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On the Promotion of Catalytic Reactions by Surface Acoustic Waves
Surface acoustic waves (SAW) allow to manipulate surfaces with potential applications in catalysis, sensor and nanotechnology. SAWs were shown to cause a strong increase in catalytic activity and selectivity in many oxidation and decomposition reactions on metallic and oxidic catalysts. However, the promotion mechanism has not been unambiguously identified. Using stroboscopic X-ray photoelectron spectro-microscopy, we were able to evidence a sub-nanosecond work function change during propagation of 500 MHz SAWs on a 9 nm thick platinum film. We quantify the work function change to 455 μeV. Such a small variation rules out that electronic effects due to elastic deformation (strain) play a major role in the SAW-induced promotion of catalysis. In a second set of experiments, SAW-induced intermixing of a five monolayers thick Rh film on top of polycrystalline platinum was demonstrated to be due to enhanced thermal diffusion caused by an increase of the surface temperature by about 75 K when SAWs were excited. Reversible surface structural changes are suggested to be a major cause for catalytic promotion. © 2020 The Authors. Published by Wiley-VCH GmbH
Ferroelectric Control of the Spin Texture in GeTe
The electric and nonvolatile control of the spin texture in semiconductors would represent a fundamental step toward novel electronic devices combining memory and computing functionalities. Recently, GeTe has been theoretically proposed as the father compound of a new class of materials, namely ferroelectric Rashba semiconductors. They display bulk bands with giant Rashba-like splitting due to the inversion symmetry breaking arising from the ferroelectric polarization, thus allowing for the ferroelectric control of the spin. Here, we provide the experimental demonstration of the correlation between ferroelectricity and spin texture. A surface-engineering strategy is used to set two opposite predefined uniform ferroelectric polarizations, inward and outward, as monitored by piezoresponse force microscopy. Spin and angular resolved photoemission experiments show that these GeTe(111) surfaces display opposite sense of circulation of spin in bulk Rashba bands. Furthermore, we demonstrate the crafting of nonvolatile ferroelectric patterns in GeTe films at the nanoscale by using the conductive tip of an atomic force microscope. Based on the intimate link between ferroelectric polarization and spin in GeTe, ferroelectric patterning paves the way to the investigation of devices with engineered spin configurations.
Scanning X-ray nanodiffraction from ferroelectric domains in strained K0.75Na0.25NbO3 epitaxial films grown on (110) TbScO3
Scanning X-ray nanodiffraction on a highly periodic ferroelectric domain pattern of a strained K0.75Na0.25NbO3 epitaxial layer has been performed by using a focused X-ray beam of about 100 14;nm probe size. A 90°-rotated domain variant which is aligned along [1 2]TSO has been found in addition to the predominant domain variant where the domains are aligned along the [12]TSO direction of the underlying (110) TbScO3 (TSO) orthorhombic substrate. Owing to the larger elastic strain energy density, the 90°-rotated domains appear with significantly reduced probability. Furthermore, the 90°-rotated variant shows a larger vertical lattice spacing than the 0°-rotated domain variant. Calculations based on linear elasticity theory substantiate that this difference is caused by the elastic anisotropy of the K0.75Na0.25NbO3 epitaxial layer.
Top-down fabrication of ordered arrays of GaN nanowires by selective area sublimation
We demonstrate the top-down fabrication of ordered arrays of GaN nanowires by selective area sublimation of pre-patterned GaN(0001) layers grown by hydride vapor phase epitaxy on Al2O3. Arrays with nanowire diameters and spacings ranging from 50 to 90 nm and 0.1 to 0.7 µm, respectively, are simultaneously produced under identical conditions. The sublimation process, carried out under high vacuum conditions, is analyzed in situ by reflection high-energy electron diffraction and line-of-sight quadrupole mass spectrometry. During the sublimation process, the GaN(0001) surface vanishes, giving way to the formation of semi-polar {1103} facets which decompose congruently following an Arrhenius temperature dependence with an activation energy of (3.54 ± 0.07) eV and an exponential prefactor of 1.58 × 1031 atoms per cm2 per s. The analysis of the samples by lowerature cathodoluminescence spectroscopy reveals that, in contrast to dry etching, the sublimation process does not introduce nonradiative recombination centers at the nanowire sidewalls. This technique is suitable for the top-down fabrication of a variety of ordered nanostructures, and could possibly be extended to other material systems with similar crystallographic properties such as ZnO. © 2019 The Royal Society of Chemistry.
Silane-Mediated Expansion of Domains in Si-Doped κ-Ga2O3 Epitaxy and its Impact on the In-Plane Electronic Conduction
Unintentionally doped (001)-oriented orthorhombic κ-Ga2O3 epitaxial films on c-plane sapphire substrates are characterized by the presence of ≈ 10 nm wide columnar rotational domains that can severely inhibit in-plane electronic conduction. Comparing the in- and out-of-plane resistance on well-defined sample geometries, it is experimentally proved that the in-plane resistivity is at least ten times higher than the out-of-plane one. The introduction of silane during metal-organic vapor phase epitaxial growth not only allows for n-type Si extrinsic doping, but also results in the increase of more than one order of magnitude in the domain size (up to ≈ 300 nm) and mobility (highest µ ≈ 10 cm2V−1s−1, with corresponding lowest ρ ≈ 0.2 Ωcm). To qualitatively compare the mean domain dimension in κ-Ga2O3 epitaxial films, non-destructive experimental procedures are provided based on X-ray diffraction and Raman spectroscopy. The results of this study pave the way to significantly improved in-plane conduction in κ-Ga2O3 and its possible breakthrough in new generation electronics. The set of cross-linked experimental techniques and corresponding interpretation here proposed can apply to a wide range of material systems that suffer/benefit from domain-related functional properties.
Beam damage of single semiconductor nanowires during X-ray nanobeam diffraction experiments
Nanoprobe X-ray diffraction (nXRD) using focused synchrotron radiation is a powerful technique to study the structural properties of individual semiconductor nanowires. However, when performing the experiment under ambient conditions, the required high X-ray dose and prolonged exposure times can lead to radiation damage. To unveil the origin of radiation damage, a comparison is made of nXRD experiments carried out on individual semiconductor nanowires in their as-grown geometry both under ambient conditions and under He atmosphere at the microfocus station of the P08 beamline at the third-generation source PETRA III. Using an incident X-ray beam energy of 9 keV and photon flux of 1010 s-1, the axial lattice parameter and tilt of individual GaAs/In0.2Ga0.8As/GaAs core-shell nanowires were monitored by continuously recording reciprocal-space maps of the 111 Bragg reflection at a fixed spatial position over several hours. In addition, the emission properties of the (In,Ga)As quantum well, the atomic composition of the exposed nanowires and the nanowire morphology were studied by cathodoluminescence spectroscopy, energy-dispersive X-ray spectroscopy and scanning electron microscopy, respectively, both prior to and after nXRD exposure. Nanowires exposed under ambient conditions show severe optical and morphological damage, which was reduced for nanowires exposed under He atmosphere. The observed damage can be largely attributed to an oxidation process from X-ray-induced ozone reactions in air. Due to the lower heat-transfer coefficient compared with GaAs, this oxide shell limits the heat transfer through the nanowire side facets, which is considered as the main channel of heat dissipation for nanowires in the as-grown geometry.
X-ray diffraction reveals the amount of strain and homogeneity of extremely bent single nanowires
Core-shell nanowires (NWs) with asymmetric shells allow for strain engineering of NW properties because of the bending resulting from the lattice mismatch between core and shell material. The bending of NWs can be readily observed by electron microscopy. Using X-ray diffraction analysis with a micro- and nano-focused beam, the bending radii found by the microscopic investigations are confirmed and the strain in the NW core is analyzed. For that purpose, a kinematical diffraction theory for highly bent crystals is developed. The homogeneity of the bending and strain is studied along the growth axis of the NWs, and it is found that the lower parts, i.e. close to the substrate/wire interface, are bent less than the parts further up. Extreme bending radii down to ∼3 μm resulting in strain variation of ∼2.5% in the NW core are found. © 2020.
Acoustically Driven Stark Effect in Transition Metal Dichalcogenide Monolayers
The Stark effect is one of the most efficient mechanisms to manipulate many-body states in nanostructured systems. In mono- and few-layer transition metal dichalcogenides, it has been successfully induced by optical and electric field means. Here, we tune the optical emission energies and dissociate excitonic states in MoSe2 monolayers employing the 220 MHz in-plane piezoelectric field carried by surface acoustic waves. We transfer the monolayers to high dielectric constant piezoelectric substrates, where the neutral exciton binding energy is reduced, allowing us to efficiently quench (above 90%) and red-shift the excitonic optical emissions. A model for the acoustically induced Stark effect yields neutral exciton and trion in-plane polarizabilities of 530 and 630 × 10-5 meV/(kV/cm)2, respectively, which are considerably larger than those reported for monolayers encapsulated in hexagonal boron nitride. Large in-plane polarizabilities are an attractive ingredient to manipulate and modulate multiexciton interactions in two-dimensional semiconductor nanostructures for optoelectronic applications. © 2021 The Authors. Published by American Chemical Society.
The impact of ultraviolet laser excitation during Raman spectroscopy of hexagonal boron nitride thin films
We utilized excitation in the ultraviolet (UV) spectral range for the study of hexagonal boron nitride (h-BN) thin films on different substrates by Raman spectroscopy. Whereas UV excitation offers fundamental advantages for the investigation of h-BN and heterostructures with graphene, the actual Raman spectra recorded under ambient conditions reveal a temporal decay of the signal intensity. The disappearance of the Raman signal is found to be induced by thermally activated chemical reactions with ambient molecules at the h-BN surface. The chemical reactions could be strongly suppressed under vacuum conditions which, however, favor the formation of a carbonaceous surface contamination layer. For the improvement of the signal-to-noise ratio under ambient conditions, we propose a line-scan method for the acquisition of UV Raman spectra in atomically thin h-BN, a material which is expected to play a key role in future technologies based on 2D van der Waals heterostructures. © 2020 The Authors. Journal of Raman Spectroscopy published by John Wiley & Sons Ltd
Threefold rotational symmetry in hexagonally shaped core–shell (In,Ga)As/GaAs nanowires revealed by coherent X-ray diffraction imaging
Coherent X-ray diffraction imaging at symmetric hhh Bragg reflections was used to resolve the structure of GaAs/In0.15Ga0.85As/GaAs core–shell–shell nanowires grown on a silicon (111) substrate. Diffraction amplitudes in the vicinity of GaAs 111 and GaAs 333 reflections were used to reconstruct the lost phase information. It is demonstrated that the structure of the core–shell–shell nanowire can be identified by means of phase contrast. Interestingly, it is found that both scattered intensity in the (111) plane and the reconstructed scattering phase show an additional threefold symmetry superimposed with the shape function of the investigated hexagonal nanowires. In order to find the origin of this threefold symmetry, elasticity calculations were performed using the finite element method and subsequent kinematic diffraction simulations. These suggest that a non-hexagonal (In,Ga)As shell covering the hexagonal GaAs core might be responsible for the observation.