Publications

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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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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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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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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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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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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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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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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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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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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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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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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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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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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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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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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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