silicon
The growth of compound semiconductors on silicon has been widely sought after for decades, but reliable methods for defect-free combination of these materials have remained elusive. Recently, interconnected GaAs nanoscale membranes have been used as templates for the scalable integration of nanowire networks on III–V substrates. Here, we demonstrate how GaAs nanoscale membranes can be seamlessly integrated on silicon by controlling the density of nuclei in the initial stages of growth. We also correlate the absence or presence of defects with the existence of a single or multiple nucleation regime for the single membranes. Certain defects exhibit well-differentiated spectroscopic features that we identify with cathodoluminescence and micro-photoluminescence techniques. Overall, this work presents a new approach for the seamless integration of compound semiconductors on silicon.
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ACS Omega 2019, 4, 25, 20972–20977
Presegmentation Procedure Generates Smooth-Sided Microfluidic Devices: Unlocking Multiangle Imaging for Everyone?
We present a simple procedure to create smooth-sided, transparent polymer-based microfluidic devices by presegmentation with hydrophobized glass slides. We study the hypothesis that the smooth side planes permit rapid multiangle imaging of microfluidic systems in contrast to the turbid side planes that result from cutting the polymer. We compare the compatibility of the entire approach with the conventional widefield microscopy, confocal and 2-photon microscopy, as well as three-dimensional (3D) rendering and discuss limitations and potential applications.
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Journal of Magnetism and Magnetic Materials, 489, 165376 (2019)
Synthesis, structure and magnetization Co4N thin films
We reviewed magnetic tetra metal nitrides – Fe4N and Co4N for their structure, magnetization and the thermodynamics of phase formation. Opposed to Fe4N, the formation of a stoichiometric Co4N turns out to be extremely difficult. A review of the literature of Co4N compound suggest that the experimental lattice parameter (LP) was always found to be smaller than the theoretical predicted value. It can also be seen that as the substrate temperature (Ts) increases, the LP of Co4N film decreases. In this work, we deposited Co4N films using molecular beam epitaxy (MBE), direct current magnetron sputtering (dcMS) and high power impulse MS (HiPIMS). Films were characterized using X-ray diffraction, X-ray reflectivity and atomic force microscopy. It was found that at high Ts, N out-diffusion significantly affects the growth of Co4N phase. We found that the MBE deposited films did not show any signature of Co4N phase when Ts<703K but at Ts=703K, the phase formed can be assigned to fcc Co rather than Co4N. On the other hand, the dcMS and HiPIMS grown films clearly show the presence of Co4N phase even at Ts=300K. Detailed analysis of Co4N films grown using dcMS and HiPIMS reveals that HiPIMS grown films are single phase and have a denser microstructure. The density of HiPIMS deposited film was also found to be close to the theoretical value. Magneto optical Kerr effect and polarized neutron reflectivity measurements were carried out to study magnetic properties. Differences in the magnetic moment and magnetic anisotropy were correlated with structural parameters. Obtained results are presented and discussed in terms of involved thin film growth mechanism.
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NANOSYSTEMS: PHYSICS, CHEMISTRY, MATHEMATICS, 2019, 10 (6), P. 654–665
Phosphors with different morphology, formed under hydrothermal conditions on the basis of ZrO2:Eu3+ nanocrystallites
Eu3+-doped ZrO2 nanostructures in the form of rods, stars, and hollow spheres were prepared by varying hydrothermal conditions. X-ray diffraction, transmission electron microscopy, ultraviolet-visible diffuse reflection spectroscopy, a low-temperature nitrogen adsorption method, Raman spectroscopy and photoluminescence spectra were used to characterize the polymorph modification, surface and optical properties of the Zr0:98Eu0:02O2 nanophosphors. The Eu3+ content in a zirconia monoclinic lattice, remained constant for all types of obtained nanostructures in order to reveal the morphology influence on the efficiency of electronic excitation energy transfer from the host matrix to photoactive centers. The decrease of the average size of the coherent scattering regions in the series rods -> stars -> hollow spheres, is associated with increasing the specific surface area values. At that, in the photoluminescence spectrum, the splitting of the sublevels associated with the monoclinic lattice D-5(0) -> F-7(1) disappears.
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J. Am. Chem. Soc. 2019, 141, 50, 19839–19849
Stable Ultraconcentrated and Ultradilute Colloids of CsPbX3 (X = Cl, Br) Nanocrystals Using Natural Lecithin as a Capping Ligand
Attaining thermodynamic stability of colloids in a broad range of concentrations has long been a major thrust in the field of colloidal ligand-capped semiconductor nanocrystals (NCs). This challenge is particularly pressing for the novel NCs of cesium lead halide perovskites (CsPbX3; X = Cl, Br) owing to their highly dynamic and labile surfaces. Herein, we demonstrate that soy lecithin, a mass-produced natural phospholipid, serves as a tightly binding surface-capping ligand suited for a high-reaction yield synthesis of CsPbX3 NCs (6–10 nm) and allowing for long-term retention of the colloidal and structural integrity of CsPbX3 NCs in a broad range of concentrations—from a few ng/mL to >400 mg/mL (inorganic core mass). The high colloidal stability achieved with this long-chain zwitterionic ligand can be rationalized with the Alexander–De Gennes model that considers the increased particle–particle repulsion due to branched chains and ligand polydispersity. The versatility and immense practical utility of such colloids is showcased by the single NC spectroscopy on ultradilute samples and, conversely, by obtaining micrometer-thick, optically homogeneous dense NC films in a single spin-coating step from ultraconcentrated colloids.
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Water 2019, 11(12), 2477
An Optimized Cr(VI)-Removal System Using Sn-based Reducing Adsorbents
Despite significant risks to human health due to elevated Cr(VI) concentrations in drinking water, a selective adsorbent capable of purifying water before consumption is still not commercially available. This work introduces an integrated household water filtration setup, for point-of-use applications, loaded with a tin-based Cr(VI)-oriented adsorbent that was tested under various contact times, pH values and Cr(VI) concentrations. The adsorbent comprises a chloride-substituted stannous oxy-hydroxide with a structure resembling that of the mineral abhurite. It demonstrated high reducing capacity that triggered the formation of insoluble Cr(III) hydroxides and the complete removal of Cr(VI) in considerably high volumes of polluted water. Test operation of the filtration system verified its ability to produce Cr(VI)-free water in compliance with the impending drinking water regulation, even for extreme initial concentrations (1000 μg/L). Apart from its high efficiency, the potential of the studied material is enhanced by its minimal-cost synthesis method carried out in a continuous-flow reactor by tin chloride precipitation under acidic conditions.
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Nano Letters 19, 12 (2019)
Three-Dimensional Superconducting Nanohelices Grown by He+-Focused-Ion-Beam Direct Writing
Novel schemes based on the design of complex three-dimensional (3D) nanoscale architectures are required for the development of the next generation of advanced electronic components. He+ focused-ion-beam (FIB) microscopy in combination with a precursor gas allows one to fabricate 3D nanostructures with an extreme resolution and a considerably higher aspect ratio than FIB-based methods, such as Ga+ FIB-induced deposition, or other additive manufacturing technologies. In this work, we report the fabrication of 3D tungsten carbide nanohelices with on-demand geometries via controlling key deposition parameters. Our results show the smallest and highest-densely packed nanohelix ever fabricated so far, with dimensions of 100 nm in diameter and aspect ratio up to 65. These nanohelices become superconducting at 7 K and show a large critical magnetic field and critical current density. In addition, given its helical 3D geometry, fingerprints of vortex and phase-slip patterns are experimentally identified and supported by numerical simulations based on the time-dependent Ginzburg–Landau equation. These results can be understood by the helical geometry that induces specific superconducting properties and paves the way for future electronic components, such as sensors, energy storage elements, and nanoantennas, based on 3D compact nanosuperconductors.
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Nanoscale, 2017,9, 18202-18207
Low-temperature benchtop-synthesis of all-inorganic perovskite nanowires
A facile, low-temperature precipitation-based method is utilized for the synthesis of ultra-thin and highly uniform cesium lead bromide perovskite nanowires (NWs). The reactions facilitate the NWs’ crystalline nature over micron-size lengths, while they impart tailored nanowire widths that range from the quantum confinement regime (∼7 nm) down to 2.6 nm. This colloidal synthesis approach is the first of its kind that is carried out on the work-bench, without demanding chemical synthesis equipment. Importantly, the NWs’ photoluminescence is shown to improve over time, with no requirement for tedious post-synthesis surface treatment.
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Adv. Energy Mater. 2020, 10, 1901524
Enhanced stability of perovskite solar cells incorporating dopant-free crystalline SpiroOMeTAD layers by vacuum sublimation
The main handicap still hindering the eventual exploitation of organometal halide perovskite-based solar cells is their poor stability under prolonged illumination, ambient conditions, and increased temperatures. This article shows for the first time the vacuum processing of the most widely used solid-state hole conductor (SSHC), i.e., the Spiro-OMeTAD [2,2′,7,7′-tetrakis (N,N-di-p-methoxyphenyl-amine) 9,9′-spirobifluorene], and how its dopant-free crystalline formation unprecedently improves perovskite solar cell (PSC) stability under continuous illumination by about two orders of magnitude with respect to the solution-processed reference and after annealing in air up to 200 °C. It is demonstrated that the control over the temperature of the samples during the vacuum deposition enhances the crystallinity of the SSHC, obtaining a preferential orientation along the π–π stacking direction. These results may represent a milestone toward the full vacuum processing of hybrid organic halide PSCs as well as light-emitting diodes, with promising impacts on the development of durable devices. The microstructure, purity, and crystallinity of the vacuum sublimated Spiro-OMeTAD layers are fully elucidated by applying an unparalleled set of complementary characterization techniques, including scanning electron microscopy, X-ray diffraction, grazing-incidence small-angle X-ray scattering and grazing-incidence wide-angle X-ray scattering, X-ray photoelectron spectroscopy, and Rutherford backscattering spectroscopy.
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Chem. Mater. 2019, 31, 22, 9462–9471
Integrated Cleanroom Process for the Vapor-Phase Deposition of Large-Area Zeolitic Imidazolate Framework Thin Films
Robust and scalable thin-film deposition methods are key to realize the potential of metal-organic frameworks (MOFs) in electronic devices. Here, we report the first integration of the chemical vapor deposition (CVD) of MOF coatings in a custom reactor within a cleanroom setting. As a test case, the MOF-CVD conditions for the zeolitic imidazolate framework-8 are optimized to enable smooth, pinhole-free, and uniform thin films on full 200 mm wafers under mild conditions. The single-chamber MOF-CVD process and the impact of the deposition parameters are elucidated via a combination of in situ monitoring and ex situ characterization. The resulting process guidelines will pave the way for new MOF-CVD formulations and a plethora of MOF-based devices.
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Applied Surface Science Volume 504, 28 February 2020, 144343
Evaluation of molecular orbital symmetry via oxygen-induced charge transfer quenching at a metal-organic interface
Thin molecular films under model conditions are often exploited as benchmarks and case studies to investigate the electronic and structural changes occurring on the surface of metallic electrodes. Here we show that the modification of a metallic surface induced by oxygen adsorption allows the preservation of the geometry of a molecular adlayer, giving access to the determination of molecular orbital symmetries by means of near-edge X-ray absorption fine structure spectroscopy, NEXAFS. As a prototypical example, we exploited nickel tetraphenylporphyrin molecules deposited on a bare and on an oxygen pre-covered Cu(1 0 0) surface. We find that adsorbed atomic oxygen quenches the charge transfer at the metal-organic interface but, in contrast to a thin film sample, maintains the ordered adsorption geometry of the organic molecules. In this way, it is possible to disentangle π* and σ* symmetry orbitals, hence estimate the relative oscillator strength of core level transitions directly from the experimental data, as well as to evaluate and localize the degree of charge transfer in a coupled system. In particular, we neatly single out the σ* contribution associated with the N 1s transition to the mixed N 2px,y-Ni 3dx2-y2 orbital, which falls close to the leading π*-symmetry LUMO resonance.
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Sustainable Energy Fuels, 2020,4, 369-379
Tailoring the composition of a one-step electrodeposited Co,Ni/Co,Ni(OH)2 composite coating for a highly active hydrogen evolution electrode
Low hydrogen evolution overpotential, along with high stability during operation and ease of preparation from inexpensive raw materials, is a crucial characteristic of an effective electrode for large-scale hydrogen generation by alkaline water electrolysis. Herein, we present a method of preparation of a low-cost electrode, applying as a substrate a carbon fiber textile derived from a technical carbon fiber reinforced polymer. Noble-metal free composite films composed of cobalt–nickel alloy and amorphous Co,Ni(OH)2 phases are obtained by a one-step electrodeposition process. Deposition is optimized in terms of the applied potential as well as metal ion concentration and Co/Ni ratio in an electroplating bath. The experimental results indicate that the hCT-Co0.4Ni0.6 electrode possesses the lowest HER overpotential of 150 mV at a current density of 10 mA cm−2 in 1.0 M KOH, with negligible activity loss within 100 h of galvanostatic operation. A significant decrease of the overpotential and electrode stability boost are achieved thanks to the precise control of the bimetallic electrode composition, which affects the morphology, electrocatalytically active surface area and electronic properties of the material.
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New J. Phys. 21 103038
Distinguishing Majorana zero modes from impurity states through time-resolved transport
We study time-resolved charge transport in a superconducting nanowire using time-dependent Landauer–Büttiker theory. We find that the steady-state Majorana zero-bias conductance peak emerges transiently accompanied by characteristic oscillations after a bias-voltage quench. These oscillations are suppressed for trivial impurity states (IS) that otherwise show a similar steady-state signal as the Majorana zero mode (MZM). In addition, we find that Andreev bound states or quasi-Majorana states (QMS) in the topologically trivial bulk phase can give rise to a zero-bias conductance peak, also retaining the transient properties of the MZM. Our results imply that (1) time-resolved transport may be used as a probe to distinguish between the topological MZM and trivial IS; and (2) the QMS mimic the transient signatures of the topological MZMs.
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Scientific Reports volume 9, 14285 (2019)
Twist Angle mapping in layered WS2 by Polarization-Resolved Second Harmonic Generation
Stacked atomically thin transition metal dichalcogenides (TMDs) exhibit fundamentally new physical properties compared to those of the individual layers. The twist angle between the layers plays a crucial role in tuning these properties. Having a tool that provides high-resolution, large area mapping of the twist angle, would be of great importance in the characterization of such 2D structures. Here we use polarization-resolved second harmonic generation (P-SHG) imaging microscopy to rapidly map the twist angle in large areas of overlapping WS2 stacked layers. The robustness of our methodology lies in the combination of both intensity and polarization measurements of SHG in the overlapping region. This allows the accurate measurement and consequent pixel-by-pixel mapping of the twist angle in this area. For the specific case of 30° twist angle, P-SHG enables imaging of individual layers.
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Nanoscale, 2019,11, 18191-18200
Scanning tunneling microscopy and Raman spectroscopy of polymeric sp–sp2 carbon atomic wires synthesized on the Au(111) surface
Long linear carbon nanostructures based on sp-hybridization can be synthesized by exploiting on-surface synthesis of halogenated precursors evaporated on Au(111), thus opening a way to investigations by surface-science techniques. By means of an experimental approach combining scanning tunneling microscopy and spectroscopy (STM and STS) with ex situ Raman spectroscopy we investigate the structural, electronic and vibrational properties of polymeric sp–sp2 carbon atomic wires composed by sp-carbon chains connected through phenyl groups. Density-functional-theory (DFT) calculations of the structure and the electronic density of states allow us to simulate STM images and to compute Raman spectra. The comparison of experimental data with DFT simulations unveil the properties and the formation stages as a function of the annealing temperature. Atomic-scale structural information from STM complement the Raman sensitivity to the single molecular bond to open the way to detailed understanding of these novel carbon nanostructures.
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J. Phys. Chem. C 2019, 123, 41, 25197–25208
Mapping the Pore Architecture of Structured Catalyst Monoliths from Nanometer to Centimeter Scale with Electron and X-ray Tomographies
The hierarchical pore systems of Pt/Al2O3 exhaust gas aftertreatment catalysts were analyzed with a collection of correlative imaging techniques to monitor changes induced by hydrothermal aging. Synergistic imaging with laboratory X-ray microtomography, synchrotron radiation ptychographic X-ray computed nanotomography, and electron tomography allowed quantitative observation of the catalyst pore architecture from centimeter to nanometer scale. Thermal aging at 750 °C in air and hydrothermal aging at 1050 °C in 10% H2O/air caused increasing structural degradation, which manifested as widespread sintering of Pt particles, increased volume and quantity of macropores (>20 nm), and reduction in effective surface area coupled with decreasing volume and frequency of mesopores (2–20 nm) and micropores (<2 nm). Electron tomography unraveled the three-dimensional (3D) structure with high resolution allowing visualization of meso- and macropores but with samples of maximum 300 nm thickness. To complement this, hard X-ray ptychographic tomography produced quantitative 3D electron density maps of 5 μm diameter samples with spatial resolution <50 nm, effectively filling the resolution gap between electron tomography and hard X-ray microtomography. The obtained 3D volumes are an essential input for future computational modeling of fluid dynamics, mass transport, or diffusion properties and may readily complement bulk one-dimensional porosimetry measurements or simulated porosity.
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Nano Lett. 2019, 19, 10, 7246–7255
Deterministic Field-Free Skyrmion Nucleation at a Nanoengineered Injector Device
Magnetic skyrmions are topological solitons promising for applications as encoders for digital information. A number of different skyrmion-based memory devices have been recently proposed. In order to demonstrate a viable skyrmion-based memory device, it is necessary to reliably and reproducibly nucleate, displace, detect, and delete the magnetic skyrmions, possibly in the absence of external applied magnetic fields, which would needlessly complicate the device design. While the skyrmion displacement and detection have both been thoroughly investigated, much less attention has been dedicated to the study of the skyrmion nucleation process and its sub-nanosecond dynamics. In this study, we investigate the nucleation of magnetic skyrmions from a dedicated nanoengineered injector, demonstrating the reliable magnetic skyrmion nucleation at the remnant state. The sub-nanosecond dynamics of the skyrmion nucleation process were also investigated, allowing us to shine light on the physical processes driving the nucleation.
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ACS Biomater. Sci. Eng. 2019, 5, 10, 5470–5480
High-Throughput Cell Motility Studies on Surface-Bound Protein Nanoparticles with Diverse Structural and Compositional Characteristics
Eighty areas with different structural and compositional characteristics made of bacterial inclusion bodies formed by the fibroblast growth factor (FGF-IBs) were simultaneously patterned on a glass surface with an evaporation-assisted method that relies on the coffee-drop effect. The resulting surface patterned with these protein nanoparticles enabled to perform a high-throughput study of the motility of NIH-3T3 fibroblasts under different conditions including the gradient steepness, particle concentrations, and area widths of patterned FGF-IBs, using for the data analysis a methodology that includes “heat maps”. From this analysis, we observed that gradients of concentrations of surface-bound FGF-IBs stimulate the total cell movement but do not affect the total net distances traveled by cells. Moreover, cells tend to move toward an optimal intermediate FGF-IB concentration (i.e., cells seeded on areas with high IB concentrations moved toward areas with lower concentrations and vice versa, reaching the optimal concentration). Additionally, a higher motility was obtained when cells were deposited on narrow and highly concentrated areas with IBs. FGF-IBs can be therefore used to enhance and guide cell migration, confirming that the decoration of surfaces with such IB-like protein nanoparticles is a promising platform for regenerative medicine and tissue engineering.
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J. Mater. Chem. C, 2019,7, 12170-12179
In situ monitoring of the charge carrier dynamics of CH3NH3PbI3 perovskite crystallization process
Although methylammonium lead iodide (CH3NH3PbI3) perovskite has attracted enormous scientific attention over the last decade or so, important information on the charge extraction dynamics and recombination processes in perovskite devices is still missing. Herein we present a novel approach to evaluate the quality of CH3NH3PbI3 layers, via in situ monitoring of the perovskite layer charge carrier dynamics during the thermal annealing crystallization process, by means of time-resolved femtosecond transient absorption spectroscopy (TAS). In particular, CH3NH3PbI3 films were deposited on two types of polymeric hole transport layers (HTL), poly(3,4-ethylenedioxythiophene)-poly-(styrenesulfonate) (PEDOT:PSS) and poly-(triarylamine) (PTAA), that are known to provide different carrier transport characteristics in perovskite solar cells. In order to monitor the evolution of the perovskite charge carrier dynamics during the crystallization process, the so-formed CH3NH3PbI3/HTL architectures were studied in situ by TAS at three different annealing temperatures, i.e., 90, 100 and 110 °C. It is revealed that the annealing time period required in order to achieve the optimum perovskite film quality in terms of the decay dynamics strongly depends on the annealing temperature, as well as, on the employed HTL. For both HTLs, the required period decreases as higher annealing temperature is used, while, for the more hydrophobic PTAA polymer, longer annealing periods were required in order to obtain the optimum charge carrier dynamics. The correlation of the TAS finding with the structural and morphological features of the perovskite films is analysed and provides useful insights on the charge extraction dynamics and recombination processes in perovskite optoelectronic devices.
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Journal of Applied Physics 126, 083109 (2019)
Absorption in ultrathin GaN-based membranes: The role of standing wave effects
A methodology is described to extract the absorption coefficient spectrum and exciton oscillator strength of GaN layers and GaN/AlGaN quantum wells by analyzing microtransmittance experiments in high-quality, free-standing membranes with thicknesses in the 160–230 nm range. The absorbance of a subwavelength GaN membrane is found to be an oscillating function of its thickness, in keeping with the standing wave effect. We analyze our results using two alternative models including interference effects and extract identical absorption coefficient values. The room-temperature absorption coefficient of bulk GaN membranes at the main exciton peak is found to be 9 × 104 cm−1. In the case of GaN/AlGaN quantum wells, the enhancement and blue shift of the excitonic absorption are observed, as a result of quantum confinement.
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Anal. Chem. 2019, 91, 18, 11834–11839
3D Imaging of Nanoparticles in an Inorganic Matrix Using TOF-SIMS Validated with STEM and EDX
Imaging nano-objects in complex systems such as nanocomposites using time-of-flight secondary ion mass spectrometry (TOF-SIMS) is a challenging task. Due to a very small amount of the material and a matrix effect, the number of generated secondary ions can be insufficient to represent a 3D elemental distribution despite being detected in a mass spectrum. Therefore, a model sample consisting of a ZrCuAg matrix with embedded Al nanoparticles is designed. A high mass difference between the light Al and heavy matrix components limits mass interference. The chemical structure measurements using a pulsed 60 keV Bi32+ beam or a continuous 30 keV Ga+ beam reveals distinct Al signal segregation. This can indicate a spatially resolved detection of single 10s of nanometer large particles and/or their agglomerates for the first time. However, TOF-SIMS images of 50 nm or smaller objects do not necessarily represent their exact size and shape but can rather be their convolutions with the primary ion beam shape. Therefore, the size of nanoparticles (25–64 nm) was measured using scanning transmission electron microscopy. Our studies prove the capability of TOF-SIMS to image chemical structure of nanohybrids which is expected to help building new functional materials and optimize their properties.
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Scientific Reports, volume 9, 10598 (2019)
Stretchable Low Impedance Electrodes for Bioelectronic Recording from Small Peripheral Nerves
Monitoring of bioelectric signals in peripheral sympathetic nerves of small animal models is crucial to gain understanding of how the autonomic nervous system controls specific body functions related to disease states. Advances in minimally-invasive electrodes for such recordings in chronic conditions rely on electrode materials that show low-impedance ionic/electronic interfaces and elastic mechanical properties compliant with the soft and fragile nerve strands. Here we report a highly stretchable low-impedance electrode realized by microcracked gold films as metallic conductors covered with stretchable conducting polymer composite to facilitate ion-to-electron exchange. The conducting polymer composite based on poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) obtains its adhesive, low-impedance properties by controlling thickness, plasticizer content and deposition conditions. Atomic Force Microscopy measurements under strain show that the optimized conducting polymer coating is compliant with the micro-crack mechanics of the underlying Au-layer, necessary to absorb the tensile deformation when the electrodes are stretched. We demonstrate functionality of the stretchable electrodes by performing high quality recordings of renal sympathetic nerve activity under chronic conditions in rats.
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J. Phys. Chem. C 2019, 123, 32, 19742–19747
Influence of Local Defects on the Dynamics of O–H Bond Breaking and Formation on a Magnetite Surface
The transport of H adatoms across oxide supports plays an important role in many catalytic reactions. We investigate the dynamics of H/Fe3O4(001) between 295 and 382 K. By scanning tunneling microscopy at frame rates of up to 19.6 fps, we observe the thermally activated switching of H between two O atoms on neighboring Fe rows. This switching rate changes in proximity to a defect, explained by density functional theory as a distortion in the Fe–O lattice shortening the diffusion path. Quantitative analysis yields an apparent activation barrier of 0.94 ± 0.07 eV on a pristine surface. The present work highlights the importance of local techniques in the study of atomic-scale dynamics at defective surfaces such as oxide supports.
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Optical Materials, 95, 109248 (2019)
Structure and spectroscopy characterization of La1-xSmxVO4 luminescent nanoparticles synthesized co-precipitation and sol-gel methods
The Sm-activated orthvanadate nanoparticles with La1-xSmxVO4 (x ≤ 0.3) composition were synthesized by co-precipitation and sol-gel methods. XRD study has shown that synthesized samples are characterized by monoclinic or tetragonal structure as well as their mixture dependently on Sm concentration and methods of synthesis. Influence of method of synthesis on morphology of nanoparticles, their absorption, diffuse reflectance and emission spectra was observed and studied. Luminescence properties and diffuse reflectance spectra of the sol-gel nanoparticles are also depend on Sm concentrations. At least two types of Sm3+ centers were found by emission spectra. These centers have different excitation efficiency by light from the 350–450 nm spectral range. Structures of the centers are discussed taking into account crystal structure, possible defects, morphology of the synthesized nanoparticles and their phase compositions.
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Applied Surface Science, 493, 948-955 (2019)
Tuning the period of femtosecond laser induced surface structures in steel: From angled incidence to quill writing
Exposure of metal surfaces to multiple ultrashort laser pulses under certain conditions leads to the formation of well-defined periodic surface structures. We show how the period of such structures in steel can be tuned over a wide range by controlling the complex interaction mechanisms triggered in the material. Amongst the different irradiation parameters that influence the properties of the induced structures, the angle of incidence of the laser beam occupies a prominent role. We present an experimental and theoretical investigation of this angle dependence in steel upon irradiation with laser pulses of 120 fs duration and 800 nm wavelength, while moving the sample at constant speed. Our findings can be grouped into two blocks. First, we observe the spatial coexistence of two different ripple periods at the steel surface, both featuring inverse scaling upon angle increase, which are related to forward and backward propagation of surface plasmon polaritons. To understand the underlying physical phenomena, we extend a recently developed model that takes into account quantitative properties of the surface roughness to the case of absorbing metals (large imaginary part of the dielectric function), and obtain an excellent match with the experimentally observed angle dependence. As second important finding, we observe a quill writing effect, also termed non-reciprocal writing, in form of a significant change of the ripple period upon reversing the sample movement direction. This remarkable phenomenon has been observed so far only inside dielectric materials and our work underlines its importance also in laser surface processing. We attribute the origin of symmetry breaking to the non-symmetric micro- and nanoscale roughness induced upon static multiple pulse irradiation, leading to non-symmetric modification of the wavevector of the coupled surface plasmon polariton.
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J. Synchrotron Rad. (2019). 26, 1115-1126
Wavefront sensing at X-ray free-electron lasers
Here a direct comparison is made between various X-ray wavefront sensing methods with application to optics alignment and focus characterization at X-ray free-electron lasers (XFELs). Focus optimization at XFEL beamlines presents unique challenges due to high peak powers as well as beam pointing instability, meaning that techniques capable of single-shot measurement and that probe the wavefront at an out-of-focus location are desirable. The techniques chosen for the comparison include single-phase-grating Talbot interferometry (shearing interferometry), dual-grating Talbot interferometry (moiré deflectometry) and speckle tracking. All three methods were implemented during a single beam time at the Linac Coherent Light Source, at the X-ray Pump Probe beamline, in order to make a direct comparison. Each method was used to characterize the wavefront resulting from a stack of beryllium compound refractive lenses followed by a corrective phase plate. In addition, difference wavefront measurements with and without the phase plate agreed with its design to within λ/20, which enabled a direct quantitative comparison between methods. Finally, a path toward automated alignment at XFEL beamlines using a wavefront sensor to close the loop is presented.
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Journal of Synchrotron Radiation 26(4) 1266-1271 (2019)
A zone-plate-based two-color spectrometer for indirect X-ray absorption spectroscopy
X-ray absorption spectroscopy (XAS) is a powerful element-specific technique that allows the study of structural and chemical properties of matter. Often an indirect method is used to access the X-ray absorption (XA). This work demonstrates a new XAS implementation that is based on off-axis transmission Fresnel zone plates to obtain the XA spectrum of La0.6Sr0.4MnO3 by analysis of three emission lines simultaneously at the detector, namely the O 2p-1s, Mn 3s-2p and Mn 3d-2p transitions. This scheme allows the simultaneous measurement of an integrated total fluorescence yield and the partial fluorescence yields (PFY) of the Mn 3s-2p and Mn 3d-2p transitions when scanning the Mn L-edge. In addition to this, the reduction in O fluorescence provides another measure for absorption often referred to as the inverse partial fluorescence yield (IPFY). Among these different methods to measure XA, the Mn 3s PFY and IPFY deviate the least from the true XA spectra due to the negligible influence of selection rules on the decay channel. Other advantages of this new scheme are the potential to strongly increase the efficiency and throughput compared with similar measurements using conventional gratings and to increase the signal-to-noise of the XA spectra as compared with a photodiode. The ability to record undistorted bulk XA spectra at high flux is crucial for future in situ spectroscopy experiments on complex materials.
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Adv. Mater. 2019, 31, 1901123
Biomimetic Omnidirectional Antireflective Glass via Direct Ultrafast Laser Nanostructuring
Here, a single-step, biomimetic approach for the realization of omnidirectional transparent antireflective glass is reported. In particular, it is shown that circularly polarized ultrashort laser pulses produce self-organized nanopillar structures on fused silica (SiO2). The laser-induced nanostructures are selectively textured on the glass surface in order to mimic the spatial randomness, pillar-like morphology, as well as the remarkable antireflection properties found on the wings of the glasswing butterfly, Greta oto, and various Cicada species. The artificial structures exhibit impressive antireflective properties, both in the visible and infrared frequency ranges, which are remarkably stable over time. Accordingly, the laser-processed glass surfaces show reflectivity smaller than 1% for various angles of incidence in the visible spectrum for s–p linearly polarized configurations. However, in the near-infrared spectrum, the laser-textured glass shows higher transmittance compared to the pristine. It is envisaged that the current results will revolutionize the technology of antireflective transparent surfaces and impact numerous applications from glass displays to optoelectronic devices.
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Energy Environ. Sci., 2019,12, 2537-2547
Ferroelectricity-free lead halide perovskites
Direct piezoelectric force microscopy (DPFM) is employed to examine whether or not lead halide perovskites exhibit ferroelectricity. Compared to conventional piezoelectric force microscopy, DPFM is a novel technique capable of measuring piezoelectricity directly. This fact is fundamental to be able to examine the existence of ferroelectricity in lead halide perovskites, an issue that has been under debate for several years. DPFM is used to detect the current signals, i.e. changes in the charge distribution under the influence of the scan direction and applied force of the atomic force microscope (AFM) tip in contact mode. For comparison, (i) we use DPFM on lead halide perovskites and well-known ferroelectric materials (i.e. periodically poled lithium niobate and lead zirconate titanate); and (ii) we conduct parallel experiments on MAPbI3 films of different grain sizes, film thicknesses, substrates, and textures using DPFM as well as piezoelectric force microscopy (PFM) and electrostatic force microscopy (EFM). In contrast to previous work that claimed there were ferroelectric domains in MAPbI3 perovskite films, our work shows that the studied perovskite films Cs0.05(FA0.83MA0.17)0.95Pb(I0.83Br0.17)3 and MAPbI3 are ferroelectricity-free. The observed current profiles of lead halide perovskites possibly originate from ion migration that happens under an applied electrical bias and in strained samples under mechanical stress. This work provides a deeper understanding of the fundamental physical properties of the organic–inorganic lead halide perovskites and solves a longstanding dispute about their non-ferroelectric character: an issue of high relevance for optoelectronic and photovoltaic applications.
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Nanosystems: Physics, Chemistry, Mathematics, 10 (3), 361–373 (2019)
Structure and photoluminescent properties of TiO2:Eu3+ nanoparticles synthesized under hydro and solvothermal conditions from different precursors
Crystalline phosphors of Eu3+-doped titania (TiO2:Eu3+) were prepared by hydro and solvothermal synthesis with luminescent ion concentration of 2 mol.%. The structure and shape of the synthesized nanoparticles were characterized using X-ray powder diffraction, transmission electron microscopy, and Raman spectroscopy. Changes in the emission, excitation spectra, and the intensity decay of the photoluminescence for TiO2:Eu3+ nanoparticles were analyzed their phase composition. The photoluminescence of synthesized TiO2:Eu3+ crystalline phosphors depends on whether the said nanophosphors are formed from organometallic or inorganic precursors under hydro- and solvothermal conditions. Indeed, photoluminescence excitation at wavelengths ranging from 350–550 nm leads to splitting of electron dipole transitions into Stark components according to the symmetry of the Eu3+ surroundings. Also, both nanoparticles with the anatase structure and phosphors predominantly containing rutile showed very short photoluminescence lifetimes.
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J. Phys.: Conf. Ser. 1190 012010 (2019)
Bandgap, electrical and structural properties of thick InN (0001) films grown under optimal conditions
The improvement potential for the structural, electrical and opto-electronic properties of heteroepitaxial InN-on-GaN (0001) films by using optimal conditions (substrate temperature, In and N fluxes) of plasma-assisted molecular beam epitaxy and increasing the epilayer thickness to few micrometres has been investigated. The increase of InN thickness to 3.7 mu m resulted to a-type component threading dislocation density of 6x10(9) cm(-2) and directly measured electron mobility of 2330 cm(2)/Vs and concentration of 4.5x10(17) cm(-3). The optical bandgap of this film at 300K was 0.637 eV. However, a degradation in the integrity of the interfacial InN/GaN region was observed in films thicker than 1. m, with the formation of voids and the nucleation of microcracks, which may be related to strain relaxation or thermal decomposition.
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J. Phys.: Condens. Matter 31 325902
Many-body perturbation theory calculations using the yambo code
yambo is an open source project aimed at studying excited state properties of condensed matter systems from first principles using many-body methods. As input, yambo requires ground state electronic structure data as computed by density functional theory codes such as Quantum ESPRESSO and Abinit. yambo's capabilities include the calculation of linear response quantities (both independent-particle and including electron–hole interactions), quasi-particle corrections based on the GW formalism, optical absorption, and other spectroscopic quantities. Here we describe recent developments ranging from the inclusion of important but oft-neglected physical effects such as electron–phonon interactions to the implementation of a real-time propagation scheme for simulating linear and non-linear optical properties. Improvements to numerical algorithms and the user interface are outlined. Particular emphasis is given to the new and efficient parallel structure that makes it possible to exploit modern high performance computing architectures. Finally, we demonstrate the possibility to automate workflows by interfacing with the yambopy and AiiDA software tools.
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Ultramicroscopy Volume 205, October 2019, Pages 49-56
The new FAST module: A portable and transparent add-on module for time-resolved investigations with commercial scanning probe microscopes
Time resolution is one of the most severe limitations of scanning probe microscopies (SPMs), since the typical image acquisition times are in the order of several seconds or even few minutes. As a consequence, the characterization of dynamical processes occurring at surfaces (e.g. surface diffusion, film growth, self-assembly and chemical reactions) cannot be thoroughly addressed by conventional SPMs. To overcome this limitation, several years ago we developed a first prototype of the FAST module, an add-on instrument capable of driving a commercial scanning tunneling microscope (STM) at and beyond video rate frequencies. Here we report on a fully redesigned version of the FAST module, featuring improved performance and user experience, which can be used both with STMs and atomic force microscopes (AFMs), and offers additional capabilities such as an atom tracking mode. All the new features of the FAST module, including portability between different commercial instruments, are described in detail and practically demonstrated.
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Phys. Rev. Lett. 122, 193602
Quantum Optical Signatures in a Strong Laser Pulse after Interaction with Semiconductors
Electrodynamical processes induced in complex systems like semiconductors by strong electromagnetic fields have traditionally been described using semiclassical approaches. Although these approaches allowed the investigation of ultrafast dynamics in solids culminating in multipetahertz electronics, they do not provide any access to the quantum-optical nature of the interaction, as they treat the driving field classically and unaffected by the interaction. Here, using a full quantum-optical approach, we demonstrate that the subcycle electronic response in a strongly driven semiconductor crystal is imprinted in the quantum state of the driving field resulting in nonclassical light states carrying the information of the interaction. This vital step towards strong-field ultrafast quantum electrodynamics unravels information inaccessible by conventional approaches and leads to the development of a new class of nonclassical light sources.
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Phys. Rev. B 99, 195201
Modelling of the ultrafast dynamics and surface plasmon properties of silicon upon irradiation with mid-IR femtosecond laser pulses
We present a theoretical investigation of the ultrafast processes and dynamics of the produced excited carriers upon irradiation of silicon with femtosecond pulsed lasers in the mid-infrared (mid-IR) spectral region. The evolution of the carrier density and thermal response of the electron-hole and lattice subsystems are analyzed for various wavelengths lambda(L) in the range between 2.2 and 3.3 mu m, where the influence of two- and three-photon absorption mechanisms is explored. The role of induced Kerr effect is highlighted and it manifests a more pronounced influence at smaller wavelengths in the mid-IR range. Elaboration on the conditions that lead to surface plasmon (SP) excitation indicate the formation of weakly bound SP waves on the material surface. The lifetime of the excited SP is shown to rise upon increasing wavelength, yielding a larger one than that predicted for higher laser frequencies. The calculation of damage thresholds for various pulse durations tau(p), shows that they rise according to a power law (similar to tau(zeta(lambda L))(p)) where the increasing rate is determined by the exponent zeta(lambda(L)). Investigation of the multiphoton absorption rates and impact ionization contribution at different tau(p) manifests a lower damage for lambda(L) = 2.5 mu m compared to that for lambda(L) = 2.2 mu m for long tau(p).
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Nano Lett. 2019, 19, 6, 3396–3408
The Role of Polarity in Nonplanar Semiconductor Nanostructures
The lack of mirror symmetry in binary semiconductor compounds turns them into polar materials, where two opposite orientations of the same crystallographic direction are possible. Interestingly, their physical properties (e.g., electronic or photonic) and morphological features (e.g., shape, growth direction, and so forth) also strongly depend on the polarity. It has been observed that nanoscale materials tend to grow with a specific polarity, which can eventually be reversed for very specific growth conditions. In addition, polar-directed growth affects the defect density and topology and might induce eventually the formation of undesirable polarity inversion domains in the nanostructure, which in turn will affect the photonic and electronic final device performance. Here, we present a review on the polarity-driven growth mechanism at the nanoscale, combining our latest investigation with an overview of the available literature highlighting suitable future possibilities of polarity engineering of semiconductor nanostructures. The present study has been extended over a wide range of semiconductor compounds, covering the most commonly synthesized III–V (GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb) and II–VI (ZnO, ZnTe, CdS, CdSe, CdTe) nanowires and other free-standing nanostructures (tripods, tetrapods, belts, and membranes). This systematic study allowed us to explore the parameters that may induce polarity-dependent and polarity-driven growth mechanisms, as well as the polarity-related consequences on the physical properties of the nanostructures.
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Optics Letters, 44, 9, 2157-2160 (2019)
Normalized single-shot X-ray absorption spectroscopy at a free-electron laser
A setup for dispersive X-ray absorption spectroscopy (XAS), employing a new reference scheme, has been implemented and tested at the soft X-ray free-electron laser (FEL) FLASH in Hamburg. A transmission grating was used to split the FEL beam into two copies (signal and reference). The spectral content of both beams was simultaneously measured for intensity normalization within the FEL bandwidth on a shot-to-shot basis. Excellent correlation between the two beams was demonstrated within a few percent for single bunch operation at 143 eV photon energy. Applying the normalization scheme, an absorption spectrum of a Gd2O3thin film sample was recorded around the Gd N4,5-edge photon energy of 143 eV, showing excellent agreement with a reference spectrum measured at a synchrotron. This scheme opens the door for time-resolved single-shot XAS with femtosecond time resolution at FELs.
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Phys. Rev. B 99, 144305 (2019)
Single-shot time-resolved magnetic x-ray absorption at a free-electron laser
Ultrafast dynamics are generally investigated using stroboscopic pump-probe measurements, which characterize the sample properties for a single, specific time delay. These measurements are then repeated for a series of discrete time delays to reconstruct the overall time trace of the process. As a consequence, this approach is limited to the investigation of fully reversible phenomena. We recently introduced an off-axis zone plate based x-ray streaking technique, which overcomes this limitation by sampling the relaxation dynamics with a single femtosecond x-ray pulse streaked over a picosecond long time window. In this article we show that the x-ray absorption cross section can be employed as the contrast mechanism in this novel technique. We show that changes of the absorption cross section on the percent level can be resolved with this method. To this end we measure the ultrafast magnetization dynamics in CoDy alloy films. Investigating different chemical compositions and infrared pump fluences, we demonstrate the routine applicability of this technique. Probing in transmission the average magnetization dynamics of the entire film, our experimental findings indicate that the demagnetization time is independent of the specific infrared laser pump fluence. These results pave the way for the investigation of irreversible phenomena in a wide variety of scientific areas.
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S Roth et al 2019 2D Mater, 6 031001
Photocarrier-induced band-gap renormalization and ultrafast charge dynamics in black phosphorus
With its tunable band-gap and its unique optical and electronic properties black phosphorus (BP) opens exciting opportunities for optoelectronic nanotechnology. The band-gap extends from the visible to the mid-infrared spectral range, as a function of sample thickness and external parameters such as electric field and pressure. This, combined with the saturable absorption and in-plane anisotropic optical properties, makes BP a versatile platform for realizing polarization-sensitive photodetectors and absorbers. Although its near-equilibrium properties have been intensively studied, the development of efficient ultrafast optical devices requires detailed knowledge of the temporal dynamics of the photoexcited hot-carriers. Here we address the electronic response of BP to an ultrafast laser excitation, by means of time-and angle-resolved photoelectron spectroscopy. Following the optical excitation, we directly observe a shift of the valence band (VB) position, indicative of band-gap renormalization (BGR). Our data also show that the hole population in the VB relaxes with a characteristic time ps, while the lifetime of the electrons accumulated at the minimum of the conduction band is ps. The experimental results are well reproduced by ab initio calculations of the out-of-equilibrium electronic properties. Our study sets the reference for the ultrafast carrier dynamics in BP and demonstrates the material's ultrafast BGR, which is promising for optoelectronic switches.
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Photonics 2019, 6(2), 38
Evidence of Intersubband Linewidth Narrowing Using Growth Interruption Technique
We report on the systematic study of two main scattering mechanisms on intersubband transitions, namely ionized impurity scattering and interface roughness scattering. The former mechanism has been investigated as a function of the dopants position within a multiple GaAs/AlGaAs quantum well structure and compared to the transition of an undoped sample. The study on the latter scattering mechanism has been conducted using the growth interruption technique. We report an improvement of the intersubband (ISB) transition linewidth up to 11% by interrupting growth at GaAs-on-AlGaAs interfaces. As a result, the lifetime of intersubband polaritons could be improved up to 9%. This leads to a reduction of 17% of the theoretical threshold intensity for polaritonic coherent emission. This work brings a useful contribution towards the realization of polariton-based devices.
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Optics Express Vol. 27, Issue 7, pp. 9733-9739 (2019)
Imaging the source of high-harmonics generated in atomic gas media
We report the application of the time gated ion microscopy technique in accessing online the position of the source of harmonics generated in atomic gas media. This is achieved by mapping the spatial extreme-ultraviolet (XUV)-intensity distribution of the harmonic source onto a spatial ion distribution, produced in a separate focal volume of the generated XUV beam through single photon ionization of atoms. It is found that the position of the harmonic source depends on the relative position of the harmonic generation gas medium and the focus of the driving infrared (IR) beam. In particular, by translating the gas medium with respect to the IR beam focus different “virtual” source positions are obtained online. Access to such online source positioning allows better control and provides increased possibilities in experiments where selection of electron trajectory is important. The present study gives also access to quantitative information which is connected to the divergence, the coherence properties and the photon flux of the harmonics. Finally, it constitutes a precise direct method for providing complementary experimental info to different attosecond metrology techniques.
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Proceedings Volume 10960, Advances in Patterning Materials and Processes XXXVI; 109600B (2019)
Advanced EUV negative tone resist and underlayer approaches exhibiting sub-20nm half-pitch resolution
The RLS trade-off of EUV resists has been a major technical issue for high-volume manufacturing using EUVL. Significant attempts to develop of chemically-amplified resists, metal-containing resists, and a variety of other material classes have been made to obtain low LER at high resolution (R) and at a reasonable sensitivity (S). Previously, we have developed and reported work on silanol-containing polyhydrogensilsesquioxane resins and their use as negative tone resists. The developed silanol-containing polymer resists have demonstrated enhanced EUV sensitivity compared to traditional hydrogen silsesquioxane resins, and at the same time maintaining excellent etch properties. The resist may enable a bilayer stack technology in EUVL. Herein we report novel functionalized polyhydrogensilsesquioxane polymers and their use as negative tone resists. These materials exhibit improved LER/LWR and reasonably good EUV sensitivity. In best cases, data suggests no residues or bridging in the non-exposed areas. The optimized resist exhibits sub-20nm halfpitch resolution, low LER (2-3nm), and reasonable sensitivity (82.5 mJ/cm2). In addition, we also investigated the effect of three organic underlayers for EUV patterning and compared with the silicon substrate.
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Phys. Rev. Materials 3, 034004
Evidence of direct electronic band gap in two-dimensional van der Waals indium selenide crystals
Metal monochalcogenide compounds offer a large variety of electronic properties depending on chemical composition, number of layers, and stacking order. Among them, the InSe has attracted much attention due to the promise of outstanding electronic properties, attractive quantum physics, and high photoresponse. Precise experimental determination of the electronic structure of InSe is sorely needed for better understanding of potential properties and device applications. Here, combining scanning tunneling spectroscopy (STS) and two-photon photoemission spectroscopy, we demonstrate that InSe exhibits a direct band gap of about 1.25 eV located at the Gamma point of the Brillouin zone. STS measurements underline the presence of a finite and almost constant density of states (DOS) near the conduction-band minimum. This particular DOS is generated by a poorly dispersive nature of the top valence band, as shown by angle-resolved photoemission spectroscopy (ARPES) investigation. In fact, a hole effective mass of about m* / m(0) = -0.95 ((Gamma K) over bar direction) was measured. Moreover, using ARPES measurements a spin-orbit splitting of the deeper-lying bands of about 0.35 eV was evidenced. These findings allow a deeper understanding of the InSe electronic properties underlying the potential of III-VI semiconductors for electronic and photonic technologies.
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Proceedings Volume 10960, Advances in Patterning Materials and Processes XXXVI; 109600C (2019)
Multi-trigger resist: novel synthesis improvements for high resolution EUV lithography
Irresistible Materials (IM) is developing novel resist systems based on the Multi-trigger concept, which incorporates a dose dependent quenching-like behaviour. The Multi Trigger Resist is a non-metal based negative tone resist, and consists of a base molecule and a crosslinker, which represent the resist matrix, together with a photoacid generator (PAG). Previously presented MTR2 showed 16 nm half pitch lines patterned with a dose of 38 mJ/cm2, giving a LER of 3.7 nm on the NXE3300. Since then, research has been undertaken to improve this resist. In particular we are focusing on improved RLS; reduced top-loss and wiggling at high aspect ratios; eliminating the antimony PAG and further reduction of chemical stochastics. In this study, we present the approaches that have been taken to attain these goals and the initial results. Using the EUV Interference Lithography tool at PSI, a multi trigger resist with a high absorbance non-metal element included in the resist matrix, MTR2627, has been patterned at a pitch of 28nm with an estimated dose of 53mJ/cm2 and LER of 4.2nm. The LWR is improved in the low dose region, and results also show that a thicker film can be used without pattern collapse below pitch 32nm due to increased stiffness. Using the Berkeley MET tool, this resist matrix with a higher MTR ratio has patterned 24nm lines at a pitch of 48nm with an LER of 1.9nm with a dose of 65mJ/cm2. Additionally, we present initial results for an MTR resist series where the antimony PAG has been replaced with a carbon based PAG.
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Computer Physics Communications, Volume 240, July 2019, 106-119
SIMPLE code: Optical properties with optimal basis functions
We present SIMPLE, a code developed to calculate optical properties of metallic and insulating extended systems using the optimal basis method originally proposed by E.L. Shirley in 1996. Two different approaches for the evaluation of the complex dielectric function are implemented: (i) the independent-particle approximation considering both interband and intraband contributions for metals and (ii) the Bethe–Salpeter equation for insulators. Since, notably, the optimal basis set is systematically improvable, accurate results can be obtained at a strongly reduced computational cost. Moreover, the simplicity of the method allows for a straightforward use of the code; improvement of the optimal basis and thus the overall precision of the simulations is simply controlled by one (for metals) or two (for insulators) input thresholds. The code is extensively tested, in terms of verification and performance, on bulk silver for metals and on bulk silicon for insulators.
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Phys. Rev. Materials 3, 033801 (2019)
Energetics and cathode voltages of LiMPO4 olivines (M = Fe, Mn) from extended Hubbard functionals
Transition-metal compounds pose serious challenges to first-principles calculations based on density-functional theory (DFT), due to the inability of most approximate exchange-correlation functionals to capture the localization of valence electrons on their d states, essential for a predictive modeling of their properties. In this work we focus on two representatives of a well known family of cathode materials for Li-ion batteries, namely the orthorhombic LiMPO4 olivines (M = Fe, Mn). We show that extended Hubbard functionals with on-site (U) and intersite (V) interactions (so called DFT+U+V) can predict the electronic structure of the mixed-valence phases, the formation energy of the materials with intermediate Li contents, and the overall average voltage of the battery with remarkable accuracy. We find, in particular, that the inclusion of intersite interactions in the corrective Hamiltonian improves considerably the prediction of thermodynamic quantities when electronic localization occurs in the presence of significant interatomic hybridization (as is the case for the Mn compound), and that the self-consistent evaluation of the effective interaction parameters as material- and ground-state-dependent quantities allows the prediction of energy differences between different phases and concentrations.
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J. of Micro/Nanolithography, MEMS, and MOEMS, 18(1), 013504 (2019).
Mechanistic insights in Zr- and Hf-based molecular hybrid EUV photoresists
Inorganic resists show promising performances in extreme ultraviolet (EUV) lithography. Yet, there is a need for understanding the exact chemical mechanisms induced by EUV light on these materials. Aim: To gain knowledge on the EUV chemistry of inorganic resists, we investigate hybrid inorganic–organic molecular compounds, metal oxoclusters (MOCs). Their molecular nature allows for the monitoring of specific structural changes by means of spectroscopy and thus for the elucidation of the mechanisms behind pattern formation.
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Nature Catalysis volume 2, pages334–341 (2019)
Structure of the catalytically active copper–ceria interfacial perimeter
Cu/CeO2 catalysts are highly active for the low-temperature water–gas shift—a core reaction in syngas chemistry for tuning the H2/CO/CO2 proportions in feed streams—but the direct identification and quantitative description of the active sites remain challenging. Here we report that the active copper clusters consist of a bottom layer of mainly Cu+ atoms bonded on the oxygen vacancies (Ov) of ceria, in a form of Cu+–Ov–Ce3+, and a top layer of Cu0 atoms coordinated with the underlying Cu+ atoms. This atomic structure model is based on directly observing copper clusters dispersed on ceria by a combination of scanning transmission electron microscopy and electron energy loss spectroscopy, in situ probing of the interfacial copper–ceria bonding environment by infrared spectroscopy and rationalization by density functional theory calculations. These results, together with reaction kinetics, reveal that the reaction occurs at the copper–ceria interfacial perimeter via a site cooperation mechanism: the Cu+ site chemically adsorbs CO whereas the neighbouring Ov–Ce3+ site dissociatively activates H2O.
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Phys. Status Solidi B, 256: 1800573
The Dissection Algorithm for the Second‐Born Self‐Energy
Here, an algorithm to efficiently compute the second-Born self-energy of many-body perturbation theory is described. The core idea consists in dissecting the set of all four-index Coulomb integrals into properly chosen subsets, thus avoiding to loop over those indices for which the Coulomb integrals are zero or negligible. The scaling properties of the algorithm with the number of basis functions is discussed. The computational gain is demonstrated in the case of one-particle Kohn–Sham basis for organic molecules.
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Phys. Rev. Materials 3, 023001(R) (2019)
Segregation scheme of indium in AlGaInAs nanowire shells
Quaternary alloys enable the independent optimization of different semiconductor properties, such as the separate tuning of the band gap and the lattice constant. Nanowire core-shell structures should allow a larger range of compositional tuning as strain can be accommodated in a more effective manner than in thin films. Still, the faceted structure of the nanowire may lead to local segregation effects. Here, we explore the incorporation of indium in AlGaAs shells up to 25%. In particular, we show the effect of In incorporation on the energy shift of the AlGaInAs single-photon emitters present in the shell. We observe a redshift up to 300 meV as a function of the group-III site fraction of In. We correlate the shift with segregation at the nanoscale. We find evidence of the segregation of the group-III elements at different positions in the nanowire, not observed before. We propose a model that takes into account the strain distribution in the nanowire shell and the adatom diffusion on the nanowire facets to explain the observations. This work provides novel insights on the segregation phenomena necessary to engineer the composition of multidinary alloys.
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Solid State Ionics 330, 17 (2019)
Nano-scale oxide formation inside electrochemically-formed Pt blisters at a solid electrolyte interface
We report on platinum oxide formation during electrochemical anodic polarization of a platinum film on yttria-stabilized zirconia (YSZ) under electrochemical oxygen potential control. The electrochemical potential drives oxygen through the YSZ electrolyte towards a nominally 175 nm thin Pt film, which we found to locally delaminate from the substrate by forming nano-scale blisters. High resolution scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDX) mapping of focused-ion beam (FIB)-prepared cross-sections of single bubbles of a few micrometers in diameter reveal them to be hollow and enclosed by a Pt outer and a few tens of nanometers thick PtOx inner shell. The oxide shell presumably formed due to the increase of local oxygen chemical activity under the applied process conditions (723 K, 500 mbar O2, bias voltage +100 mV). Interface X-ray diffraction indicates that the solid electrolyte surface morphology is largely unaffected by the process suggesting that the YSZ surface is stable on the atomic scale under application relevant oxygen transport conditions. Platinum is known to be rather stable towards oxidation, even at elevated oxygen pressure, leading to oxide-scale thicknesses of the order of 1 nm. Our results however indicate that many of the kinetic barriers for oxidation during the nano-confined blistering process are lowered. This may have implications in general for the mechanism how oxygen is stored in an electrode at such an internal metal - oxide/metal - gas interface, which is important for the functionality of many solid-state electrochemical and memresistive devices.
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Water 2019, 11(1), 181
Uptake of Sb(V) by Nano Fe3O4-Decorated Iron Oxy-Hydroxides
The presence of antimony in water remains a major problem for drinking water technology, defined by the difficulty of available adsorbents to comply with the very low regulation limit of 5 μg/L for the dominant Sb(V) form. This study attempts to develop a new class of water adsorbents based on the combination of amorphous iron oxy-hydroxide with Fe3O4 nanoparticles and optimized to the sufficient uptake of Sb(V). Such a Fe3O4/FeOOH nanocomposite is synthesized by a two-step aqueous precipitation route from iron salts under different oxidizing and acidity conditions. A series of materials with various contents of Fe3O4 nanoparticles in the range 0–100 wt % were prepared and tested for their composition, and structural and morphological features. In order to evaluate the performance of prepared adsorbents, the corresponding adsorption isotherms, in the low concentration range for both Sb(III) and Sb(V), were obtained using natural-like water. The presence of a reducing agent such as Fe3O4 results in the improvement of Sb(V) uptake capacity, which is found around 0.5 mg/g at a residual concentration of 5 μg/L. The intermediate reduction of Sb(V) to Sb(III) followed by Sb(III) adsorption onto FeOOH is the possible mechanism that explains experimental findings.
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Journal of Alloys and Compounds, 783, 2019, 237-245
Magnetoelectric dual-particulate composites with wasp-waisted magnetic response for broadband energy harvesting
Dual-particulate composites of cobalt ferrite dispersed in a fully dense PZT matrix are produced by quite-fast sintering of mechanically activated powders. By high-energy milling of the powders a bi-modal grain size distribution, with octahedral nano-grains and larger grains grown by multiple parallel twinning, are achieved in the final microstructure. The material display a “wasp-waisted” magnetic response as a consequence of the two main CoFe2O4 grain populations and can be exploited for broadband energy harvesting or field sensors. After poling under 5 kV/mm, a maximum d33 of 30 pC/N was achieved. This value is an order of magnitude lower than that of bulk PZT. Nevertheless, a magnetoelectric coefficient of 1.74 mV cm−1 Oe−1 is obtained, which suggests the high potentiality of these materials, since this value is higher than that shown by magnetoelectric composites with similar composition and connectivity reported in literature. This is so for a partially poled material and thus, magnetoelectric coefficients should be significantly increased by improving the poling process.
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Scientific Reports 8, 18054 (2018)
GeVn complexes for silicon-based room-temperature single-atom nanoelectronics
We propose germanium-vacancy complexes (GeVn) as a viable ingredient to exploit single-atom quantum effects in silicon devices at room temperature. Our predictions, motivated by the high controllability of the location of the defect via accurate single-atom implantation techniques, are based on ab-initio Density Functional Theory calculations within a parameterfree screened-dependent hybrid functional scheme, suitable to provide reliable bandstructure energies and defect-state wavefunctions. The resulting defect-related excited states, at variance with those arising from conventional dopants such as phosphorous, turn out to be deep enough to ensure device operation up to room temperature and exhibit a far more localized wavefunction.
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Phys. Rev. B 98, 224103 (2018)
Ultrafast dynamics and subwavelength periodic structure formation following irradiation of GaAs with femtosecond laser pulses
A theoretical investigation of the ultrafast processes and dynamics of the excited carriers upon irradiation of GaAs with femtosecond pulsed lasers is performed in conditions that induce material damage and eventually surface modification of the heated solid. A parametric study is followed to correlate the produced transient carrier density with the damage threshold for various pulse duration values τp (it increases as ∼τp0.053±0.011 at relatively small values of τp while it drops for pulse durations of the order of some picoseconds) based on the investigation of the fundamental multiscale physical processes following femtosecond laser irradiation. Moreover, fluence values for which the originally semiconducting material demonstrates a metallic behaviour are estimated. It is shown that a sufficient number of carriers in the conduction band are produced to excite surface-plasmon waves that upon coupling with the incident beam and a fluid-based surface modification mechanism lead to the formation of subwavelength periodic structures orientated perpendicularly to the laser beam polarization. Experimental results for the damage threshold and the frequencies of induced periodic structures show a good agreement with the theoretical predictions.
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Phys. Rev. B 98, 224103
Ultrafast dynamics and subwavelength periodic structure formation following irradiation of GaAs with femtosecond laser pulses
A theoretical investigation of the ultrafast processes and dynamics of the excited carriers upon irradiation of GaAs with femtosecond pulsed lasers is performed in conditions that induce material damage and eventually surface modification of the heated solid. A parametric study is followed to correlate the produced transient carrier density with the damage threshold for various pulse duration values tau(p) (it increases as similar to tau(0.053 +/- 0.011)(p) at relatively small values of tau(p) while it drops for pulse durations of the order of some picoseconds) based on the investigation of the fundamental multiscale physical processes following femtosecond laser irradiation. Moreover, fluence values for which the originally semiconducting material demonstrates a metallic behaviour are estimated. It is shown that a sufficient number of carriers in the conduction band are produced to excite surface-plasmon waves that upon coupling with the incident beam and a fluid-based surface modification mechanism lead to the formation of subwavelength periodic structures orientated perpendicularly to the laser beam polarization. Experimental results for the damage threshold and the frequencies of induced periodic structures show a good agreement with the theoretical predictions.
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ACS Omega 2018, 3, 12, 16728–16734
Unveiling the Structure of MoSx Nanocrystals Produced upon Laser Fragmentation of MoS2 Platelets
Transition-metal dichalcogenide MoS2 nanostructures have attracted tremendous attention due to their unique properties, which render them efficient nanoscale functional components for multiple applications ranging from sensors and biomedical probes to energy conversion and storage devices. However, despite the wide application range, the possibility to tune their size, shape, and composition is still a challenge. At the same time, the correlation of the structure with the optoelectronic properties is still unresolved. Here, we propose a new method to synthesize various morphologies of molybdenum sulfide nanocrystals, on the basis of ultrashort-pulsed laser fragmentation of MoS2 platelets. Depending on the irradiation conditions, multiple MoSx morphologies in the form of nanoribbons, nanospheres, and photoluminescent quantum dots are obtained. Besides the detailed structural analysis of the various crystals formed, the structure-property relation is investigated and discussed.
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Mol. Syst. Des. Eng.,4, 175 (2019)
Self-assembly morphology of block copolymers in sub-10 nm topographical guiding patterns
In this paper, we investigate the directed self-assembly of block copolymers in topographical guiding patterns with feature sizes in the range of the block copolymer half-pitch. In particular, we present the self-assembly of an 11.7 nm half-pitch block copolymer in sub-10 nm resolution guiding patterns fabricated by the direct e-beam exposure of hydrogen silsesquioxane (HSQ). One result of this analysis is that the block copolymer self-assembles such that the guiding pattern features form part of the 3-D architecture of the film. We are capable of determining a shift in the block copolymer pitch as a function of the guiding pattern pitch with sub-nanometer accuracy by means of both real-space (AFM, SEM) and reciprocal-space techniques (GISAXS). An interesting result is that the block copolymer self-assembly in the studied structures depends on the guiding pattern pitch rather than on the trench width as in standard graphoepitaxy. We analyze the structures by means of a free energy model and present both theoretical and experimental evidence of a narrower processing window for such kind of guiding patterns than for regular directed self-assembly using wide topographical guiding patterns, and discuss the origin of this effect. We argue that chain deformation in the vicinity of the top cap of the guiding pattern feature is responsible for an increase of the free energy of the ordered state, which leads to a smaller energy difference between the defect-free and defective self-assembly than that for the observed self-assembly morphology.
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Applied Surface Science, 471, 31, 2019, 753-758
Growth, morphology and stability of Au in contact with the Bi2Se3(0 0 0 1) surface
We report a combined microscopy and spectroscopy study of Au deposited on the Bi2Se3(0001) single crystal surface. At room temperature Au forms islands, according to the Volmer–Weber growth mode. Upon annealing to 100 °C the Au deposits are not stable and assemble into larger and thicker islands. The topological surface state of Bi2Se3 is weakly affected by the presence of Au. Contrary to other metals, such as Ag or Cr, a strong chemical instability at the Au/Bi2Se3 interface is ruled out. Core level analysis highlights Bi diffusion toward the surface of Au islands, in agreement with previous findings, while chemical interaction between Au and atomic Se is limited at the interfacial region. For the investigated range of Au coverages, the Au/Bi2Se3 heterostructure is inert towards CO and CO2 exposure at low pressure (10−8 mbar) regime.
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ACS Photonics, 5, 12, 4817 (2018)
Single crystal diamond membranes and Photonic Resonators containing germanium vacancy color centers
Single crystal diamond membranes that host optically active emitters are highly attractive components for integrated quantum nanophotonics. In this work we demonstrate bottom-up synthesis of single crystal diamond membranes containing germanium vacancy (GeV) color centers. We employ a lift-off technique to generate the membranes and perform chemical vapor deposition in the presence of a germanium source to realize the in situ doping. Finally, we show that these membranes are suitable for engineering of photonic resonators such as microdisk cavities with quality factors of ∼1500. The robust and scalable approach to engineer single crystal diamond membranes containing emerging color centers is a promising pathway for the realization of diamond integrated quantum nanophotonic circuits on a chip.
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J. Phys. Condens. Matter 30 465901 (2018)
CHEERS: a tool for correlated hole-electron evolution from real-time simulations
We put forward a practical nonequilibrium Green's function (NEGF) scheme to perform real-time evolutions of many-body interacting systems driven out of equilibrium by external fields. CHEERS is a computational tool to solve the NEGF equation of motion in the so called generalized Kadanoff–Baym ansatz and it can be used for model systems as well as first-principles Hamiltonians. Dynamical correlation (or memory) effects are added to the Hartree–Fock dynamics through a many-body self-energy. Applications to time-dependent quantum transport, time-resolved photoabsorption and other ultrafast phenomena are discussed.
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Microscopie; 15:7803 (2018)
A combined in operando approach for low-energy Scanning Transmission Electron Microscopy and Grazing Incident Small Angle X-ray Scattering
Probing the evolution of electronic, structural, and chemical properties of nanostructured materials under reaction conditions is a crucial issue to determine their structure-functionality relationships. A relevant example is represented by heterogeneous catalysts, whose properties change dramatically with respect to the environment. Much of effort has been made lately in designing new solutions and technologies, or modifying the existing ones for purpose of operando conditions analysis. The use of micro- or nanoreactors, is a second approach, where ultrathin membranes can efficiently separate the high-pressure volume from the (ultra)high vacuum of the characterization chamber. Very recently, microreactor cells have been developed to integrate the capabilities of ensemble-averaging synchrotron techniques with local probe ones, as TEM to analyze the same catalytic process with different instruments. Despite the great power of this method, the extremely small probing size of TEMs restricts the application of a combined approach to a limited set of micro-focused synchrotron techniques. We propose here the development of a novel multifunctional microreactor for operando low voltage Scanning TEM in a SEM compatible with a broad range of synchrotron techniques. We successfully designed a device compatible with Grazing Incident Small Angle X-ray Scattering (GISAXS), demonstrating the feasibility of our approach by studying the shape and size evolution of PVP-capped Pd nanocrystals under oxidation/reaction conditions.
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2D Mater. 6 015003 (2019)
Spatially selective reversible charge carrier density tuning in WS2 monolayers via photochlorination
Chlorine-doped tungsten disulfide monolayer (1L-WS2) with tunable charge carrier concentration has been realized by pulsed laser irradiation of the atomically thin lattice in a precursor gas atmosphere. This process gives rise to a systematic shift of the neutral exciton peak towards lower energies, indicating reduction of the crystal's electron density. The capability to progressively tune the carrier density upon variation of the exposure time is demonstrated; this indicates that the Fermi level shift is directly correlated to the respective electron density modulation due to the chlorine species. Notably, this electron withdrawing process enabled the determination of the trion binding energy of the intrinsic crystal, found to be as low as 20 meV, in accordance to theoretical predictions. At the same time, it is found that the effect can be reversed upon continuous wave laser scanning of the monolayer in air. Scanning auger microscopy (SAM) and x-ray photoelectron spectroscopy (XPS) are used to link the actual charge carrier doping to the different chlorine configurations in the monolayer lattice. The spectroscopic analyses, complemented by density functional theory calculations, reveal that chlorine physisorption is responsible for the carrier density modulation induced by the pulsed laser photochemical reaction process. Such bidirectional control of the Fermi level, coupled with the capability offered by lasers to process at pre-selected locations, can be advantageously used for spatially resolved doping modulation in 1L-WS2 with micrometric resolution. This method can also be extended for the controllable doping of other TMD monolayers.
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Science and Technology of Advanced Materials, 19:1, 702-710 (2018)
Epitaxial La0.7Sr0.3MnO3 thin films on silicon with excellent magnetic and electric properties by combining physical and chemical methods
Half-metallic ferromagnetic La0.7Sr0.3MnO3 (LSMO) represents an appealing candidate to be integrated on silicon substrates for technological devices such as sensors, data storage media, IR detectors, and so on. Here, we report high-quality epitaxial LSMO thin films obtained by an original combination of chemical solution deposition (CSD) and molecular beam epitaxy (MBE). A detailed study of the thermal, chemical, and physical compatibility between SrTiO3 (STO)/Si buffer layers and LSMO films, grown by MBE and CSD, respectively, enables a perfect integration of both materials. Importantly, we show a precise control of the coercive field of LSMO films by tuning the mosaicity of the STO/Si buffer layer. These results demonstrate the enormous potential of combining physical and chemical processes for the development of low-cost functional oxide-based devices compatible with the complementary metal oxide semiconductor technology.
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V. 10809, International Conf. on Extreme Ultraviolet Lithography (2018)
New resist and underlayer approaches toward EUV lithography
Extreme ultraviolet lithography (EUVL, λ = 13.5 nm) is the most promising candidate to pattern the finest features in the next-generation integrated circuit manufacturing. Chemically-amplified resists (CARs) have long been used as state-of-the art photoresists and have been considered as EUV resist. Recently, inorganic and metal-containing resist materials have received significant attention in both academia and industry areas, with the aim to improve the resist performance in terms of resist resolution (R), line-edge roughness (LER), and sensitivity (S) to solve the well-known RLS trade-off. However, the resists reported to date usually have either problem in terms of RLS trade-off or pose metal contamination, which is a serious issue in expensive EUV equipment. Differently, in this report, we demonstrate our recent success in the development of the photochemistry of silicon compounds and resist formulations to obtain novel EUV negative tone resists with high resolution (up to 22nm pitch line/space patterns), low line-edge roughness (1-3nm) with reasonable EUV sensitivity. We also discuss their high etch selectivity to a PiBond’s SOC organic underlayer, which enable a bilayer lithography stack for EUVL patterning. Their excellent etch performances by RIE plasma is also reported.
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Phys. Rev. Materials 2, 106001 (2018)
Faceting of local droplet-etched nanoholes in AlGaAs
Nanoholes, drilled in the (001) surface of AlGaAs by local Al droplet etching, are shown to consist of faceted inner walls. The most prominent facets of the inverted pyramidlike nano-sized etch pits are the {111}A and {1¯11}B surfaces, which differ in their atomic surface terminations. In the [110] direction, the {111} facets change to {112} and/or {113}, which are both stepped surfaces with (111)A terraces. Etching-temperature-dependent data indicate that this facet transition seems kinetically hindered up to etch temperatures above 660 °C, at which point the walls along [1¯10] have already evolved completely towards {1¯11}B facets. The redeposited ring material outside the nanohole develops facets with indices of (115) and higher, thereby forming relatively flat structures. The facets and their indices are unraveled by a combination of atomic force microscopy, scanning electron microscopy, and x-ray diffraction, which is performed on an ensemble as well as on a single hole using nanodiffraction. These results imply that this nanoconfined etching process can be largely understood in a vapor-liquid-solid scheme, which includes the bulk thermodynamics in the Al-Ga-As system, the surface energies of low index facets, and their etch rates and surface terminations.
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Eur. Phys. J. B 91, 216 (2018)
Benchmarking nonequilibrium Green’s functions against configuration interaction for time-dependent Auger decay processes
We have recently proposed a Nonequilibrium Green's Function (NEGF) approach to include Auger decay processes in the ultrafast charge dynamics of photoionized molecules. Within the so called Generalized Kadanoff-Baym Ansatz the fundamental unknowns of the NEGF equations are the reduced one-particle density matrix of bound electrons and the occupations of the continuum states. Both unknowns are one-time functions like the density in Time-Dependent Functional Theory (TDDFT). In this work we assess the accuracy of the approach against Configuration Interaction (CI) calculations in one-dimensional model systems. Our results show that NEGF correctly captures qualitative and quantitative features of the relaxation dynamics provided that the energy of the Auger electron is much larger than the Coulomb repulsion between two holes in the valence shells. For the accuracy of the results dynamical electron-electron correlations or, equivalently, memory effects play a pivotal role. The combination of our NEGF approach with the Sham-Schlüter equation may provide useful insights for the development of TDDFT exchange-correlation potentials with a history dependence.
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Journal of Vacuum Science & Technology B 36, 06J501 (2018)
Improving the resolution and throughput of achromatic Talbot lithography
High-resolution patterning of periodic structures over large areas has several applications in science and technology. One such method, based on the long-known Talbot effect observed with diffraction gratings, is achromatic Talbot lithography (ATL). This method offers many advantages over other techniques, such as high resolution, large depth-of-focus, and high throughput. Although the technique has been studied in the past, its limits have not yet been explored. Increasing the efficiency and the resolution of the method is essential and might enable many applications in science and technology. In this work, the authors combine this technique with spatially coherent and quasimonochromatic light at extreme ultraviolet (EUV) wavelengths and explore new mask design schemes in order to enhance its throughput and resolution. They report on simulations of various mask designs in order to explore their efficiency. Advanced and optimized nanofabrication techniques have to be utilized to achieve high quality and efficient masks for ATL. Exposures using coherent EUV radiation from the Swiss light source have been performed, pushing the resolution limits of the technique for dense hole or dot patterning down to 40 nm pitch. In addition, through extensive simulations, alternative mask designs with rings instead of holes are explored for the efficient patterning of hole/dot arrays. They show that these rings exhibit similar aerial images to hole arrays, while enabling higher efficiency and thereby increased throughput for ATL exposures. The mask designs with rings show that they are less prone to problems associated with pattern collapse during the nanofabrication process and therefore are promising for achieving higher resolution.
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Phys. Rev. B 98, 115148 (2018)
The generalized Kadanoff-Baym ansatz with initial correlations
Within the nonequilibrium Green's function (NEGF) formalism, the generalized Kadanoff-Baym ansatz (GKBA) has stood out as a computationally cheap method to investigate the dynamics of interacting quantum systems driven out of equilibrium. Current implementations of the NEGF-GKBA, however, suffer from a drawback: real-time simulations require noncorrelated states as initial states. Consequently, initial correlations must be built up through an adiabatic switching of the interaction before turning on any external field, a procedure that can be numerically highly expensive. In this work, we extend the NEGF-GKBA to allow for correlated states as initial states. Our scheme makes it possible to efficiently separate the calculation of the initial state from the real-time simulation, thus paving the way for enlarging the class of systems and external drivings accessible by the already successful NEGF-GKBA. We demonstrate the accuracy of the method and its improved performance in a model donor-acceptor dyad driven out of equilibrium by an external laser pulse.
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V. 10775, 34th European Mask and Lithography Conference; 1077502 (2018)
Multi-trigger resist for electron beam and extreme ultraviolet lithography
The multi-trigger resist (MTR) is a new negative tone molecular resist platform for electron beam lithography, as well as extreme ultraviolet and optical lithography. The performance of xMT resist, the precursor to MTR resist, which shows a good combination of sensitivity, low line edge roughness and high-resolution patterning has previously been reported.[1] In order to overcome limitations induced by acid diffusion, a new mechanism - the multi-trigger concept - has been introduced. The results obtained so far as the behaviour of the resist is driven towards the multi-trigger regime by manipulating the resist formulation are presented. A feature size of 13 nm in semi-dense (1:1.5 line/space) patterns, and 22nm diameter pillar patterns are demonstrated in electron beam, and 16 nm half-pitch resolution patterns are demonstrated in (extreme ultraviolet) EUV. An improvement in the LER value is seen in the higher MTR formulations. © (2018) COPYRIGHT Society of Photo-Optical Instrumentation Engineers (SPIE). Downloading of the abstract is permitted for personal use only.
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Materials Today 21, 7, 798-799 (2018)
Diamond: a gem for micro-optics
Photonics have developed greatly over the last several decades and brought about a variety of new concepts in communications, sensing, solar energy and many other fields. With the emerging applications of quantum technologies and all-optical data processing, the impact of photonics on technology is undeniable, as evidenced through the international Year of Light and Light-based Technologies in 2015.
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Nanoscale, 43 (2018)
Direct and converse piezoelectric responses at the nanoscale from epitaxial BiFeO3 thin films grown by polymer assisted deposition
We use an original water-based chemical method to grow pure epitaxial BiFeO3 (BFO) ultra-thin films with excellent piezoelectric properties. Particularly, we show that this novel chemical route produces higher natural ferroelectric domain size distribution and coercive field compared to similar BFO films grown by physical methods. Moreover, we measured the d33 piezoelectric coefficient of 60 nm thick BFO films by a direct approach, using Direct Piezoelectric Force Microscopy (DPFM). As a result, first piezo-generated charge maps of a very thin BFO layer were obtained applying this novel technology. We also performed a comparative study of the d33 coefficients between standard PFM analysis and DPFM microscopy showing similar values i.e. 17 pm V−1 and 22 pC N−1, respectively. Finally, we proved that the directionality of the piezoelectric effect in BFO ferroelectric thin films is preserved at low thickness dimensions demonstrating the potential of chemical processes for the development of low cost functional ferroelectric and piezoelectric devices.
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Adv. Energy. Mater. 8. 1802120 (2018)
Optical Analysis of Oxygen Self‐Diffusion in Ultrathin CeO2 Layers at Low Temperatures
An optical in situ strategy for the analysis of oxygen diffusion in ultrathin ceria layers with a thickness of 2–10 nm at temperatures between 50 and 200 °C is presented, which allows for the determination of diffusion coefficients. This method is based on the sensitivity of the photoluminescence (PL) intensity of InGaN nanowires to adsorbed oxygen. The oxygen diffusion through an ultrathin CeO2 coating deposited on the InGaN nanowires is monitored by analyzing the transient PL behavior of the InGaN nanowires, which responds to changes of the oxygen concentration in the environment when the corresponding oxygen concentration is established at the CeO2/InGaN interface due to diffusion through the coating. Quantitative evaluation of the oxygen diffusion in CeO2 based on a model considering Langmuir Adsorption and recombination yields a diffusion coefficient D of (2.55 ± 0.05) × 10−16 cm2 s−1 at a temperature of 100 °C. Temperature‐dependent measurements reveal an Arrhenius type behavior of D with an activation energy of (0.28 ± 0.04) eV. In contrast, no oxygen diffusion is detected for an ultrathin layer (≥5 nm) of Al2O3, which is known as a poor oxygen ion conductor within the analyzed temperature regime.
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ACS Appl. Energy Mater. 2018, 1, 9, 5101–5111
Improved Charge Carrier Dynamics of CH3NH3PbI3 Perovskite Films Synthesized by Means of Laser-Assisted Crystallization
Although it has been recently demonstrated that the laser-assisted (LA) crystallization process leads to the formation of perovskite absorber films of superior photovoltaic performance compared to conventional thermal annealing (TA), the physical origin behind this important discovery is missing. In this study, CH3NH3PbI3 perovskite thin films have been synthesized by means of LA and TA crystallization on the surface of two hole transport layers (HTL) namely poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) and poly(triarylamine) (PTAA). A systematic study of the effect of laser irradiation conditions on the crystalline quality and morphology of the perovskite films was performed via scanning electron microscopy, X-Ray diffraction and absorption spectroscopy. Meanwhile, time-resolved transient absorption spectroscopy under inert atmosphere conditions was used to evaluate the carrier transport dynamics. It is found that for the PEDOT:PSS/CH3NH3PbI3, structures the LA process resulted to perovskite layers of larger grains, faster charge carrier extraction properties and slower bimolecular recombination, when compared to TA. On the contrary, the LA-assisted formation of the PTAA/CH3NH3PbI3 heterostructures leads to extensive presence of residual PbI2 and thus inferior performance and charge carrier dynamics.
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Scientific Data vol. 5, 180172 (2018)
The first annotated set of scanning electron microscopy images for nanoscience
In this paper, we present the first publicly available human-annotated dataset of images obtained by the Scanning Electron Microscopy (SEM). A total of roughly 26,000 SEM images at the nanoscale are classified into 10 categories to form 4 labeled training sets, suited for image recognition tasks. The selected categories span the range of 0D objects such as particles, 1D nanowires and fibres, 2D films and coated surfaces as well as patterned surfaces, and 3D structures such as microelectromechanical system (MEMS) devices and pillars. Additional categories such as tips and biological are also included to expand the spectrum of possible images. A preliminary degree of hierarchy is introduced, by creating a subtree structure for the categories and populating them with the available images, wherever possible.
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Nanoscale,10, 17080 (2018)
Optimizing the yield of A-polar GaAs nanowires to achieve defect-free zinc blende structure and enhanced optical functionality
Compound semiconductors exhibit an intrinsic polarity, as a consequence of the ionicity of their bonds. Nanowires grow mostly along the (111) direction for energetic reasons. Arsenide and phosphide nanowires grow along (111)B, implying a group V termination of the (111) bilayers. Polarity engineering provides an additional pathway to modulate the structural and optical properties of semiconductor nanowires. In this work, we demonstrate for the first time the growth of Ga-assisted GaAs nanowires with (111)A-polarity, with a yield of up to ∼50%. This goal is achieved by employing highly Ga-rich conditions which enable proper engineering of the energies of A and B-polar surfaces. We also show that A-polarity growth suppresses the stacking disorder along the growth axis. This results in improved optical properties, including the formation of AlGaAs quantum dots with two orders or magnitude higher brightness. Overall, this work provides new grounds for the engineering of nanowire growth directions, crystal quality and optical functionality.
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Phys. Rev. A 98, 023426 (2018)
Multiple ionization of argon via multi-XUV-photon absorption induced by 20-GW high-order harmonic laser pulses
We report the observation of multiple ionization of argon through multi-XUV-photon absorption induced by an unprecedentedly powerful laser driven high-order harmonic generation source. Comparing the measured intensity dependence of the yield of the different argon charge states with numerical calculations we can infer the different channels—direct and sequential—underlying the interaction. While such studies were feasible so far only with free electron laser (FEL) sources, this paper connects highly nonlinear XUV processes with the ultrashort time scales inherent to the harmonic pulses and highlights the advanced perspectives of emerging large scale laser research infrastructures.
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Microelectronic Engineering 195, 7 (2018)
Laser ablation and injection moulding as techniques for producing micro channels compatible with Small Angle X-Ray Scattering
Microfluidic mixing is an important means for in-situ sample preparation and handling while Small Angle X-Ray Scattering (SAXS) is a proven tool for characterising (macro-)molecular structures. In combination those two techniques enable investigations of fast reactions with high time resolution (<1 ms). The goal of combining a micro mixer with SAXS, however, puts constraints on the materials and production methods used in the device fabrication. The measurement channel of the mixer needs good X-ray transparency and a low scattering background. While both depend on the material used, the requirement for low scattering especially limits the techniques suitable for producing the mixer, as the fabrication process can induce molecular orientations and stresses that can adversely influence the scattering signal.
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Appl. Phys. Lett. 113, 052403 (2018)
Room temperature biaxial magnetic anisotropy in La0.67Sr0.33MnO3 thin films on SrTiO3 buffered MgO (001) substrates for spintronic applications
Spintronics exploits the magnetoresistance effects to store or sense the magnetic information. Since the magnetoresistance strictly depends on the magnetic anisotropy of a system, it is fundamental to set a defined anisotropy to the system. Here, we investigate half-metallic La0.67Sr0.33MnO3 thin films by means of vectorial Magneto-Optical Kerr Magnetometry and found that they exhibit pure biaxial magnetic anisotropy at room temperature if grown onto a MgO (001) substrate with a thin SrTiO3 buffer. In this way, we can avoid unwanted uniaxial magnetic anisotropy contributions that may be detrimental for specific applications. The detailed study of the angular evolution of the magnetization reversal pathways and critical fields (coercivity and switching) discloses the origin of the magnetic anisotropy, which is magnetocrystalline in nature and shows fourfold symmetry at any temperature.
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Phys. Rev. B 98, 075105 (2018)
Functional approach to the electronic and bosonic dynamics of many-body systems perturbed with an arbitrary strong electron-boson interaction
We present a formal derivation of the many-body perturbation theory for a system of electrons and bosons subject to a nonlinear electron-boson coupling. The interaction is treated at an arbitrary high order of bosons scattered. The considered Hamiltonian includes the well-known linear coupling as a special limit. This is the case, for example, of the Holstein and Fröhlich Hamiltonians. Indeed, whereas linear coupling has been extensively studied, the scattering processes of electrons with multiple bosonic quasiparticles are largely unexplored. We focus here on a self-consistent theory in terms of dressed propagators and generalize the Hedin's equations using the Schwinger technique of functional derivatives. The method leads to an exact derivation of the electronic and bosonic self-energies, expressed in terms of a new family of vertex functions, high-order correlators, and bosonic and electronic mean-field potentials. In the electronic case we prove that the mean-field potential is the nth-order extension of the well-known Debye-Waller potential.
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Eur. Phys. J. B 91: 171. (2018)
An ab-initio approach to describe coherent and non-coherent exciton dynamics
The use of ultra-short laser pulses to pump and probe materials activates a wealth of processes which involve the coherent and non coherent dynamics of interacting electrons out of equilibrium. Non equilibrium (NEQ) many body perturbation theory (MBPT) offers an equation of motion for the density–matrix of the system which well describes both coherent and non coherent processes. In the non correlated case there is a clear relation between these two regimes and the matrix elements of the density–matrix. The same is not true for the correlated case, where the potential binding of electrons and holes in excitonic states need to be considered. In the present work we discuss how NEQ-MBPT can be used to describe the dynamics of both coherent and non-coherent excitons in the low density regime. The approach presented is well suited for an ab initio implementation.
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Phys. Rev. B 98, 041405(R) (2018)
Molecular junctions and molecular motors: Including Coulomb repulsion in electronic friction using nonequilibrium Green's functions
We present a theory of molecular motors based on the Ehrenfest dynamics for nuclear coordinates and the adiabatic limit of the Kadanoff-Baym equations for current-induced forces. Electron-electron interactions can be systematically included through many-body perturbation theory, making the nonequilibrium Green's function formulation suitable for first-principles treatments of realistic junctions. The method is benchmarked against simulations via real-time Kadanoff-Baym equations, finding an excellent agreement. Results on a paradigmatic model of a molecular motor show that correlations can change dramatically the physical scenario by, e.g., introducing a sizable damping in self-sustained van der Pol oscillations.
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Int. J. Mol. Sci., 19(7), 2053 (2018)
Engineering Cell Adhesion and Orientation via Ultrafast Laser Fabricated Microstructured Substrates
Cell responses depend on the stimuli received by the surrounding extracellular environment, which provides the cues required for adhesion, orientation, proliferation, and differentiation at the micro and the nano scales. In this study, discontinuous microcones on silicon (Si) and continuous microgrooves on polyethylene terephthalate (PET) substrates were fabricated via ultrashort pulsed laser irradiation at various fluences, resulting in microstructures with different magnitudes of roughness and varying geometrical characteristics. The topographical models attained were specifically developed to imitate the guidance and alignment of Schwann cells for the oriented axonal regrowth that occurs in nerve regeneration. At the same time, positive replicas of the silicon microstructures were successfully reproduced via soft lithography on the biodegradable polymer poly(lactide-co-glycolide) (PLGA). The anisotropic continuous (PET) and discontinuous (PLGA replicas) microstructured polymeric substrates were assessed in terms of their influence on Schwann cell responses. It is shown that the micropatterned substrates enable control over cellular adhesion, proliferation, and orientation, and are thus useful to engineer cell alignment in vitro. This property is potentially useful in the fields of neural tissue engineering and for dynamic microenvironment systems that simulate in vivo conditions.
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ACS Appl. Mater. Interfaces, 10 (30), pp 25779 (2018)
Surface-Bound Gradient Deposition of Protein Nanoparticles for Cell Surface-Bound Gradient Deposition of Protein Nanoparticles for Cell
A versatile evaporation-assisted methodology based on the coffee-drop effect is described to deposit nanoparticles on surfaces, obtaining for the first time patterned gradients of protein nanoparticles (pNPs) by using a simple custom-made device. Fully controllable patterns with specific periodicities consisting of stripes with different widths and distinct nanoparticle concentration as well as gradients can be produced over large areas (∼10 cm2) in a fast (up to 10 mm2/min), reproducible, and cost-effective manner using an operational protocol optimized by an evolutionary algorithm. The developed method opens the possibility to decorate surfaces “a-la-carte” with pNPs enabling different categories of high-throughput studies on cell motility.
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Soft Matter 14, 6799 (2018)
Nano-confinement of block copolymers in high accuracy topographical guiding patterns: modelling the emergence of defectivity due to incommensurability
Extreme ultraviolet interference lithography (EUV-IL) is used to manufacture topographical guiding patterns to direct the self-assembly of block copolymers. High-accuracy silicon oxide-like patterns with trenches ranging from 68 nm to 117 nm width are fabricated by exposing a hydrogen silsesquioxane (HSQ) resist layer using EUV-IL. We investigate how the accuracy, the low line width roughness and the low line edge roughness of the resulting patterns allow achieving DSA line/space patterns of a PS-b-PMMA (polystyrene-block-poly methyl methacrylate) block copolymer of 11 nm half-pitch with low defectivity. We conduct an in-depth study of the dependence of the DSA pattern morphology on the trench width and on how the neutral brush covers the guiding pattern. We identify the relation between trench width and the emergence of defects with nanometer precision. Based on these studies, we develop a model that extends available free energy models, which allows us to predict the patterning process window.
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Nanotechnology Vol. 29, No. 36 (2018)
Changes in the near edge x-ray absorption fine structure of hybrid organic–inorganic resists upon exposure
We report on the near edge x-ray absorption fine structure (NEXAFS) spectroscopy of hybrid organic–inorganic resists. These materials are nonchemically amplified systems based on Si, Zr, and Ti oxides, synthesized from organically modified precursors and transition metal alkoxides by a sol–gel route and designed for ultraviolet, extreme ultraviolet (EUV) and electron beam lithography. The experiments were conducted using a scanning transmission x-ray microscope (STXM) which combines high spatial-resolution microscopy and NEXAFS spectroscopy. The absorption spectra were collected in the proximity of the carbon edge (~290 eV) before and after in situ exposure, enabling the measurement of a significant photo-induced degradation of the organic group (phenyl or methyl methacrylate, respectively), the degree of which depends on the configuration of the ligand. Photo-induced degradation was more efficient in the resist synthesized with pendant phenyl substituents than it was in the case of systems based on bridging phenyl groups. The degradation of the methyl methacrylate group was relatively efficient, with about half of the initial ligands dissociated upon exposure. Our data reveal that such dissociation can produce different outcomes, depending on the structural configuration. While all the organic groups were expected to detach and desorb from the resist in their entirety, a sizeable amount of them remained and formed undesired byproducts such as alkene chains. In the framework of the materials synthesis and engineering through specific building blocks, these results provide a deeper insight into the photochemistry of resists, in particular for EUV lithography.
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Adv. Mater. 2018, 30, 1802078
A Shape-Induced Orientation Phase within 3D Nanocrystal Solids
When nanocrystals self assemble into ordered superstructures they form functional solids that may inherit the electronical properties of the single nanocrystals. To what extent these properties are enhanced depends on the positional and orientational order of the nanocrystals within the superstructure. Here, the formation of micrometer-sized free-standing supercrystals of faceted 20 nm Bi nanocrystals is investigated. The self-assembly process, induced by nonsolvent into solvent diffusion, is probed in situ by synchrotron X-ray scattering. The diffusion-gradient is identified as the critical parameter for controlling the supercrystal-structure as well as the alignment of the supercrystals with respect to the substrate. Monte Carlo simulations confirm the positional order of the nanocrystals within these superstructures and reveal a unique orientation phase: the nanocrystal shape, determined by the atomic Bi crystal structure, induces a total of 6 global orientations based on facet-to-facet alignment. This parallel alignment of facets is a prerequisite for optimized electronic and optical properties within designed nanocrystal solids.
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J. Photopolym. Sci. Technol., Vol. 31, No. 2 (2018)
Dual-tone Application of a Tin-Oxo Cage Photoresist Under E-beam and EUV Exposure
We report on the dual-tone property of the tin-oxo cage (BuSn)12O14(OH)6](OH)2 photoresist. After exposing the resist film to a low dose extreme ultraviolet radiation or electron beam, applying a post exposure bake step and development with isopropanol/H2O (2:1), a positive tone image is observed. The previously observed negative tone is found at higher doses. Atomic force microscopy and scanning electron microscopy were used to characterize the topography of the patterns. X-ray photoelectron spectroscopy was used to elucidate the chemical changes of the tin-oxo cages under different conditions. The photoresist, which has dual-tone property, paves the way to fabricate sophisticated structures in a single photoresist layer or may lead to metal-containing resists with improved sensitivity.
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J. Synchrotron Rad. 25, 1238 (2018)
SwissFEL Aramis beamline photon diagnostics
The SwissFEL Aramis beamline, covering the photon energies between 1.77 keV and 12.7 keV, features a suite of online photon diagnostics tools to help both users and FEL operators in analysing data and optimizing experimental and beamline performance. Scientists will be able to obtain information about the flux, spectrum, position, pulse length, and arrival time jitter versus the experimental laser for every photon pulse, with further information about beam shape and size available through the use of destructive screens. This manuscript is an overview of the diagnostics tools available at SwissFEL and presents their design, working principles and capabilities. It also features new developments like the first implementation of a THz-streaking based temporal diagnostics for a hard X-ray FEL, capable of measuring pulse lengths to 5 fs r.m.s. or better.
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Phys. Rev. A 97, 061401(R) (2018)
Real-time dynamics of Auger wave packets and decays in ultrafast charge migration processes
The Auger decay is a relevant recombination channel during the first few femtoseconds of molecular targets impinged by attosecond XUV or soft x-ray pulses. Including this mechanism in time-dependent simulations of charge-migration processes is a difficult task, and Auger scatterings are often ignored altogether. In this work we present an advance of the current state-of-the-art by putting forward a real-time approach based on nonequilibrium Green's functions suitable for first-principles calculations of molecules with tens of active electrons. To demonstrate the accuracy of the method we report comparisons against accurate grid simulations of one-dimensional systems. We also predict a highly asymmetric profile of the Auger wave packet, with a long tail exhibiting ripples temporally spaced by the inverse of the Auger energy.
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Microelectronic Engineering 193, p. 18–22 (2018)
Sub-10 nm Electron and Helium Ion Beam Lithography Using a Recently Developed Alumina Resist
Electron Beam Lithography (EBL) at sub-10 nm resolution is mainly limited by resist contrast and proximity effects. In this work, we investigate the use of a recently developed alumina-based resist as a negative-tone resist for EBL at 100 keV and focused helium ion beam lithography (FHIBL). The resist is synthesized using a sol-gel method and turns into a near completely inorganic alumina system when exposed to the electron/ion beam. We first investigate the effect on the resist contrast curve on i) development temperature; ii) stability of the resist after exposure and before post-baking and development; and iii) aging of the resist solution. We demonstrate the patterning of isolated features as small as 6.5 nm using an EBL and 5 nm using FHIBL and a resolution down to 10 nm for FHIB exposed films. Finally, we demonstrate the pattern transfer of 10 nm lines with an aspect ratio of 10 in silicon, using an optimized reactive ion etching process.
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Struct. Dyn. 5, 034501 (2018)
Laser induced phase transition in epitaxial FeRh layers studied by pump-probe valence band photoemission
We use time-resolved X-ray photoelectron spectroscopy to probe the electronic and magnetization dynamics in FeRh films after ultrafast laser excitations. We present experimental and theoretical results which investigate the electronic structure of FeRh during the first-order phase transition, identifying a clear signature of the magnetic phase. We find that a spin polarized feature at the Fermi edge is a fingerprint of the magnetic status of the system that is independent of the long-range ferromagnetic alignment of the magnetic domains. We use this feature to follow the phase transition induced by a laser pulse in a pump-probe experiment and find that the magnetic transition occurs in less than 50 ps and reaches its maximum in 100 ps.
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IUCrJ Vol. 5, 4, 390-401 (2018)
Dummy-atom modelling of stacked and helical nanostructures from solution scattering data
The availability of dummy-atom modelling programs to determine the shape of monodisperse globular particles from small-angle solution scattering data has led to outstanding scientific advances. However, there is no equivalent procedure that allows modelling of stacked, seemingly endless structures, such as helical systems. This work presents a bead-modelling algorithm that reconstructs the structural motif of helical and rod-like systems. The algorithm is based on a `projection scheme': by exploiting the recurrent nature of stacked systems, such as helices, the full structure is reduced to a single building-block motif. This building block is fitted by allowing random dummy-atom movements without an underlying grid. The proposed method is verified using a variety of analytical models, and examples are presented of successful shape reconstruction from experimental data sets. To make the algorithm available to the scientific community, it is implemented in a graphical computer program that encourages user interaction during the fitting process and also includes an option for shape reconstruction of globular particles.
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New J. Chem.42, 9635-9644 (2018)
Encapsulation of cationic iridium(III) tetrazole complexes into a silica matrix: synthesis, characterization and optical properties
Herein we report the easy incorporation of brightly phosphorescent cationic iridium(III) tetrazole complexes into a silica based matrix via an easily scalable colloidal process. For this purpose, two cationic Ir(III) emitters bearing 5-aryl tetrazole ligands (R-CN4) were selected: blue [F2IrPTZ-Me]+ (C^N = F2ppy; N^N = PTZ-Me – 2-(2-methyl-2H-tetrazol-5-yl)pyridine) and red [IrQTZ-Me]+ (C^N = ppy; N^N = QTZ-Me – 2-(2-methyl-2H-tetrazol-5-yl)quinoline). The cationic complexes were readily adsorbed to negatively charged silica nanoparticles and trapped in the sol–gel matrix. The sol-to-solid phase transfer was performed by using an innovative spray-freeze-drying technique, leading to the formation of phosphorescent solid micro-granules.
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Nano Lett. , 18, 6, 3839 (2018)
Theory and Ab Initio Computation of the Anisotropic Light Emission in Monolayer Transition Metal Dichalcogenides
Monolayer transition metal dichalcogenides (TMDCs) are direct gap semiconductors with a unique potential for use in ultrathin light emitters. However, their photoluminescence (PL) is not completely understood. We develop an approach to compute the radiative recombination rate in monolayer TMDCs as a function of photon emission direction and polarization. Using exciton wavefunctions and energies obtained with the ab initio Bethe−Salpeter equation, we obtain polar plots of the PL for different scenarios. Our results can explain the PL anisotropy and polarization dependence measured in recent experiments and predict that light is emitted with a peak intensity normal to the exciton dipole in monolayer TMDCs. We show that excitons emit light anisotropically upon recombination when they are in any quantum superposition state of the K and K′ inequivalent valleys. When averaged over the emission angle and exciton momentum, our new treatment recovers the temperature-dependent radiative lifetimes that we previously derived. Our work demonstrates a generally applicable first-principles approach to studying anisotropic light emission in two-dimensional materials.
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Microelectronic Engineering 191, p. 25-31 (2018)
Beyond 100 nm resolution in 3D laser lithography — Post processing solutions
Laser polymerization has emerged as a direct writing technique allowing the fabrication of complex 3D structures with microscale resolution. The technique provides rapid prototyping capabilities for a broad range of applications, but to meet the growing interest in 3D nanoscale structures the resolution limits need to be pushed beyond the 100 nm benchmark, which is challenging in practical implementations. As a possible path towards this goal, a post processing of laser polymerized structures is presented. Precise control of the cross-sectional dimensions of structural elements as well as tuning of an overall size of the entire 3D structure was achieved by combining isotropic plasma etching and pyrolysis. The smallest obtainable feature sizes are mostly limited by the mechanical properties of the polymerized resist and the geometry of the 3D structure. Thus, the demonstrated post processing steps open new avenues to explore free form 3D structures at the nanoscale.
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Microelectronic Engineering 191, p. 91–96 (2018)
Exploiting atomic layer deposition for fabricating sub-10 nm X-ray lenses
Moving towards significantly smaller nanostructures, direct structuring techniques such as electron beam lithography approach fundamental limitations in feature size and aspect ratios. Application of nanostructures like diffractive X-ray lenses requires feature sizes of below 10 nm to enter a new regime in high resolution X-ray microscopy. As such dimensions are difficult to obtain using conventional electron beam lithography, we pursue a line-doubling approach. We demonstrate that this method yields structure sizes as small as 6.4 nm. X-ray lenses fabricated in this way are tested for their efficiency and microscopic resolution. In addition, the line-doubling technique is successfully extended to a six-fold scheme, where each line in a template structure written by electron beam lithography evolves into six metal lines.
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Light: Science & Applications volume 7, page 18005 (2018)
Ultrahigh-resolution nonlinear optical imaging of the armchair orientation in 2D transition metal dichalcogenides
We used nonlinear laser scanning optical microscopy to study atomically thin transition metal dichalcogenides (TMDs) and revealed, with unprecedented resolution, the orientational distribution of armchair directions and their degree of organization in the two-dimensional (2D) crystal lattice. In particular, we carried out polarization-resolved second-harmonic generation (PSHG) imaging for monolayer WS2 and obtained, with high-precision, the orientation of the main crystallographic axis (armchair orientation) for each individual 120 × 120 nm2 pixel of the 2D crystal area. Such nanoscale resolution was realized by fitting the experimental PSHG images, obtained with sub-micron precision, to a new generalized theoretical model that accounts for the nonlinear optical properties of TMDs. This enabled us to distinguish between different crystallographic domains, locate boundaries and reveal fine structure. As a consequence, we can calculate the mean orientational average of armchair angle distributions in specific regions of interest and define the corresponding standard deviation as a figure-of-merit for the 2D crystal quality.
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Microelectronic Engineering 190, p. 73–78 (2018)
Nanoimprint Stamps with Ultra-High Resolution: Optimal Fabrication Techniques
Single-digit nanometer patterning by nanoimprint lithography is a challenging task, which requires optimum stamp fabrication technique. In the current work, we present different strategies for technology of hard master stamps to make intermediate working stamps with sub-10 nm features. Methods of both negative and positive master stamps fabrication, based on EBL, RIE and ALD are described and compared. A single-step copying of negative master stamps using a polymer material is a preferred strategy to reach the ultra high-resolution. Lines as small as 5.6 nm are demonstrated in a resist using a combined thermal and UV-imprint with OrmoStamp material as a working stamp.
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Nano Lett. 18, 4, 2666 (2018)
Template-assisted scalable nanowire networks
Topological qubits based on Majorana Fermions have the potential to revolutionize the emerging field of quantum computing by making information processing significantly more robust to decoherence. Nanowires are a promising medium for hosting these kinds of qubits, though branched nanowires are needed to perform qubit manipulations. Here we report a gold-free templated growth of III–V nanowires by molecular beam epitaxy using an approach that enables patternable and highly regular branched nanowire arrays on a far greater scale than what has been reported thus far. Our approach relies on the lattice-mismatched growth of InAs on top of defect-free GaAs nanomembranes yielding laterally oriented, low-defect InAs and InGaAs nanowires whose shapes are determined by surface and strain energy minimization. By controlling nanomembrane width and growth time, we demonstrate the formation of compositionally graded nanowires with cross-sections less than 50 nm. Scaling the nanowires below 20 nm leads to the formation of homogeneous InGaAs nanowires, which exhibit phase-coherent, quasi-1D quantum transport as shown by magnetoconductance measurements. These results are an important advance toward scalable topological quantum computing.
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Proc. SPIE 105830A (2018)
Ti, Zr, and Hf-based molecular hybrid materials as EUV photoresists
Metal oxoclusters are hybrid inorganic-organic molecular compounds with a well-defined number of metal and oxygen atoms in their cores. This type of materials is a promising platform for extreme ultraviolet (EUV) photoresists: their inorganic cores provide them with tunable EUV absorptivity and their molecular nature might favour smaller resolution and roughness while it also renders specific spectroscopic fingerprints that allow to monitor the chemical changes induced by EUV light. In this work, we compare the EUV photochemistry of metal oxoclusters based on Ti, Zr, and Hf and methacrylate ligands (Mc) and their sensitivity as resist materials for EUV lithography.
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Proc. SPIE 10583, 105831L (2018)
High-resolution EUV lithography using a multi-trigger resist
As minimum lithographic size continues to shrink, the development of techniques and resist materials capable of high resolution, high sensitivity and low line edge roughness (LER) have become increasingly important for next-generation lithography. In this study we present results where the behaviour of the resist is driven towards the multi-trigger regime by manipulating the resist formulation. We also present results obtained after enhancements of the base molecule to give high resolution, better LER, and a significant sensitivity enhancement of 40% over the standard material. Finally, we present the inclusion of non-metallic high-Z elements into the formulation to allow for a further reduction in LER at the same resolution and sensitivity as seen for the enhanced MTR molecule, indicating a direction for further improvements.
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Proc. SPIE 10583, 105831R (2018)
Ultra-sensitive EUV resists based on acid-catalyzed polymer backbone breaking
The main target of the current work was to develop new sensitive polymeric materials for lithographic applications, focusing in particular to EUV lithography, the main chain of which is cleaved under the influence of photogenerated acid. Resist materials based on the cleavage of polymer main chain are in principle capable to create very small structures, to the dimensions of the monomers that they consist of. Nevertheless, in the case of the commonly used nonchemically amplified materials of this type issues like sensitivity and poor etch resistance limit their areas of application, whereas inadequate etch resistance and non- satisfactory process reliability are the usual problems encountered in acid catalysed materials based on main chain scission. In our material design the acid catalyzed chain cleavable polymers contain very sensitive moieties in their backbone while they remain intact in alkaline ambient. These newly synthesized polymers bear in addition suitable functional groups for the achievement of desirable lithographic characteristics (thermal stability, acceptable glass transition temperature, etch resistance, proper dissolution behavior, adhesion to the substrate).
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Science 359, 1243-1246 (2018)
Real-time imaging of adatom-promoted graphene growth on nickel
Single adatoms are expected to participate in many processes occurring at solid surfaces, such as the growth of graphene on metals. We demonstrate, both experimentally and theoretically, the catalytic role played by single metal adatoms during the technologically relevant process of graphene growth on nickel (Ni). The catalytic action of individual Ni atoms at the edges of a growing graphene flake was directly captured by scanning tunneling microscopy imaging at the millisecond time scale, while force field molecular dynamics and density functional theory calculations rationalize the experimental observations. Our results unveil the mechanism governing the activity of a single-atom catalyst at work.
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Applied Physics A 124:311 (2018)
Ultrafast dynamics of non-equilibrium electrons and strain generation under femtosecond laser irradiation of Nickel
We present a theoretical study of the ultrafast electron dynamics in transition metals of large electron–phonon coupling constant using ultrashort pulsed laser beams. The significant influence of the dynamics of produced nonthermal electrons to electron thermalisation and electron–phonon interaction is thoroughly investigated for various values of the pulse duration (i.e., from 10 fs to 2.3 ps). The model correlates the role of nonthermal electrons, relaxation processes and induced stress–strain fields. Simulations are presented by choosing Nickel (Ni) as a test material to compute electron–phonon relaxation time due to its large electron–phonon coupling constant. We demonstrate that the consideration of the aforementioned factors leads to significant changes compared to the results the traditional two-temperature model provides. The proposed model predicts a substantially (~ 33%) smaller damage threshold and a large increase of the stress (~ 20%, at early times) which first underlines the role of the nonthermal electron interactions and second enhances its importance with respect to the precise determination of laser specifications in material micromachining techniques.
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Biomater. Sci.,6, 1469 (2018)
Cells on hierarchically-structured platforms hosting functionalized nanoparticles
In this work, we report on a novel approach to develop hierarchically-structured cell culture platforms incorporating functionalized gold nanoparticles (AuNPs). In particular, the hierarchical substrates comprise primary pseudo-periodic arrays of silicon microcones combined with a secondary nanoscale pattern of homogeneously deposited AuNPs terminated with bio-functional moieties. AuNPs with various functionalities (i.e. oligopeptides, small molecules and oligomers) were successfully attached onto the microstructures. Experiments with PC12 cells on hierarchical substrates incorporating AuNPs carrying the RGD peptide showed an impressive growth and NGF-induced differentiation of the PC12 cells, compared to that on the NP-free, bare, micropatterned substrates. The exploitation of the developed methodology for the binding of AuNPs as carriers of specific bio-functional moieties onto micropatterned culture substrates for cell biology studies is envisaged.
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Appl Nanosci 8: 627 (2018)
Monitoring dynamic electrochemical processes with in situ ptychography
The present work reports novel soft X-ray Fresnel CDI ptychography results, demonstrating the potential of this method for dynamic in situ studies. Specifically, in situ ptychography experiments explored the electrochemical fabrication of Co-doped Mn-oxide/polypyrrole nanocomposites for sustainable and cost-effective fuel-cell air-electrodes. Oxygen-reduction catalysts based on Mn-oxides exhibit relatively high activity, but poor durability: doping with Co has been shown to improve both reduction rate and stability. In this study, we examine the chemical state distribution of the catalytically crucial Co dopant to elucidate details of the Co dopant incorporation into the Mn/polymer matrix. The measurements were performed using a custom-made three-electrode thin-layer microcell, developed at the TwinMic beamline of Elettra Synchrotron during a series of experiments that were continued at the SXRI beamline of the Australian Synchrotron. Our time-resolved ptychography-based investigation was carried out in situ after two representative growth steps, controlled by electrochemical bias. In addition to the observation of morphological changes, we retrieved the spectroscopic information, provided by multiple ptychographic energy scans across Co L3-edge, shedding light on the doping mechanism and demonstrating a general approach for the molecular-level investigation complex multimaterial electrodeposition processes.
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JINST 13 C03007 (2018)
In-situ spectroscopic analysis of the traditional dyeing pigment Turkey red inside textile matrix
Turkey red is a traditional pigment for textile dyeing and its use has been proven for various cultures within the last three millennia. The pigment is a dye-mordant complex consisting of Al and an extract from R. tinctorum that contains mainly the anthraquinone derivative alizarin. The chemical structure of the complex has been analyzed by various spectroscopic and crystallographic techniques for extractions from textiles or directly in solution. We present an in-situ study of Turkey red by means of μ-XRF mapping and NEXAFS spectroscopy on textile fibres dyed according to a traditional process to gain insight into the coordination chemistry of the pigment in realistic matrix. We find an octahedral coordination of Al that corresponds well to the commonly accepted structure of the Al alizarin complex derived from ex-situ studies.
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Phys. Rev. B 97, 115301 (2018)
Linear negative magnetoresistance in two-dimensional Lorentz gases
Two-dimensional Lorentz gases formed by obstacles in the shape of circles, squares, and retroreflectors are reported to show a pronounced linear negative magnetoresistance at small magnetic fields. For circular obstacles at low number densities, our results agree with the predictions of a model based on classical retroreflection. In extension to the existing theoretical models, we find that the normalized magnetoresistance slope depends on the obstacle shape and increases as the number density of the obstacles is increased. The peaks are furthermore suppressed by in-plane magnetic fields as well as by elevated temperatures. These results suggest that classical retroreflection can form a significant contribution to the magnetoresistivity of two-dimensional Lorentz gases, while contributions from weak localization cannot be excluded, in particular for large obstacle densities.
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J. Phys. Chem. Lett., 9, 6, 1353 (2018)
Ultrafast Charge Migration in XUV Photoexcited Phenylalanine: A First-Principles Study Based on Real-Time Nonequilibrium Green’s Functions
The early-stage density oscillations of the electronic charge in molecules irradiated by an attosecond XUV pulse takes place on femto- or subfemtosecond time scales. This ultrafast charge migration process is a central topic in attoscience because it dictates the relaxation pathways of the molecular structure. A predictive quantum theory of ultrafast charge migration should incorporate the atomistic details of the molecule, electronic correlations, and the multitude of ionization channels activated by the broad-bandwidth XUV pulse. We propose a first-principles nonequilibrium Green’s function method fulfilling all three requirements and apply it to a recent experiment on the photoexcited phenylalanine amino acid. Our results show that dynamical correlations are necessary for a quantitative overall agreement with the experimental data. In particular, we are able to capture the transient oscillations at frequencies 0.15 and 0.30 PHz in the hole density of the amine group as well as their suppression and the concomitant development of a new oscillation at frequency 0.25 PHz after ∼14 fs.
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Journal of Applied Physics 123, 085903 (2018)
The influence of dynamical change of optical properties on the thermomechanical response and damage threshold of noble metals under femtosecond laser irradiation
We present a theoretical investigation of the dynamics of the dielectric constant of noble metals following heating with ultrashort pulsed laser beams and the influence of the temporal variation of the associated optical properties on the thermomechanical response of the material. The effect of the electron relaxation time on the optical properties based on the use of a critical point model is thoroughly explored for various pulse duration values (i.e., from 110 fs to 8 ps). The proposed theoretical framework correlates the dynamical change in optical parameters, relaxation processes and induced strains-stresses. Simulations are presented by choosing gold as a test material, and we demonstrate that the consideration of the aforementioned factors leads to significant thermal effect changes compared to results when static parameters are assumed. The proposed model predicts a substantially smaller damage threshold and a large increase of the stress which firstly underlines the significant role of the temporal variation of the optical properties and secondly enhances its importance with respect to the precise determination of laser specifications in material micromachining techniques.
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Nanoscale,10, 5591 (2018)
Optical Emission of GaN/AlN Quantum-Wires - The Role of Charge Transfer from a Nanowire Template
We show that one-dimensional (1d) GaN quantum-wires (QWRs) exhibit intense and spectrally sharp emission lines. These QWRs are realized in an entirely self-assembled growth process by molecular beam epitaxy (MBE) on the side facets of GaN/AlN nanowire (NW) heterostructures. Time-integrated and time-resolved photoluminescence (PL) data in combination with numerical calculations allow the identification and assignment of the manifold emission features to three different spatial recombination centers within the NWs. The recombination processes in the QWRs are driven by efficient charge carrier transfer effects between the different optically active regions, providing high intense QWR luminescence despite their small volume. This is deduced by a fast rise time of the QWR PL, which is similar to the fast decay-time of adjacent carrier reservoirs. Such processes, feeding the ultra-narrow QWRs with carriers from the relatively large NWs, can be the key feature towards the realization of future QWR-based devices. While processing of single quantum structures with diameters in the nm range presents a serious obstacle with respect to their integration into electronic or photonic devices, the QWRs presented here can be analyzed and processed using existing techniques developed for single NWs.
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J Raman Spectrosc. 2018; 49: 1015– 1022
Influence of substrate on molecular order for self-assembled adlayers of CoPc and FePc
Self-assembled metal phthalocyanine thin films are receiving considerable interest due to their potential technological applications. In this study, we present a comprehensive study of CoPc and FePc thin films of about 50 nm thickness on technologically relevant substrates such as SiOx/Si, indium tin oxide (ITO) and polycrystalline gold in order to investigate the substrate induced effects on molecular stacking and crystal structure. Raman spectroscopic analysis reveals lower intensity for the vibrational bands corresponding to phthalocyanine macrocycle for the CoPc and FePc thin films grown on ITO as compared to SiOx/Si due to the higher order of phthalocyanine molecules on SiOx/Si. Atomic force microscopy analysis displays higher grain size for FePc and CoPc thin films on ITO as compared to SiOx/Si and polycrystalline gold indicating towards the influence of molecule–substrate interactions on the molecular stacking. Grazing incidence X-ray diffraction reciprocal space maps reveal that FePc and CoPc molecules adopt a combination of herringbone and brickstone arrangement on SiOx/Si and polycrystalline gold substrate, which can have significant implications on the optoelectronic properties of the films due to unique molecular stacking.
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npj 2D Materials and Applications v. 2 : 2 (2018)
Large-grain MBE-grown GaSe on GaAs with a Mexican hat-like valence band dispersion
Atomically thin GaSe has been predicted to have a non-parabolic, Mexican hat-like valence band structure due to the shift of the valence band maximum (VBM) near the Γ point which is expected to give rise to novel, unique properties such as tunable magnetism, high effective mass suppressing direct tunneling in scaled transistors, and an improved thermoelectric figure of merit. However, the synthesis of atomically thin GaSe remains challenging. Here, we report on the growth of atomically thin GaSe by molecular beam epitaxy (MBE) and demonstrate the high quality of the resulting van der Waals epitaxial films. The full valence band structure of nominal bilayer GaSe is revealed by photoemission electron momentum microscopy (k-PEEM), confirming the presence of a distorted valence band near the Γ point. Our results open the way to demonstrating interesting new physical phenomena based on MBE-grown GaSe films and atomically thin monochalcogenides in general.
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Nano Lett. 18, 2, 1379-1386 (2018)
Vertical Growth of Superconducting Crystalline Hollow Nanowires by He+ Focused Ion Beam Induced Deposition
Novel physical properties appear when the size of a superconductor is reduced to the nanoscale, in the range of its superconducting coherence length (ξ0). Such nanosuperconductors are being investigated for potential applications in nanoelectronics and quantum computing. The design of three-dimensional nanosuperconductors allows one to conceive novel schemes for such applications. Here, we report for the first time the use of a He+ focused-ion-beam-microscope in combination with the W(CO)6 precursor to grow three-dimensional superconducting hollow nanowires as small as 32 nm in diameter and with an aspect ratio (length/diameter) of as much as 200.
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Applied Physics A 124:146 (2018)
Formation of periodic surface structures on dielectrics after irradiation with laser beams of spatially variant polarisation: a comparative study
A comparative study is performed to explore the periodic structure formation upon intense femtosecond-pulsed irradiation of dielectrics with radially and azimuthally polarised beams. Laser conditions have been selected appropriately to produce excited carriers with densities below the optical breakdown threshold in order to highlight the role of phase transitions in surface modification mechanisms. The frequency of the laser-induced structures is calculated based on a theoretical model that comprises estimation of electron density excitation, heat transfer, relaxation processes, and hydrodynamics-related mass transport. The influence of the laser wavelength in the periodicity of the structures is also unveiled. The decreased energy absorption for azimuthally polarised beams yields periodic structures with smaller frequencies which are more pronounced as the number of laser pulses applied to the irradiation spot increases. Similar results are obtained for laser pulses of larger photon energy and higher fluences. All induced periodic structures are oriented parallel to the laser beam polarisation.
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J. Phys.: Condens. Matter 30 044003 (2018)
Accuracy of dielectric-dependent hybrid functionals in the prediction of optoelectronic properties of metal oxide semiconductors: a comprehensive comparison
Understanding the electronic structure of metal oxide semiconductors is crucial to their numerous technological applications, such as photoelectrochemical water splitting and solar cells. The needed experimental and theoretical knowledge goes beyond that of pristine bulk crystals, and must include the effects of surfaces and interfaces, as well as those due to the presence of intrinsic defects (e.g. oxygen vacancies), or dopants for band engineering. In this review, we present an account of the recent efforts in predicting and understanding the optoelectronic properties of oxides using ab initio theoretical methods. In particular, we discuss the performance of recently developed dielectric-dependent hybrid functionals, providing a comparison against the results of many-body GW calculations, including G 0 W 0 as well as more refined approaches, such as quasiparticle self-consistent GW. We summarize results in the recent literature for the band gap, the band level alignment at surfaces, and optical transition energies in defective oxides, including wide gap oxide semiconductors and transition metal oxides. Correlated transition metal oxides are also discussed. For each method, we describe successes and drawbacks, emphasizing the challenges faced by the development of improved theoretical approaches. The theoretical section is preceded by a critical overview of the main experimental techniques needed to characterize the optoelectronic properties of semiconductors, including absorption and reflection spectroscopy, photoemission, and scanning tunneling spectroscopy (STS).
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Nano Energy Volume 45, 94-100 (2018)
Topological distribution of reversible and non-reversible degradation in perovskite solar cells
Lead halide perovskites have recently raised as an easy to process and cost-effective photovoltaic material. However, stability issues have to be addressed to meet the market need for 25 years durable technology. The stability of the perovskite itself, as well as the stability of the perovskite embedded in a complete device under real working conditions, are a key challenge for perovskite solar cells. Within this study, we used Photoconductive Atomic Force Microscopy (pcAFM) and Photoluminescence imaging (PL) to investigate at the nanoscale level the degradation of the perovskite film under light and voltage stress. Then, we correlate the nanoscale pcAFM and PL analysis to the macroscopic device behaviour in similar ageing condition. We found that non-reversible performance losses in a complete device originate from degradation localised at the grain boundaries of the perovskite film. Interesting, within the bulk of the perovskite grains we observed fully reversible behaviours. We conclude that the grain boundaries are detrimental to the device stability and they need to be minimized or passivated to achieve fully stable perovskite solar cells even under anhydrous conditions.
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Nano Lett., 18, 2, 785 (2018)
Charge Separation in Donor–C 60 Complexes with Real-Time Green Functions: The Importance of Nonlocal Correlations
We use the nonequilibrium Green function (NEGF) method to perform real-time simulations of the ultrafast electron dynamics of photoexcited donor–C60 complexes modeled by a Pariser–Parr–Pople Hamiltonian. The NEGF results are compared to mean-field Hartree–Fock (HF) calculations to disentangle the role of correlations. Initial benchmarking against numerically highly accurate time-dependent density matrix renormalization group calculations verifies the accuracy of NEGF. We then find that charge-transfer (CT) excitons partially decay into charge separated (CS) states if dynamical nonlocal correlation corrections are included. This CS process occurs in ∼10 fs after photoexcitation. In contrast, the probability of exciton recombination is almost 100% in HF simulations. These results are largely unaffected by nuclear vibrations; the latter become however essential whenever level misalignment hinders the CT process. The robust nature of our findings indicates that ultrafast CS driven by correlation-induced decoherence may occur in many organic nanoscale systems, but it will only be correctly predicted by theoretical treatments that include time-nonlocal correlations.
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Separation Science and Technology (2017)
One step preparation of ZnFe2O4/Zn5(OH)6(CO3)2 nanocomposite with improved As(V) removal capacity
Novel adsorbents consisting of ZnFe2O4/Zn5(OH)6(CO3)2 (hydrozincite) nanocomposite materials were studied for efficient As(V) removal from water. Nanocomposites were synthesized by the co-precipitation of Zn and Fe salts in alkaline conditions. Depending on the Zn/Fe molar ratio, a variety of materials was produced with different ZnFe2O4/Zn5(OH)6(CO3)2 contents. The adsorbent’s efficiency for As(V) removal was enhanced proportionally to the percentage of Zn5(OH)6(CO3)2 content. The nanocomposite with 74 ± 7 wt% of Zn5(OH)6(CO3)2 provided a capacity of 18.4 μg As(V)/mg for residual concentration of 10 μg/L (pH 7) which is over twice that of an iron oxy-hydroxide prepared under similar conditions.
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Journal of Applied Physics 122, 223106 (2017)
Partial ablation of Ti/Al nano-layer thin film by single femtosecond laser pulse
The interaction of ultra-short laser pulses with Titanium/Aluminium (Ti/Al) nano-layered thin film was investigated. The sample composed of alternating Ti and Al layers of a few nanometres thick was deposited by ion-sputtering. A single pulse irradiation experiment was conducted in an ambient air environment using focused and linearly polarized femtosecond laser pulses for the investigation of the ablation effects. The laser induced morphological changes and the composition were characterized using several microscopy techniques and energy dispersive X-ray spectroscopy. The following results were obtained: (i) at low values of pulse energy/fluence, ablation of the upper Ti layer only was observed; (ii) at higher laser fluence, a two-step ablation of Ti and Al layers takes place, followed by partial removal of the nano-layered film. The experimental observations were supported by a theoretical model accounting for the thermal response of the multiple layered structure upon irradiation with ultra-short laser pulses.
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Applied Physics A 124:27 (2018)
Modelling periodic structure formation on 100Cr6 steel after irradiation with femtosecond-pulsed laser beams
We investigate the periodic structure formation upon intense femtosecond pulsed irradiation of chrome steel (100Cr6) for linearly polarised laser beams. The underlying physical mechanism of the laser-induced periodic structures is explored, their spatial frequency is calculated and theoretical results are compared with experimental observations. The proposed theoretical model comprises estimations of electron excitation, heat transfer, relaxation processes, and hydrodynamics-related mass transport. Simulations describe the sequential formation of sub-wavelength ripples and supra-wavelength grooves. In addition, the influence of the laser wavelength on the periodicity of the structures is discussed. The proposed theoretical investigation offers a systematic methodology towards laser processing of steel surfaces with important applications.
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ACS Appl. Mater. Interfaces 9 (50), 43910 (2017)
Improved Carrier Transport in Perovskite Solar Cells Probed by Femtosecond Transient Absorption Spectroscopy
CH3NH3PbI3 perovskite thin films have been deposited on glass/indium tin oxide/hole transport layer (HTL) substrates, utilizing two different materials as the HTLs. In the first configuration, the super hydrophilic polymer poly(3,4 ethylenedioxythiophene)-poly(styrenesulfonate), known as PEDOT:PSS, was employed as the HTL material, whereas in the second case, the nonwetting poly(triarylamine) semiconductor polymer, known as PTAA, was used. It was found that when PTAA is used as the HTL material, the averaged power conversion efficiency (PCE) of the perovskite solar cells (PSCs) remarkably increases from 12.60 to 15.67%. To explore the mechanism behind this enhancement, the aforementioned perovskite/HTL arrangements were investigated by time-resolved transient absorption spectroscopy (TAS) performed under inert conditions. By means of TAS, the charge transfer, carrier trapping, and hole injection dynamics from the photoexcited perovskite layers to the HTL can be directly monitored via the characteristic bleaching profile of the perovskite at ∼750 nm. TAS studies revealed faster relaxation times and decay dynamics when the PTAA polymer is employed, which potentially account for the enhanced PCE observed. The TAS results are correlated with the structure and crystalline quality of the corresponding perovskite films, investigated by scanning electron microscopy, X-ray diffraction, atomic force microscopy, micro-photoluminescence, and transmittance spectroscopy. It is concluded that TAS is a benchmark technique for the understanding of the carrier transport mechanisms in PSCs and constitutes a figure-of-merit tool toward their efficiency improvement.
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Chem. Sci., Advance Article (2018)
Are multiple Oxygen Species Selective in Ethylene Epoxidation on Silver?
The nature of the oxygen species active in ethylene epoxidation is a long-standing question. While the structure of the oxygen species that participates in total oxidation (nucleophilic oxygen) is known the atomic structure of the selective species (electrophilic oxygen) is still debated. Here, we use both in situ and UHV X-ray Photoelectron Spectroscopy (XPS) to study the interaction of oxygen with a silver surface. We show experimental evidence that the unreconstructed adsorbed atomic oxygen (Oads) often argued to be active in epoxidation has a binding energy (BE) ≤ 528 eV, showing a core-level shift to lower BE with respect to the O-reconstructions, as previously predicted by DFT. Thus, contrary to the frequent assignment, adsorbed atomic oxygen cannot account for the electrophilic oxygen species with an O 1s BE of 530–531 eV, thought to be the active species in ethylene epoxidation. Moreover, we show that Oads is present at very low O-coverages during in situ XPS measurements and that it can be obtained at slightly higher coverages in UHV at low temperature. DFT calculations support that only low coverages of Oads are stable. The highly reactive species is titrated by background gases even at low temperature in UHV conditions. Our findings suggest that at least two different species could participate in the partial oxidation of ethylene on silver.
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Optics Express Vol. 25, 24, 30686-30695 (2017)
High Resolution Beam Profiling of X-ray Free Electron Laser Radiation by Polymer Imprint Development
High resolution metrology of beam profiles is presently a major challenge at X-ray free electron lasers. We demonstrate a characterization method based on beam imprints in poly (methyl methacrylate). By immersing the imprints formed at 47.8 eV into organic solvents, the regions exposed to the beam are removed similar to resist development in grayscale lithography. This allows for extending the sensitivity of the method by more than an order of magnitude compared to the established analysis of imprints created solely by ablation. Applying the Beer-Lambert law for absorption, the intensity distribution in a micron-sized focus can be reconstructed from one single shot with a high dynamic range, exceeding 103. The procedure described here allows for beam characterization at free electron lasers revealing even faint beam tails, which are not accessible when using ablation imprint methods. We demonstrate the greatly extended dynamic range on developed imprints taken in focus of conventional Fresnel zone plates and spiral zone plates producing beams with a topological charge.
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J. Vac. Sci. Technol.B35, 061603 (2017)
Lithographic performance of ZEP520A and mr-PosEBR resists exposed by electron beam and extreme ultraviolet lithography
Pattern transfer by deep anisotropic etch is a well-established technique for fabrication of nanoscale devices and structures. For this technique to be effective, the resist material plays a key role and must have a high resolution, reasonable sensitivity, and high etch selectivity against the conventional silicon substrate or underlayer film. In this work, the lithographic performance of two high etch resistance materials was evaluated: ZEP520A (Nippon Zeon Co.) and mr-PosEBR (micro resist technology GmbH). Both materials are positive tone, polymer-based, and nonchemically amplified resists. Two exposure techniques were used: electron beam lithography (EBL) and extreme ultraviolet (EUV) lithography. These resists were originally designed for EBL patterning, where high quality patterning at sub-100 nm resolution was previously demonstrated.
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Communications in Computer and Information Science 755: 247 (2017)
Metadata for nanotechnology: Interoperability aspects
The work outlines the landscape of emerging metadata models for nanotechnology. A gap analysis and possible cross-walks for a few metadata recommendations are presented. The role of interoperability in the design of metadata for nanotechnology is discussed.
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Optics Letters V. 42, 21, 4327 (2017)
Tunable kinoform x-ray beam splitter
We demonstrate an x-ray beam splitter with high performances for multi-kilo-electron-volt photons. The device is based on diffraction on kinoform structures, which overcome the limitations of binary diffraction gratings. This beam splitter achieves a dynamical splitting ratio in the range 0–99.1% by tilting the optics and is tunable, here shown in a photon energy range of 7.2–19 keV. High diffraction efficiency of 62.6%, together with an extinction ratio of 0.6%, is demonstrated at 12.4 keV, with angular separation for the split beam of 0.5 mrad. This device can find applications in beam monitoring at synchrotrons, at x-ray free electron lasers for online diagnostics and beamline multiplexing and, possibly, as key elements for delay lines or ultrashort x-ray pulses manipulation.
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Scientific Reports 7, 13282 (2017)
Neural Network for Nanoscience Scanning Electron Microscope Image Recognition
In this paper we applied transfer learning techniques for image recognition, automatic categorization, and labeling of nanoscience images obtained by scanning electron microscope (SEM). Roughly 20,000 SEM images were manually classified into 10 categories to form a labeled training set, which can be used as a reference set for future applications of deep learning enhanced algorithms in the nanoscience domain. The categories chosen spanned the range of 0-Dimensional (0D) objects such as particles, 1D nanowires and fibres, 2D films and coated surfaces, and 3D patterned surfaces such as pillars. The training set was used to retrain on the SEM dataset and to compare many convolutional neural network models (Inception-v3, Inception-v4, ResNet). We obtained compatible results by performing a feature extraction of the different models on the same dataset. We performed additional analysis of the classifier on a second test set to further investigate the results both on particular cases and from a statistical point of view. Our algorithm was able to successfully classify around 90% of a test dataset consisting of SEM images, while reduced accuracy was found in the case of images at the boundary between two categories or containing elements of multiple categories. In these cases, the image classification did not identify a predominant category with a high score. We used the statistical outcomes from testing to deploy a semi-automatic workflow able to classify and label images generated by the SEM. Finally, a separate training was performed to determine the volume fraction of coherently aligned nanowires in SEM images. The results were compared with what was obtained using the Local Gradient Orientation method. This example demonstrates the versatility and the potential of transfer learning to address specific tasks of interest in nanoscience applications.
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nanoscale, 2017,9, 17342 (2017)
Self-texturizing electronic properties of a 2-dimensional GdAu2 layer on Au(111): the role of out-of-plane atomic displacement
Here, we show that the electronic properties of a surface-supported 2-dimensional (2D) layer structure can self-texturize at nanoscale. The local electronic properties are determined by structural relaxation processes through variable adsorption stacking configurations. We demonstrate that the spatially modulated layer-buckling, which arises from the lattice mismatch and the layer/substrate coupling at the GdAu2/Au(111) interface, is sufficient to locally open an energy gap of ∼0.5 eV at the Fermi level in an otherwise metallic layer. Additionally, this out-of-plane displacement of the Gd atoms patterns the character of the hybridized Gd-d states and shifts the center of mass of the Gd 4f multiplet proportionally to the lattice distortion. These findings demonstrate the close correlation between the electronic properties of the 2D-layer and its planarity. We demonstrate that the resulting template shows different chemical reactivities which may find important applications.
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Proc. SPIE 10446 (2017)
Multi-trigger resist for electron beam lithography
Irresistible Materials is developing a new molecular resist system that demonstrates high-resolution capability based on the Multi-trigger concept. In a Multi-Trigger resist, multiple distinct chemical reactions in chemical amplification process must take place in close proximity simultaneously during resist exposure. Thus, at the edge of a pattern feature, where the density of photo-initiators that drive the chemical reactions is low, the amplification process ceases. This significantly reduces blurring effects and enables much improved resolution and line edge roughness while maintaining the sensitivity advantages of chemical amplification. A series of studies such as enhanced resist crosslinking, elimination of the nucleophilic quencher and the addition of high-Z additives to e-beam resist (as a means to increase sensitivity and modify secondary electron blur) were conducted in order to optimize the performance of this material. The optimized conditions allowed patterning down to 28 nm pitch lines with a dose of 248 μC/cm2 using 100kV e-beam lithography, demonstrating the potential of the concept. Furthermore, it was possible to pattern 26 nm diameter pillars on a 60 nm pitch with dose of 221μC/cm2 with a line edge roughness of 2.3 nm.
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Phys. Chem. Chem. Phys., (2017)
Imaging on-surface hierarchical assembly of chiral supramolecular networks
The bottom-up assembly of chiral structures usually relies on a cascade of molecular recognition interactions. A thorough description of these complex stereochemical mechanisms requires the capability of imaging multilevel coordination in real-time. Here we report the first direct observation of hierarchical expression of supramolecular chirality at work, for 10,10′-dibromo-9,9′-bianthryl (DBBA) on Cu(111). Molecular recognition first steers the growth of chiral organometallic chains and then leads to the formation of enantiopure islands. The structure of the networks was determined by noncontact atomic force microscopy (nc-AFM), while high-speed scanning tunnelling microscopy (STM) revealed details of the assembly mechanisms at the ms time-scale. The direct observation of the chirality transfer pathways allowed us to evaluate the enantioselectivity of the interchain coupling.
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Phys. Rev. X 7, 031036 (2017)
Extreme-Ultraviolet Vortices from a Free-Electron Laser
Extreme-ultraviolet vortices may be exploited to steer the magnetic properties of nanoparticles, increase the resolution in microscopy, and gain insight into local symmetry and chirality of a material; they might even be used to increase the bandwidth in long-distance space communications. However, in contrast to the generation of vortex beams in the infrared and visible spectral regions, production of intense, extreme-ultraviolet and x-ray optical vortices still remains a challenge. Here, we present an in-situ and an ex-situ technique for generating intense, femtosecond, coherent optical vortices at a free-electron laser in the extreme ultraviolet. The first method takes advantage of nonlinear harmonic generation in a helical undulator, producing vortex beams at the second harmonic without the need for additional optical elements, while the latter one relies on the use of a spiral zone plate to generate a focused, micron-size optical vortex with a peak intensity approaching 10^14 W/cm^2, paving the way to nonlinear optical experiments with vortex beams at short wavelengths.
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Chem, VOLUME 3, ISSUE 3, P494-508, SEPTEMBER 14, 2017
Aggregation-Induced Energy Transfer in a Decanuclear Os(II)/Ru(II) Polypyridine Light-Harvesting Antenna Dendrimer
Design of synthetic light-harvesting (LH) antenna systems is a key step for achieving efficient artificial photosynthesis. Self-assembly is a convenient approach for preparing antennas, but photophysical studies of self-assembled LH dendrimers—although dendrimers with photoactive subunits are relatively small antennas by themselves—are quite unknown. We show that dendrimers made of Ru(II) and Os(II) polypyridine subunits spontaneously self-assemble in solution and that this process induces changes in their photophysical properties. In particular, aggregation-driven energy transfer from higher-energy states based on Ru(II) subunits to lower-lying levels involving Os(II) subunits occurs, most likely via an inter-dendrimer mechanism. A similitude with natural photosynthetic systems is evident. The result can open the way to the construction of new synthetic LH antennas, possibly with the perspective of incorporating molecular catalysts within the self-assembled structures.
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Scientific Reports, 7, 8849 (2017)
Transmission zone plates as analyzers for efficient parallel 2D RIXS-mapping
We have implemented and successfully tested an off-axis transmission Fresnel zone plate as spectral analyzer for resonant inelastic X-ray scattering (RIXS). The imaging capabilities of zone plates allow for advanced two-dimensional (2D) mapping applications. By varying the photon energy along a line focus on the sample, we were able to simultaneously record the emission spectra over a range of excitation energies. Moreover, by scanning a line focus across the sample in one dimension, we efficiently recorded RIXS spectra spatially resolved in 2D, increasing the throughput by two orders of magnitude. The presented scheme opens up a variety of novel measurements and efficient, ultra-fast time resolved investigations at X-ray Free-Electron Laser sources.
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Optics Express Vol. 25, 14, pp. 15624-15634 (2017)
Zone plates as imaging analyzers for resonant inelastic x-ray scattering
We have implemented and successfully tested an off-axis transmission Fresnel zone plate as a novel type of analyzer optics for resonant inelastic x-ray scattering (RIXS). We achieved a spectral resolution of 64 meV at the nitrogen K-edge (E/dE = 6200), closely matching theoretical predictions. The fundamental advantage of transmission optics is the fact that it can provide stigmatic imaging properties. This opens up a variety of advanced RIXS configurations, such as efficient scanning RIXS, parallel detection for varying incident energy and time-resolved measurements.
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Nano Lett. 17, 8, 4549 (2017)
Ab Initio Calculations of Ultrashort Carrier Dynamics in Two-Dimensional Materials: Valley Depolarization in Single-Layer WSe 2
In single-layer WSe2, a paradigmatic semiconducting transition metal dichalcogenide, a circularly polarized laser field can selectively excite electronic transitions in one of the inequivalent K± valleys. Such selective valley population corresponds to a pseudospin polarization. This can be used as a degree of freedom in a “valleytronic” device provided that the time scale for its depolarization is sufficiently large. Yet, the mechanism behind the valley depolarization still remains heavily debated. Recent time-dependent Kerr experiments have provided an accurate way to visualize the valley dynamics by measuring the rotation of a linearly polarized probe pulse applied after a circularly polarized pump pulse. We present here a clear, accurate and parameter-free description of the valley dynamics. By using an atomistic, ab initio approach, we fully disclose the elemental mechanisms that dictate the depolarization effects. Our results are in excellent agreement with recent time-dependent Kerr experiments. We explain the Kerr dynamics and its temperature dependence in terms of electron–phonon-mediated processes that induce spin–flip intervalley transitions.
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Nanophotonics 6(5): 923–941 (2017)
Tipping solutions: emerging 3D nano-fabrication/ -imaging technologies
The evolution of optical microscopy from an imaging technique into a tool for materials modification and fabrication is now being repeated with other characterization techniques, including scanning electron microscopy (SEM), focused ion beam (FIB) milling/imaging, and atomic force microscopy (AFM). Fabrication and in situ imaging of materials undergoing a three-dimensional (3D) nano-structuring within a 1−100 nm resolution window is required for future manufacturing of devices. This level of precision is critically in enabling the cross-over between different device platforms (e.g. from electronics to micro-/nano-fluidics and/or photonics) within future devices that will be interfacing with biological and molecular systems in a 3D fashion. Prospective trends in electron, ion, and nano-tip based fabrication techniques are presented.
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ACS Omega 2 (6), 2649 (2017)
Short Pulse Laser Synthesis of Transition-Metal Dichalcogenide Nanostructures under Ambient Conditions
The study of inorganic nanometer-scale materials with hollow closed-cage structures, such as inorganic fullerene-like (IF) nanostructures and inorganic nanotubes (INTs), is a rapidly growing field. Numerous kinds of IF nanostructures and INTs were synthesized for a variety of applications, particularly for lubrication, functional coatings, and reinforcement of polymer matrices. To date, such nanostructures have been synthesized mostly by heating a transition metal or oxide thereof in the presence of precursor gases, which are however toxic and hazardous. In this context, one frontier of research in this field is the development of new avenues for the green synthesis of IF structures and INTs, directly from the bulk of layered compounds. In the present work, we demonstrate a simple room-temperature and environmentally friendly approach for the synthesis of IF nanostructures and INTs via ultrashort-pulse laser ablation of a mixture of transition-metal dichalcogenides in bulk form mixed with Pb/PbO, in ambient air. The method can be considered as a synergy of photothermally and photochemically induced chemical transformations. The ultrafast-laser-induced excitation of the material, complemented with the formation of extended hot annealing regions in the presence of the metal catalyst, facilitates the formation of different nanostructures. Being fast, easy, and material-independent, our method offers new opportunities for the synthesis of IF nanostructures and INTs from different bulk metal chalcogenide compounds. On the basis of the capabilities of laser technology as well, this method could advantageously be further developed into a versatile tool for the simultaneous growth and patterning of such nanostructures in preselected positions for a variety of applications.
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Appl. Phys. Lett. 110, 232103 (2017)
Current conduction mechanism and electric break-down in InN grown on GaN
Current conduction mechanism, including electron mobility, electron drift velocity (vd) and electrical break-down have been investigated in a 0.5 μm-thick (0001) InN layer grown by molecular-beam epitaxy on a GaN/sapphire template. Electron mobility (μ) of 1040 cm2/Vs and a free electron concentration (n) of 2.1 × 1018 cm−3 were measured at room temperature with only a limited change down to 20 K, suggesting scattering on dislocations and ionized impurities.
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Microelectron. Eng. 177, 25 (2017)
Systematic efficiency study of line-doubled zone plates
Line-doubled Fresnel zone plates provide nanoscale, high aspect ratio structures required for efficient high resolution imaging in the multi-keV x-ray range. For the fabrication of such optics a high aspect ratio HSQ resist template is produced by electron-beam lithography and then covered with Ir by atomic layer deposition (ALD). The diffraction efficiency of a line-doubled zone plate depends on the width of the HSQ resist structures as well as on the thickness of the deposited Ir layer. It is very difficult to measure these dimensions by inspection in a scanning electron microscope (SEM) without performing laborious and destructive cross-sections by focus ion beams (FIB). On the other hand, a systematic measurement of the diffraction efficiencies using synchrotron radiation in order to optimize the fabrication parameters is not realistic, as access to synchrotron radiation is sparse. We present a fast and reliable method to study the diffraction efficiency using filtered radiation from an x-ray tube with a copper anode, providing an effective spectrum centered around 8 keV. A large number of Fresnel zone plates with varying dimensions of the resist structures and the ALD coating were measured in an iterative manner. Our results show an excellent match with model calculations. Moreover, this systematic study enables us to identify the optimum fabrication parameters, resulting in a significant increase in diffraction efficiency compared to Fresnel zone plates fabricated earlier without having feedback from a systematic efficiency measurement.
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JINST, 12, P05024 (2017)
The hard X-ray Photon Single-Shot Spectrometer of SwissFEL—initial characterization
SwissFEL requires the monitoring of the photon spectral distribution at a repetition rate of 100 Hz for machine optimization and experiment online diagnostics. The Photon Single Shot Spectrometer has been designed for the photon energy range of 4 keV to 12 keV provided by the Aramis beamline. It is capable of measuring the spectrum in a non-destructive manner, with an energy resolution of Δ E/E = (2–5) × 10−5 over a bandwidth of 0.5% on a shot-to-shot basis. This article gives a detailed description about the technical challenges, structures, and considerations when building such a device, and to further enhance the performance of the spectrometer.
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Biofabrication 9 (2), 025024 (2017)
Cell patterning via laser micro/nano structured silicon surfaces
The surface topography of biomaterials can have an important impact on cellular adhesion, growth and proliferation. Apart from the overall roughness, the detailed morphological features, at all length scales, significantly affect the cell-biomaterial interactions in a plethora of applications including structural implants, tissue engineering scaffolds and biosensors. In this study, we present a simple, one-step direct laser patterning technique to fabricate nanoripples and dual-rough hierarchical micro/nano structures to control SW10 cell attachment and migration. It is shown that, depending on the laser processing conditions, distinct cell-philic or cell-repellant patterned areas can be attained with a desired motif. We envisage that our technique could enable spatial patterning of cells in a controllable manner, giving rise to advanced capabilities in cell biology research.
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Microelectron. Eng. 176, 75 (2017)
Fabrication of diamond diffraction gratings for experiments with intense hard x-rays
The demands on optical components to tolerate high radiation dose and manipulate hard x-ray beams that can fit the experiment requirements, are constantly increasing due to the advancements in the available x-ray sources. Here we have successfully fabricated the transmission type gratings using diamond, with structure sizes ranging from few tens of nanometres up to micrometres, and aspect ratio of up to 20. The efficiencies of the gratings were measured over a wide range of photon energies and their radiation tolerance was confirmed using the most intense x-ray source in the world. The fidelity of these grating structures was confirmed by the quality of the measured experimental results.
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Appl. Phys. Lett. 110, 193102 (2017)
Room temperature observation of biexcitons in exfoliated WS2 monolayers
Single layers of WS2 are direct gap semiconductors with high photoluminescence (PL) yield holding great promise for emerging applications in optoelectronics. The spatial confinement in a 2D monolayer together with the weak dielectric screening lead to huge binding energies for the neutral excitons as well as other excitonic complexes, such as trions and biexcitons whose binding energies scale accordingly. Here, we report on the existence of biexcitons in mechanically exfoliated WS2 flakes from 78 K up to room temperature. Performing temperature and power dependent PL measurements, we identify the biexciton emission channel through the superlinear behavior of the integrated PL intensity as a function of the excitation power density. On the contrary, neutral and charged excitons show a linear to sublinear dependence in the whole temperature range. From the energy difference between the emission channels of the biexciton and neutral exciton, a biexciton binding energy of 65-70 meV is determined.
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Nanotechnology 28, 175301 (2017)
Thermal scanning probe lithography for the directed self-assembly of block copolymers
Thermal scanning probe lithography (t-SPL) is applied to the fabrication of chemical guiding patterns for directed self-assembly (DSA) of block copolymers (BCP). The two key steps of the overall process are the accurate patterning of a poly(phthalaldehyde) resist layer of only 3.5 nm thickness, and the subsequent oxygen-plasma functionalization of an underlying neutral poly(styrene-random-methyl methacrylate) brush layer. We demonstrate that this method allows one to obtain aligned line/space patterns of poly(styrene-block-methyl methacrylate) BCP of 18.5 and 11.7 nm half-pitch. Defect-free alignment has been demonstrated over areas of tens of square micrometres. The main advantages of t-SPL are the absence of proximity effects, which enables the realization of patterns with 10 nm resolution, and its compatibility with standard DSA methods. In the brush activation step by oxygen-plasma exposure, we observe swelling of the brush. This effect is discussed in terms of the chemical reactions occurring in the exposed areas. Our results show that t-SPL can be a suitable method for research activities in the field of DSA, in particular for low-pitch, high-χ BCP to achieve sub-10 nm line/space patterns.
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Journal of Applied Physics 121, 163106 (2017)
Ripple formation on silver after irradiation with radially polarised ultrashort-pulsed lasers
We report on the morphological effects induced by the inhomogeneous absorption of cylindrically polarized femtosecond laser irradiation of silver (Ag) in sub-ablation conditions. A theoretical prediction of the role of surface plasmon excitation and thermal effects in the production of self-formed periodic ripples structures is evaluated. To this end, a combined hydrodynamical and thermoelastic model is presented to account for the influence of temperature-related lattice movements in laser beam conditions that are sufficient to produce material melting. The results indicate that material displacements due to hydrodynamics are substantially larger than strain-related movements, which also emphasises the predominant role of fluid transport in surface modification. Moreover, theoretical simulations highlight the influence of the polarisation state in the size of ripple periodicity for a specialized case of cylindrically polarized beams, the radially polarized beams. The results show that the ripple periodicity is larger if linearly polarized beams are used. This is the opposite trend to the behaviour for materials with decreasing electron-phonon coupling constant g with increasing electron temperature, which highlights the significant role of g.
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DAMDID/RCDL 2016, 706, 248-262 (2017)
Metadata for Experiments in Nanoscience Foundries
Metadata is a key aspect of data management. This paper describes the work of NFFA-EUROPE project on the design of a metadata standard for nanoscience, with a focus on data lifecycle and the needs of data practitioners who manage data resulted from nanoscience experiments. The methodology and the resulting high-level metadata model are presented. The paper explains and illustrates the principles of metadata design for data-intensive research. This is value to data management practitioners in all branches of research and technology that imply a so-called “visitor science” model where multiple researchers apply for a share of a certain resource on large facilities (instruments).
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Phys. Rev. B 95, 155203 (2017)
Optical properties of periodic systems within the current-current response framework: Pitfalls and remedies
We compare the optical absorption of extended systems using the density-density and current-current linear response functions calculated within many-body perturbation theory. The two approaches are formally equivalent for a finite momentum q of the external perturbation. At q=0, however, the equivalence is maintained only if a small q expansion of the density-density response function is used. Moreover, in practical calculations, this equivalence can be lost if one naively extends the strategies usually employed in the density-based approach to the current-based approach.
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Proceedings Volume 10146, Advances in Patterning Materials and Processes XXXIV; 101461F (2017)
Chemical changes in hybrid photoresists before and after exposure by in situ NEXAFS analysis
Due to its chemical specificity, the near edge X-ray absorption fine structure spectroscopy is an interesting technique to study the changes in hybrid organic-inorganic photoresists. In this work, we analyzed the chemical changes occurring in photoresists synthesized from organically modified precursors and transition metal alkoxides by sol-gel route. These systems are nonchemically amplified resists for ultraviolet, extreme ultraviolet, and electron beam lithography. They are based on Si, Zr, and Ti oxides or a combination of these. The experiments were conducted at the PolLux beamline of the Swiss Light Source, by a scanning transmission X-ray microscopy, which combines the spatially-resolved microscopy and fine structure spectroscopy at once. The absorption spectra were collected in the energy range of the carbon edge (≈ 290 eV) before and after in situ exposure of the photoresists to 500 eV photons. The variations in peak intensity after exposure reveal the changes in the chemical environment of carbon and the chemical configuration of the organic ligands, regardless of the inorganic part. It was found that the photon exposure induced sizable photodegradation or photopolymerization of organic groups (phenyl or methyl methacrylate, respectively). These mechanisms contribute to the foundation for the exposure reaction in negative-tone hybrid photoresists. Interestingly, it was also found that the detachment of the phenyl ligand occurs in a variety of possible pathways to condensation. We believe that our results and approach can provide a better understanding of photochemistry of resists, in particular for extreme ultraviolet lithography.
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Proceedings SPIE 10143, 1-10 (2017)
Extreme ultraviolet patterning of tin-oxo cages
We report on the extreme ultraviolet (EUV) patterning performance of tin-oxo cages: molecular building blocks that are known to turn insoluble upon EUV exposure, thus having the properties of a negative tone photoresist. In this work, we focus on contrast curves of the materials using open-frame EUV exposures and their patterning capabilities using EUV interference lithography. It is shown that baking steps, such as post-exposure baking (PEB) can significantly affect both the sensitivity and contrast in the open-frame experiments as well as the patterning experiments. In addition, we show that the exchange of the anions of the cage can make a difference in terms of their physical properties. Our results demonstrate the significance of process optimization while evaluating the resist performance of novel molecular materials.
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Acta Biomaterialia 51, 21–52 (2017)
Controlling the morphology and outgrowth of nerve and neuroglial cells: The effect of surface topography
Unlike other tissue types, like epithelial tissue, which consist of cells with a much more homogeneous structure and function, the nervous tissue spans in a complex multilayer environment whose topographical features display a large spectrum of morphologies and size scales. Traditional cell cultures, which are based on two-dimensional cell-adhesive culture dishes or coverslips, are lacking topographical cues and mainly simulate the biochemical microenvironment of the cells. With the emergence of micro- and nano-fabrication techniques new types of cell culture platforms are developed, where the effect of various topographical cues on cellular morphology, proliferation and differentiation can be studied. Different approaches (regarding the material, fabrication technique, topographical characteristics, etc.) have been implemented. The present review paper aims at reviewing the existing body of literature on the use of artificial micro- and nano-topographical features to control neuronal and neuroglial cells’ morphology, outgrowth and neural network topology. The cell responses–from phenomenology to investigation of the underlying mechanisms- on the different topographies, including both deterministic and random ones, are summarized.
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Phys. Rev. B 94, 245303 (2016)
First-principles approach to excitons in time-resolved and angle-resolved photoemission spectra
In this work we put forward a first-principles approach and propose an accurate diagrammatic approximation to calculate the time-resolved (TR) and angle-resolved photoemission spectrum of systems with excitons. We also derive an alternative formula to the TR photocurrent which involves a single time-integral of the lesser Green's function. The diagrammatic approximation applies to the relaxed regime characterized by the presence of quasistationary excitons and vanishing polarization. The nonequilibrium self-energy diagrams are evaluated using excited Green's functions; since this is not standard, the analytic derivation is presented in detail. The final result is an expression for the lesser Green's function in terms of quantities that can all be calculated in a first-principles manner. The validity of the proposed theory is illustrated in a one-dimensional model system with a direct gap. We discuss possible scenarios and highlight some universal features of the exciton peaks. Our results indicate that the exciton dispersion can be observed in TR and angle-resolved photoemission.
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Review of Scientific Instruments, 87/12, 123909 (2016)
A versatile UHV transport and measurement chamber for neutron reflectometry
We report on a versatile mini ultra high vacuum (UHV) chamber which is designed to be used on the MAgnetic Reflectometer with high Incident Angle (MARIA) of the J¨ulich Centre for Neutron Science at Heinz Maier-Leibnitz Zentrum in Garching, Germany. Samples are prepared in the adjacent thin film laboratory by molecular beam epitaxy and moved into the compact chamber for transfer without exposure to ambient air. The chamber is based on DN 40 CF flanges and equipped with sapphire view ports, a small getter pump and a wobble stick, which serves also as sample holder. Here, we present polarized neutron reflectivity measurements which have been performed on Co thin films at room temperature in UHV and in ambient air in a magnetic field of 200 mT and in the Q-range of 0.18 ˚A −1 . The results confirm that the Co film is not contaminated during the polarized neutron reflectivity measurement. Herewith it is demonstrated that the mini UHV transport chamber also works as measurement chamber which opens new possibilities for polarized neutron measurements under UHV conditions.
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Europhysics Lett., 116, 4, 43001 (2016)
Lamb shift of the Dirac cone of graphene
The fluctuations of the electromagnetic vacuum are one of the most powerful manifestations of the quantum structure of nature. Their effect on the Dirac electrons of graphene is known to induce some spectacular and purely quantistic phenomena, like the Casimir and the Aharanov-Bohm effects. In this work we demonstrate, by using a first-principles approach, that the Dirac cone of graphene is also affected by a sizeable Lamb shift. We show that the microscopic electronic currents flowing on the graphene plane are strongly coupled with the vacuum fluctuations causing a renormalisation of the electronic levels (as large as 4 meV). This shift is one order of magnitude larger than the value predicted for an isolated carbon atom, which imposes a reinterpretation of the Lamb shift as a collective effect.
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J. Vac. Sci. Technol. B 34, 06K702 (2016)
Comparative study of resists and lithographic tools using the Lumped Parameter Model
A comparison of the performance of high resolution lithographic tools is presented here. The authors use extreme ultraviolet interference lithography, electron beam lithography, and He ion beam lithography tools on two different resists that are processed under the same conditions. The dose-to-clear and the lithographic contrast are determined experimentally and are used to compare the relative efficiency of each tool. The results are compared to previous studies and interpreted in the light of each tool-specific secondary electron yield. In addition, the patterning performance is studied by exposing dense lines/spaces patterns, and the relation between critical dimension and exposure dose is discussed. Finally, the lumped parameter model is employed in order to quantitatively estimate the critical dimension of lines/spaces, using each tool specific aerial image. Our implementation is then validated by fitting the model to the experimental data from interference lithography exposures and extracting the resist contrast.
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Appl. Surf. Sci. 385, 145 (2016)
Patterning of diamond like carbon films for sensor applications using silicon containing thermoplastic resist (SiPol) as a hard mask
Patterning of diamond-like carbon (DLC) and DLC:metal nanocomposites is of interest for an increasing number of applications. We demonstrate a nanoimprint lithography process based on silicon containing thermoplastic resist combined with plasma etching for straightforward patterning of such films. A variety of different structures with few hundred nanometer feature size and moderate aspect ratios were successfully realized. The quality of produced patterns was directly investigated by the means of optical and scanning electron microscopy (SEM). Such structures were further assessed by employing them in the development of gratings for guided mode resonance (GMR) effect. Optical characterization of such leaky waveguide was compared with numerical simulations based on rigorous coupled wave analysis method with good agreement. The use of such structures as refractive index variation sensors is demonstrated with sensitivity up to 319 nm/RIU, achieving an improvement close to 450% in sensitivity compared to previously reported similar sensors. This pronounced GMR signal fully validates the employed DLC material, the technology to pattern it and the possibility to develop DLC based gratings as corrosion and wear resistant refractometry sensors that are able to operate under harsh conditions providing great value and versatility.
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Phys. Rev. B 94, 134306 (2016)
Electron-phonon scattering effects on electronic and optical properties of orthorhombic GeS
Group-VI monochalcogenides are attracting a great deal of attention due to their peculiar anisotropic properties. Very recently, it has been suggested that GeS could act as a promissory absorbing material with high input-output ratios, relevant features for designing prospective optoelectronic devices. In this work, we use the ab-initio many body perturbation theory to study the role of the electron-phonon coupling on orthorhombic GeS. We identify the vibrational modes that efficiently couple with the electronic states responsible for giving rise to the first and second excitonic state. We also study the finite-temperature optical absorption and show that even at T → 0K, the role of the electron-phonon interaction is crucial to properly describe the main experimental excitation peaks position and width. Our results suggest that the electron-phonon coupling is essential to properly describe the optical properties of the monochalcogenides family.
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Acta Biomaterialia 43, 230 (2016)
Functional protein-based nanomaterial produced in microorganisms recognized as safe: A new platform for biotechnology
Inclusion bodies (IBs) are protein-based nanoparticles formed in Escherichia coli through stereospecific aggregation processes during the overexpression of recombinant proteins. In the last years, it has been shown that IBs can be used as nanostructured biomaterials to stimulate mammalian cell attachment, proliferation, and differentiation. In addition, these nanoparticles have also been explored as natural delivery systems for protein replacement therapies. Although the production of these protein-based nanomaterials in E. coli is economically viable, important safety concerns related to the presence of endotoxins in the products derived from this microorganism need to be addressed. Lactic acid bacteria (LAB) are a group of food-grade microorganisms that have been classified as safe by biologically regulatory agencies. In this context, we have demonstrated herein, for the first time, the production of fully functional, IB-like protein nanoparticles in LAB. These nanoparticles have been fully characterized using a wide range of techniques, including field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), dynamic light scattering (DLS), Fourier transform infrared (FTIR) spectroscopy, zymography, cytometry, confocal microscopy, and wettability and cell coverage measurements.
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Phys. Rev. B 94, 035149 (2016)
Dielectrics in a time-dependent electric field: A real-time approach based on density-polarization functional theory
In the presence of a (time-dependent) macroscopic electric field the electron dynamics of dielectrics cannot be described by the time-dependent density only. We present a real-time formalism that has the density and the macroscopic polarization P as key quantities. We show that a simple local function of P already captures long-range correlation in linear and nonlinear optical response functions. Specifically, after detailing the numerical implementation, we examine the optical absorption, the second- and third-harmonic generation of bulk Si, GaAs, AlAs, and CdTe, at different levels of approximation. We highlight links with ultranonlocal exchangecorrelation functional approximations proposed within a linear response time-dependent density functional theory framework.
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Nano Lett. 16, 5095 (2016)
Anomalous temperature dependence of the band-gap in Black Phosphorus
Black Phosphorus (BP) has gained renewed attention due to its singular anisotropic electronic and optical properties that might be exploited for a wide range of technological applications. In this respect, the thermal properties are particularly important both to predict its room temperature operation and to determine its thermoelectric potential. From this point of view, one of the most spectacular and poorly understood phenomena is, indeed, the BP temperature-induced band-gap opening: when temperature is increased the fundamental band-gap increases instead of decreasing. This anomalous thermal dependence has also been observed, recently, in its monolayer counterpart. In this work, based on \textit{ab-initio} calculations, we present an explanation for this long known, and yet not fully explained, effect. We show that it arises from a combination of harmonic and lattice thermal expansion contributions, which are, in fact, highly interwined. We clearly narrow down the mechanisms that cause this gap opening by identifying the peculiar atomic vibrations that drive the anomaly. The final picture we give explains both the BP anomalous band-gap opening and the frequency increase with increasing volume (tension effect).
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Nanoscale , 8 , 16197 (2016)
Spatial non-uniformity in exfoliated WS 2 single layers
Monolayers of transition metal dichalcogenides (TMDs) are atomically thin two-dimensional crystals with attractive optoelectronic properties, which are promising for emerging applications in nanophotonics. Here, we report on the extraordinary spatial non-uniformity of the photoluminescence (PL) and strain properties of exfoliated WS2 monolayers. Specifically, it is shown that the edges of such monolayers exhibit remarkably enhanced PL intensity compared to their respective central area. A comprehensive analysis of the recombination channels involved in the PL process demonstrates a spatial non-uniformity across the monolayer’s surface and reflects on the non-uniformity of the intrinsic electron density across the monolayer. Auger electron imaging and spectroscopy studies complemented with PL measurements in different environments indicate that oxygen chemisorption and physisorption are the two fundamental mechanisms responsible for the observed non-uniformity. At the same time Raman spectroscopy analysis shows remarkable strain variations among the different locations of an individual monolayer, however such variations cannot be strictly correlated with the non-uniform PL emission. Our results shed light on the role of the chemical bonding in the competition between exciton complexes in monolayer WS2, providing a method of engineering new nanophotonic functions using WS2 monolayers. It is therefore envisaged that our findings could find diverse applications towards the development of TMD-based optoelectronic devices.
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Phys. Rev. B 93, 195205 (2016)
Non equilibrium optical properties in semiconductors from first principles: a combined theoretical and experimental study of bulk silicon
The calculation of the equilibrium optical properties of bulk silicon by using the Bethe–Salpeter equation solved in the Kohn–Sham basis represents a cornerstone in the development of an ab– initio approach to the optical and electronic properties of materials. Nevertheless calculations of the transient optical spectrum using the same efficient and successful scheme are scarce. We report, here, a joint theoretical and experimental study of the transient reflectivity spectrum of bulk silicon. Femtosecond transient reflectivity is compared to a parameter–free calculation based on the non–equilibrium Bethe–Salpeter equation. By providing an accurate description of the experimental results we disclose the different phenomena that determine the transient optical response of a semiconductor. We give a parameter–free interpretation of concepts like bleaching, photo–induced absorption and stimulated emission, beyond the Fermi golden rule. We also introduce the concept of optical gap renormalization, as a generalization of the known mechanism of band gap renormalization. The present scheme successfully describes the case of bulk silicon, showing its universality and accuracy.
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Phys. Rev. B 93, 155435 (2016)
Temperature dependent excitonic effects in the optical properties of single-layer MoS2
Temperature influences the performance of two-dimensional materials in optoelectronic devices. Indeed, the optical characterization of these materials is usually realized at room temperature. Nevertheless most ab-initio studies are yet performed without including any temperature effect. As a consequence, important features are thus overlooked, such as the relative intensity of the excitonic peaks and their broadening, directly related to the temperature and to the non-radiative exciton relaxation time. We present ab-initio calculations of the optical response of single-layer MoS2, a prototype 2D material, as a function of temperature using density functional theory and manybody perturbation theory. We compute the electron-phonon interaction using the full spinorial wave functions, i.e., fully taking into account effects of spin-orbit interaction. We find that bound excitons (A and B peaks) and resonant excitons (C peak) exhibit different behavior with temperature, displaying different non-radiative linewidths. We conclude that the inhomogeneous broadening of the absorption spectra is mainly due to electron-phonon scattering mechanisms. Our calculations explain the shortcomings of previous (zero-temperature) theoretical spectra and match well with the experimental spectra acquired at room temperature. Moreover, we disentangle the contributions of acoustic and optical phonon modes to the quasi-particles and exciton linewidths. Our model also allows to identify which phonon modes couple to each exciton state, useful for the interpretation of resonant Raman scattering experiments.
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Nature Communications 7, 11327 (2016)
Electron–vibration coupling induced renormalization in the photoemission spectrum of diamondoids
The development of theories and methods devoted to the accurate calculation of the electronic quasi-particle states and levels of molecules, clusters and solids is of prime importance to interpret the experimental data. These quantum systems are often modelled by using the Born–Oppenheimer approximation where the coupling between the electrons and vibrational modes is not fully taken into account, and the electrons are treated as pure quasi-particles. Here, we show that in small diamond cages, called diamondoids, the electron–vibration coupling leads to the breakdown of the electron quasi-particle picture. More importantly, we demonstrate that the strong electron–vibration coupling is essential to properly describe the overall lineshape of the experimental photoemission spectrum. This cannot be obtained by methods within Born–Oppenheimer approximation. Moreover, we deduce a link between the vibronic states found by our many-body perturbation theory approach and the well-known Jahn–Teller effect.
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Phys. Rev. B 93/15, (2016)
An unified theory of quantised electrons, phonons and photons out-of-equilibrium: a simplified ab-initio approach based on the Generalised Baym-Kadanoff ansatz
We present a full ab-inito description of the coupled out-of-equilibrium dynamics of photons, phonons, and electrons. In the present approach the quantised nature of the electromagnetic field as well as of the nuclear oscillations is fully taken into account. The result is a set of integro-differential equations, written on the Keldysh contour, for the Green's functions of electrons, phonons, and photons where the different kind of interactions are merged together. We then concentrate on the electronic dynamics in order to reduce the problem to a computationally feasible approach. By using the Generalised Baym-Kadanoff ansatz and the Completed Collision approximation we introduce a series of efficient but controllable approximations. In this way we reduce all equations to a set of decoupled equations for the density matrix that describe all kind of static and dynamical correlations. The final result is a coherent, general, and inclusive scheme to calculate several physical quantities: carrier dynamics, transient photo-absorption and light-emission. All of which include, at the same time, electron-electron, electron-phonon, and electron-photon interaction. We further discuss how all these observables can be easily calculated within the present scheme using a fully atomistic ab-initio approach.
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ACS Nano 10, 1182 (2016)
Photo-Induced Bandgap Renormalization Governs the Ultrafast Response of Single-Layer MoS2
Transition metal dichalcogenides (TMDs) are emerging as promising two-dimensional (2d) semiconductors for optoelectronic and flexible devices. However, a microscopic explanation of their photophysics -- of pivotal importance for the understanding and optimization of device operation -- is still lacking. Here we use femtosecond transient absorption spectroscopy, with pump pulse tunability and broadband probing, to monitor the relaxation dynamics of single-layer MoS2 over the entire visible range, upon photoexcitation of different excitonic transitions. We find that, irrespective of excitation photon energy, the transient absorption spectrum shows the simultaneous bleaching of all excitonic transitions and corresponding red-shifted photoinduced absorption bands. First-principle modeling of the ultrafast optical response reveals that a transient bandgap renormalization, caused by the presence of photo-excited carriers, is primarily responsible for the observed features. Our results demonstrate the strong impact of many-body effects in the transient optical response of TMDs even in the low-excitation-density regime.
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Phys. Rev. B 92, 205304 (2015)
Nonequilibrium Bethe-Salpeter equation for transient photoabsorption spectroscopy
In this work, we propose an accurate first-principles approach to calculate the transient photoabsorption spectrum measured in pump-and-probe experiments. We formulate a condition of adiabaticity and thoroughly analyze the simplifications brought about by the fulfillment of this condition in the nonequilibrium Green's function (NEGF) framework. Starting from the Kadanoff-Baym equations, we derive a nonequilibrium Bethe-Salpeter equation (BSE) for the response function that can be implemented in most of the already existing ab initio codes. In addition, the adiabatic approximation is benchmarked against full NEGF simulations in simple model Hamiltonians, even under extreme, nonadiabatic conditions in which it is expected to fail. We find that the nonequilibrium BSE is very robust and captures important spectral features in a wide range of experimental configurations.
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