Bending and reverse bending during the fabrication of novel GaAs/(In,Ga)As/GaAs core-shell nanowires monitored byin situx-ray diffraction.

We report on the fabrication of a novel design of GaAs/(In,Ga)As/GaAs radial nanowire heterostructures on a Si 111 substrate, where, for the first time, the growth of inhomogeneous shells on a lattice mismatched core results in straight nanowires instead of bent. Nanowire bending caused by axial tensile strain induced by the (In,Ga)As shell on the GaAs core is reversed by axial compressive strain caused by the GaAs outer shell on the (In,Ga)As shell. Progressive nanowire bending and reverse bending in addition to the axial strain evolution during the two processes are accessed byin situby x-ray diffraction. The diameter of the core, thicknesses of the shells, as well as the indium concentration and distribution within the (In,Ga)As quantum well are revealed by 2D energy dispersive x-ray spectroscopy using a transmission electron microscope. Shell(s) growth on one side of the core without substrate rotation results in planar-like radial heterostructures in the form of free standing straight nanowires.

Exploiting flux shadowing for strain and bending engineering in core-shell nanowires.

Here we report on the non-uniform shell growth of InxGa1-xAs on the GaAs nanowire (NW) core by molecular beam epitaxy (MBE). The growth was realized on pre-patterned silicon substrates with the pitch size (p) ranging from 0.1 µm to 10 µm. Considering the preferable bending direction with respect to the MBE cells as well as the layout of the substrate pattern, we were able to modify the strain distribution along the NW growth axis and the subsequent bending profile. For NW arrays with a high number density, the obtained bending profile of the NWs is composed of straight (barely-strained) and bent (strained) segments with different lengths which depend on the pitch size. A precise control of the bent and straight NW segment length provides a method to design NW based devices with length selective strain distribution.

In situx-ray analysis of misfit strain and curvature of bent polytypic GaAs-InxGa1-xAs core-shell nanowires.

Misfit strain in core-shell nanowires can be elastically released by nanowire bending in case of asymmetric shell growth around the nanowire core. In this work, we investigate the bending of GaAs nanowires during the asymmetric overgrowth by an InxGa1-xAs shell caused by avoiding substrate rotation. We observe that the nanowire bending direction depends on the nature of the substrate's oxide layer, demonstrated by Si substrates covered by native and thermal oxide layers. Further, we follow the bending evolution by time-resolvedin situx-ray diffraction measurements during the deposition of the asymmetric shell. The XRD measurements give insight into the temporal development of the strain as well as the bending evolution in the core-shell nanowire.

Correlating in situ RHEED and XRD to study growth dynamics of polytypism in nanowires.

Design of novel nanowire (NW) based semiconductor devices requires deep understanding and technological control of NW growth. Therefore, quantitative feedback over the structure evolution of the NW ensemble during growth is highly desirable. We analyse and compare the methodical potential of reflection high-energy electron diffraction (RHEED) and X-ray diffraction reciprocal space imaging (XRD) for in situ growth characterization during molecular-beam epitaxy (MBE). Simultaneously recorded in situ RHEED and in situ XRD intensities show strongly differing temporal behaviour and provide evidence of the highly complementary information value of both diffraction techniques. Exploiting the complementarity by a correlative data analysis presently offers the most comprehensive experimental access to the growth dynamics of statistical NW ensembles under standard MBE growth conditions. In particular, the combination of RHEED and XRD allows for translating quantitatively the time-resolved information into a height-resolved information on the crystalline structure without a priori assumptions on the growth model. Furthermore, we demonstrate, how careful analysis of in situ RHEED if supported by ex situ XRD and scanning electron microscopy (SEM), all usually available at conventional MBE laboratories, can also provide highly quantitative feedback on polytypism during growth allowing validation of current vapour-liquid-solid (VLS) growth models.

Cyclic Deformation Induced Residual Stress Evolution and 3D Short Fatigue Crack Growth Investigated by Advanced Synchrotron Tomography Techniques.

Diffraction and phase contrast tomography techniques were successfully applied to an austenitic-ferritic duplex stainless steel representing exemplarily a metallic material containing two phases with different crystal structures. The reconstructed volumes of both phases were discretized by finite elements. A crystal plasticity finite-element analysis was executed in order to simulate the development of the experimentally determined first and second order residual stresses, which built up due to the manufacturing process of the material. Cyclic deformation simulations showed the single-grain-resolved evolution of initial residual stresses in both phases and were found to be in good agreement with the experimental results. Solely in ferritic grains, residual stresses built up due to cyclic deformation, which promoted crack nucleation in this phase. Furthermore, phase contrast tomography was applied in order to analyze the mechanisms of fatigue crack nucleation and short fatigue crack propagation three-dimensionally and nondestructively. The results clearly showed the significance of microstructural barriers for short fatigue crack growth at the surface, as well as into the material. The investigation presented aims for a better understanding of the three-dimensional mechanisms governing short fatigue crack propagation and, in particular, the effect of residual stresses on these mechanisms. The final goal was to generate tailored microstructures for improved fatigue resistance and enhanced fatigue life.

Transition from elastic to plastic strain release in core-shell nanowires revealed by in-plane x-ray diffraction.

We investigate the strain evolution and relaxation process as function of increasing lattice mismatch between the GaAs core and surrounding In x Ga1-x As shell in core-shell nanowire heterostructures grown on Si(111) substrates. The dimensions of the core and shell are kept constant whereas the indium concentration inside the shell is varied. Measuring the [Formula: see text] and [Formula: see text] in-plane Bragg reflections normal to the nanowire side edges and side facets, we observe a transition from elastic to plastic strain release for a shell indium content x > 0.5. Above the onset of plastic strain relaxation, indium rich mounds and an indium poor coherent shell grow simultaneously around the GaAs core. Mound formation was observed for indium contents x = 0.5 and 0.6 by scanning electron microscopy. Considering both the measured radial reflections and the axial 111 Bragg reflection, the 3D strain variation was extracted separately for the core and the In x Ga1-x As shell.

Sub-nanograin metal based high efficiency multilayer reflective optics for high energies.

The present finding illuminates the physics of the formation of interfaces of metal based hetero-structures near layer continuous limit as an approach to develop high-efficiency W/B4C multilayer (ML) optics with ML periodicity varying d = 1.86-1.23 nm at a fixed number of layer pairs N = 400. The microstructure of metal layers is tailored near the onset of grain growth to control the surface density of grains resulting in small average sizes of grains to sub-nanometers. This generates concurrently desirable atomically sharp interfaces, high optical contrast, and desirable stress properties over a large number of periods, which have evidence through the developed ML optics. We demonstrate significantly high reflectivities of ML optics measured in the energy range 10-20 keV, except for d = 1.23 nm due to quasi-continuous layers. The reflectivities at soft gamma-rays are predicted.

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.

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.

Quantitative analysis of time-resolved RHEED during growth of vertical nanowires.

We present an approach for quantitative evaluation of time-resolved reflection high-energy electron diffraction (RHEED) intensity patterns measured during the growth of vertical, free-standing nanowires (NWs). The approach considers shadowing due to attenuation by absorption and extinction within the individual nanowires and estimates the time dependence of its influence on the RHEED signal of the nanowire ensemble as a function of instrumental RHEED parameters and the growth dynamics averaged over the nanowire ensemble. The developed RHEED simulation model takes into account the nanowire structure evolution related to essential growth aspects, such as axial growth, radial growth with tapering and facet growth, as well as so-called parasitic intergrowth on the substrate. It also considers the influence of the NW density, which turns out to be a sensitive parameter for the time-dependent interpretation of the intensity patterns. Finally, the application potential is demonstrated by evaluating experimental data obtained during molecular beam epitaxy (MBE) of self-catalysed GaAs nanowires. We demonstrate, how electron shadowing enables a time-resolved analysis of the crystal structure evolution at the top part of the growing NWs. The approach offers direct access to study growth dynamics of polytypism in nanowire ensembles at the growth front region under standard growth conditions.

Energy-dispersive Laue diffraction by means of a pnCCD detector coupled to a CsI(Tl) scintillator using ultra-hard X-ray synchrotron radiation.

The lattice parameters and unit-cell orientation of an SrLaAlO4 crystal have been determined by means of energy-dispersive X-ray Laue diffraction (EDLD) using a pnCCD detector coupled to a columnar structure CsI(Tl) scintillator in the energy range between 40 and 130 keV. By exploiting the high quantum efficiency (QE) achieved by this combined detection system for hard X-rays, a large number of Bragg reflections could be recorded by the relatively small detector area, allowing accurate and fast determination of the lattice parameters and the moduli of the structure factors. The experiment was performed on the energy-dispersive diffraction (EDDI) beamline at the BESSY II synchrotron using a pnCCD detector with 128 × 128 pixels. Since the energies and positions of the Laue peaks can be recorded simultaneously by the pnCCD system, the tetragonal structure of the investigated specimen was determined without any prior information. The unit-cell parameters and the angles between the lattice vectors were evaluated with an accuracy of better than 0.7%, while the structure-factor moduli of the reflections were determined with a mean deviation of 2.5% relative to the theoretical values.

Impact of the Shadowing Effect on the Crystal Structure of Patterned Self-Catalyzed GaAs Nanowires.

The growth of regular arrays of uniform III-V semiconductor nanowires is a crucial step on the route toward their application-relevant large-scale integration onto the Si platform. To this end, not only does optimal vertical yield, length, and diameter uniformity have to be engineered, but also, control over the nanowire crystal structure has to be achieved. Depending on the particular application, nanowire arrays with varying area density are required for optimal device efficiency. However, the nanowire area density substantially influences the nanowire growth and presents an additional challenge for nanowire device engineering. We report on the simultaneous in situ X-ray investigation of regular GaAs nanowire arrays with different area density during self-catalyzed vapor-liquid-solid growth on Si by molecular-beam epitaxy. Our results give novel insight into selective-area growth and demonstrate that shadowing of the Ga flux, occurring in dense nanowire arrays, has a crucial impact on the evolution of nanowire crystal structure. We observe that the onset of Ga flux shadowing, dependent on array pitch and nanowire length, is accompanied by an increase of the wurtzite formation rate. Our results moreover reveal the paramount role of the secondary reflected Ga flux for VLS NW growth (specifically, that flux that is reflected directly into the liquid Ga droplet).

Phase Transitions and Formation of a Monolayer-Type Structure in Thin Oligothiophene Films: Exploration with a Combined In Situ X-ray Diffraction and Electrical Measurements.

A combination of in situ electrical and grazing-incidence X-ray diffraction (GIXD) is a powerful tool for studies of correlations between the microstructure and charge transport in thin organic films. The information provided by such experimental approach can help optimizing the performance of the films as active layers of organic electronic devices. In this work, such combination of techniques was used to investigate the phase transitions in vacuum-deposited thin films of a common organic semiconductor dihexyl-quarterthiophene (DH4T). A transition from the initial highly crystalline phase to a mesophase was detected upon heating, while only a partial backward transition was observed upon cooling to room temperature. In situ electrical conductivity measurements revealed the impact of both transitions on charge transport. This is partly accounted for by the fact that the initial crystalline phase is characterized by inclination of molecules in the plane perpendicular to the π-π stacking direction, whereas the mesophase is built of molecules tilted in the direction of π-π stacking. Importantly, in addition to the two phases of DH4T characteristic of the bulk, a third interfacial substrate-stabilized monolayer-type phase was observed. The existence of such interfacial structure can have important implications for the charge mobility, being especially favorable for lateral two-dimensional charge transport in the organic field-effect transistors geometry.

Correlated Nanoscale Analysis of the Emission from Wurtzite versus Zincblende (In,Ga)As/GaAs Nanowire Core-Shell Quantum Wells.

While the properties of wurtzite GaAs have been extensively studied during the past decade, little is known about the influence of the crystal polytype on ternary (In,Ga)As quantum well structures. We address this question with a unique combination of correlated, spatially resolved measurement techniques on core-shell nanowires that contain extended segments of both the zincblende and wurtzite polytypes. Cathodoluminescence hyperspectral imaging reveals a blue-shift of the quantum well emission energy by 75 ± 15 meV in the wurtzite polytype segment. Nanoprobe X-ray diffraction and atom probe tomography enable k·p calculations for the specific sample geometry to reveal two comparable contributions to this shift. First, there is a 30% drop in In mole fraction going from the zincblende to the wurtzite segment. Second, the quantum well is under compressive strain, which has a much stronger impact on the hole ground state in the wurtzite than in the zincblende segment. Our results highlight the role of the crystal structure in tuning the emission of (In,Ga)As quantum wells and pave the way to exploit the possibilities of three-dimensional band gap engineering in core-shell nanowire heterostructures. At the same time, we have demonstrated an advanced characterization toolkit for the investigation of semiconductor nanostructures.

Ferroelectric domain wall dynamics characterized with X-ray photon correlation spectroscopy.

Technologically important properties of ferroic materials are determined by their intricate response to external stimuli. This response is driven by distortions of the crystal structure and/or by domain wall motion. Experimental separation of these two mechanisms is a challenging problem which has not been solved so far. Here, we apply X-ray photon correlation spectroscopy (XPCS) to extract the contribution of domain wall dynamics to the overall response. Furthermore, we show how to distinguish the dynamics related to the passing of domain walls through the periodic (Peierls) potential of the crystal lattice and through the random potential caused by lattice defects (pinning centers). The approach involves the statistical analysis of correlations between X-ray speckle patterns produced by the interference of coherent synchrotron X-rays scattered from different nanosize volumes of the crystal and identification of Poisson-type contribution to the statistics. We find such a contribution in the thermally driven response of the monoclinic phase of a ferroelectric PbZr0.55Ti0.45O3 crystal and calculate the number of domain wall jumps in the studied microvolume.

Radial Growth of Self-Catalyzed GaAs Nanowires and the Evolution of the Liquid Ga-Droplet Studied by Time-Resolved in Situ X-ray Diffraction.

We report on a growth study of self-catalyzed GaAs nanowires based on time-resolved in situ X-ray structure characterization during molecular-beam-epitaxy in combination with ex situ scanning-electron-microscopy. We reveal the evolution of nanowire radius and polytypism and distinguish radial growth processes responsible for tapering and side-wall growth. We interpret our results using a model for diameter self-stabilization processes during growth of self-catalyzed GaAs nanowires including the shape of the liquid Ga-droplet and its evolution during growth.

Strain relaxation and ambipolar electrical transport in GaAs/InSb core-shell nanowires.

The growth, crystal structure, strain relaxation and room temperature transport characteristics of GaAs/InSb core-shell nanowires grown using molecular beam epitaxy are investigated. Due to the large lattice mismatch between GaAs and InSb of 14%, a transition from island-based to layer-like growth occurs during the formation of the shell. High resolution transmission electron microscopy in combination with geometric phase analyses as well as X-ray diffraction with synchrotron radiation are used to investigate the strain relaxation and prove the existence of different dislocations relaxing the strain on zinc blende and wurtzite core-shell nanowire segments. While on the wurtzite phase only Frank partial dislocations are found, the strain on the zinc blende phase is relaxed by dislocations with perfect, Shockley partial and Frank partial dislocations. Even for ultrathin shells of about 2 nm thickness, the strain caused by the high lattice mismatch between GaAs and InSb is relaxed almost completely. Transfer characteristics of the core-shell nanowires show an ambipolar conductance behavior whose strength strongly depends on the dimensions of the nanowires. The interpretation is given based on an electronic band profile which is calculated for completely relaxed core/shell structures. The peculiarities of the band alignment in this situation implies simultaneously occupied electron and hole channels in the InSb shell. The ambipolar behavior is then explained by the change of carrier concentration in both channels by the gate voltage.

Characterization of individual stacking faults in a wurtzite GaAs nanowire by nanobeam X-ray diffraction.

Coherent X-ray diffraction was used to measure the type, quantity and the relative distances between stacking faults along the growth direction of two individual wurtzite GaAs nanowires grown by metalorganic vapour epitaxy. The presented approach is based on the general property of the Patterson function, which is the autocorrelation of the electron density as well as the Fourier transformation of the diffracted intensity distribution of an object. Partial Patterson functions were extracted from the diffracted intensity measured along the [000\bar{1}] direction in the vicinity of the wurtzite 00\bar{1}\bar{5} Bragg peak. The maxima of the Patterson function encode both the distances between the fault planes and the type of the fault planes with the sensitivity of a single atomic bilayer. The positions of the fault planes are deduced from the positions and shapes of the maxima of the Patterson function and they are in excellent agreement with the positions found with transmission electron microscopy of the same nanowire.

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.

κ-Carrageenan Enhances the Biomineralization and Osteogenic Differentiation of Electrospun Polyhydroxybutyrate and Polyhydroxybutyrate Valerate Fibers.

Novel electrospun materials for bone tissue engineering were obtained by blending biodegradable polyhydroxybutyrate (PHB) or polyhydroxybutyrate valerate (PHBV) with the anionic sulfated polysaccharide κ-carrageenan (κ-CG) in varying ratios. In both systems, the two components phase separated as shown by FTIR, DSC and TGA. According to the contact angle data, κ-CG was localized preferentially at the fiber surface in PHBV/κ-CG blends in contrast to PHB/κ-CG, where the biopolymer was mostly found within the fiber. In contrast to the neat polyester fibers, the blends led to the formation of much smaller apatite crystals (800 nm vs 7 µm). According to the MTT assay, NIH3T3 cells grew in higher density on the blend mats in comparison to neat polyester mats. The osteogenic differentiation potential of the fibers was determined by SaOS-2 cell culture for 2 weeks. Alizarin red-S staining suggested an improved mineralization on the blend fibers. Thus, PHBV/κ-CG fibers resulted in more pronounced bioactive and osteogenic properties, including fast apatite-forming ability and deposition of nanosized apatite crystals.