3D electron diffraction goes multipolar.

Over 30 years ago, it was shown that bonding between atoms has a noticeable effect on convergent beam electron diffraction patterns. The paper by Olech et al. [(2024). IUCrJ, 11, 309-324] demonstrates that its influence is also clearly present in 3D electron diffraction data, opening up new possibilities for quantum crystallography.

Parameterized absorptive electron scattering factors.

In electron diffraction, thermal atomic motion produces incoherent scattering over a relatively wide angular range, which appears as a diffuse background that is usually subtracted from measurements of Bragg spot intensities in structure solution methods. The transfer of electron flux from Bragg spots to diffuse scatter is modelled using complex scattering factors f + if' in the Bloch wave methodology. In a two-beam Einstein model the imaginary `absorptive' scattering factor f' can be obtained by the evaluation of an integral containing f over all possible scattering angles. While more sophisticated models of diffuse scatter are widely used in the electron microscopy community, it is argued in this paper that this simple model is appropriate for current structure solution and refinement methods. The two-beam model is a straightforward numerical calculation, but even this simplistic approach can become time consuming for simulations of materials with large numbers of atoms in the unit cell and/or many incident beam orientations. Here, a parameterized form of f' is provided for 103 elements as neutral, spherical atoms that reduces calculation time considerably.

A new electron diffraction approach for structure refinement applied to Ca3Mn2O7.

The digital large-angle convergent-beam electron diffraction (D-LACBED) technique is applied to Ca3Mn2O7 for a range of temperatures. Bloch-wave simulations are used to examine the effects that changes in different parameters have on the intensity in D-LACBED patterns, and atomic coordinates, thermal atomic displacement parameters and apparent occupancy are refined to achieve a good fit between simulation and experiment. The sensitivity of the technique to subtle changes in structure is demonstrated. Refined structures are in good agreement with previous determinations of Ca3Mn2O7 and show the decay of anti-phase oxygen octahedral tilts perpendicular to the c axis of the A21am unit cell with increasing temperature, as well as the robustness of oxygen octahedral tilts about the c axis up to ∼400°C. The technique samples only the zero-order Laue zone and is therefore insensitive to atom displacements along the electron-beam direction. For this reason it is not possible to distinguish between in-phase and anti-phase oxygen octahedral tilting about the c axis using the [110] data collected in this study.

Structure refinement from 'digital' large angle convergent beam electron diffraction patterns.

We use semi-automated data acquisition and processing to produce digital large angle CBED (D-LACBED) patterns. We demonstrate refinements of atomic coordinates and isotropic Debye-Waller factors for well-known materials using simulations produced with a neutral, spherical independent atom model. We find that atomic coordinate refinements in Al2O3 have sub-pm precision and accuracy. Isotropic DWFs are accurate for Cu, a simple fcc metal, but do not agree with X-ray measurements of GaAs or Al2O3. This lack of agreement is probably caused by bonding and change transfer between atoms. While it has long been appreciated that CBED is sensitive to bonding, examination of D-LACBED data shows that some regions exhibit large changes in diffracted intensity from small changes in the periodic crystal potential. Models of bonding will be essential to fully interpret D-LACBED data.

Stable Defects in Semiconductor Nanowires.

Semiconductor nanowires are commonly described as being defect-free due to their ability to expel mobile defects with long-range strain fields. Here, we describe previously undiscovered topologically protected line defects with null Burgers vector that, unlike dislocations, are stable in nanoscale crystals. We analyze the defects present in semiconductor nanowires in regions of imperfect crystal growth, i.e., at the nanowire tip formed during consumption of the droplet in self-catalyzed vapor-liquid-solid growth and subsequent vapor-solid shell growth. We use a form of the Burgers circuit method that can be applied to multiply twinned material without difficulty. Our observations show that the nanowire microstructure is very different from bulk material, with line defects either (a) trapped by locks or other defects, (b) arranged as dipoles or groups with a zero total Burgers vector, or (c) have a zero Burgers vector. We find two new line defects with a null Burgers vector, formed from the combination of partial dislocations in twinned material. The most common defect is the three-monolayer high twin facet with a zero Burgers vector. Studies of individual nanowires using cathodoluminescence show that optical emission is quenched in defective regions, showing that they act as strong nonradiative recombination centers.

Fabrication, mechanical properties and in vitro degradation behavior of newly developed ZnAg alloys for degradable implant applications.

Zn and Zn-based alloys have been recognized as highly promising biodegradable materials for orthopedic implants and cardiovascular stents, due to their proved biocompatibility and, more importantly, lower corrosion rates compared to Mg alloys. However, pure Zn has poor mechanical properties. In this study, Ag is used as a promising alloying element to improve the mechanical properties of the Zn matrix as well as its biocompatibility and antibacterial properties. Accordingly, we design three ZnAg alloys with Ag content ranging from 2.5 to 7.0wt% and investigate the influence of the Ag content on mechanical and corrosion behavior of the alloys. The alloys are developed by casting process and homogenized at 410°C for 6h and 12h, followed by hot extrusion at 250°C with extrusion ratio of 14:1. Degradation behavior is assessed by electrochemical and static immersion tests in Hank's modified solution. Microstructural analysis reveals that hot extrusion significantly reduces the grain size of the alloys. Zn-7.0%Ag alloy shows a reasonably equiaxed and considerably refined microstructure with mean grain size of 1.5µm. Tensile tests at room temperature suggest that increasing the Ag content steadily enhances the tensile strength, while it does not affect the tensile ductility significantly. Zn-7.0%Ag shows high yield strength and ultimate tensile strength of 236MPa and 287MPa, respectively, which is due to the grain refinement and high volume fraction of fine AgZn3 particles precipitating along the grain boundaries during the extrusion process. Among all these alloys, Zn-7.0%Ag displayed superplasticity over a wide range of strain rates (from 5×10-4s-1 to 1.0×10-2s-1) providing the possibility of exploiting forming processes at rapid rates and/or even at lower temperatures. In addition, extruded alloys exhibit slightly faster degradation rate than pure Zn. X-ray diffraction results show the presence of ZnO and Zn(OH)2 on the degraded surfaces. Moreover, scanning electron microscopy imaging reveals that micro-galvanic corrosion is more pronounced on the alloys with higher Ag content due to the higher volume fraction of AgZn3 particles.

Novel Zn-based alloys for biodegradable stent applications: Design, development and in vitro degradation.

The search for a degradable metal simultaneously showing mechanical properties equal or higher to that of stainless steel and uniform degradation is still an open challenge. Several magnesium-based alloys have been studied, but their degradation rate has proved to be too fast and rarely homogeneous. Fe-based alloys show appropriate mechanical properties but very low degradation rate. In the present work, four novel Zn-Mg and two Zn-Al binary alloys were investigated as potential biodegradable materials for stent applications. The alloys were developed by casting process and homogenized at 350°C for 48h followed by hot extrusion at 250°C. Tube extrusion was performed at 300°C to produce tubes with outer/inner diameter of 4/1.5mm as precursors for biodegradable stents. Corrosion tests were performed using Hanks׳ modified solution. Extruded alloys exhibited slightly superior corrosion resistance and slower degradation rate than those of their cast counterparts, but all had corrosion rates roughly half that of a standard purity Mg control. Hot extrusion of Zn-Mg alloys shifted the corrosion regime from localized pitting to more uniform erosion, mainly due to the refinement of second phase particles. Zn-0.5Mg is the most promising material for stent applications with a good combination of strength, ductility, strain hardening exponent and an appropriate rate of loss of mechanical integrity during degradation. An EBSD analysis in the vicinity of the laser cut Zn-0.5Mg tube found no grain coarsening or texture modification confirming that, after laser cutting, the grain size and texture orientation of the final stent remains unchanged. This work shows the potential for Zn alloys to be considered for stent applications.

Structural, optical and vibrational properties of self-assembled Pbn+1(Ti1-x Fex)nO(3n+1)-δ Ruddlesden-Popper superstructures.

Bulk crystals and thin films of PbTi(1-x)FexO3(-δ) (PTFO) are multiferroic, exhibiting ferroelectricity and ferromagnetism at room temperature. Here we report that the Ruddlesden-Popper phase Pbn+1(Ti(1-x)Fex)nO3(n+1)-δ forms spontaneously during pulsed laser deposition of PTFO on LaAlO3 substrates. High-resolution transmission electron microscopy, x-ray diffraction and x-ray photoemission spectroscopy were utilised to perform a structural and compositional analysis, demonstrating that n ≃ 8 and x ≃ 0.5. The complex dielectric function of the films was determined from far-infrared to ultraviolet energies using a combination of terahertz time-domain spectroscopy, Fourier transform spectroscopy, and spectroscopic ellipsometry. The simultaneous Raman and infrared activity of phonon modes and the observation of second harmonic generation establishes a non-centrosymmetric point group for Pbn+1(Ti0.5Fe0.5)nO3(n+1)-δ, a prerequisite for (but not proof of) ferroelectricity. No evidence of macroscopic ferromagnetism was found in SQUID magnetometry. The ultrafast optical response exhibited coherent magnon oscillations compatible with local magnetic order, and additionally was used to study photocarrier cooling on picosecond timescales. An optical gap smaller than that of BiFeO3 and long photocarrier lifetimes may make this system interesting as a ferroelectric photovoltaic.

III-V quantum light source and cavity-QED on silicon.

Non-classical light sources offer a myriad of possibilities in both fundamental science and commercial applications. Single photons are the most robust carriers of quantum information and can be exploited for linear optics quantum information processing. Scale-up requires miniaturisation of the waveguide circuit and multiple single photon sources. Silicon photonics, driven by the incentive of optical interconnects is a highly promising platform for the passive optical components, but integrated light sources are limited by silicon's indirect band-gap. III-V semiconductor quantum-dots, on the other hand, are proven quantum emitters. Here we demonstrate single-photon emission from quantum-dots coupled to photonic crystal nanocavities fabricated from III-V material grown directly on silicon substrates. The high quality of the III-V material and photonic structures is emphasized by observation of the strong-coupling regime. This work opens-up the advantages of silicon photonics to the integration and scale-up of solid-state quantum optical systems.

Structural analysis of strained quantum dots using nuclear magnetic resonance.

Strained semiconductor nanostructures can be used to make single-photon sources, detectors and photovoltaic devices, and could potentially be used to create quantum logic devices. The development of such applications requires techniques capable of nanoscale structural analysis, but the microscopy methods typically used to analyse these materials are destructive. NMR techniques can provide non-invasive structural analysis, but have been restricted to strain-free semiconductor nanostructures because of the significant strain-induced quadrupole broadening of the NMR spectra. Here, we show that optically detected NMR spectroscopy can be used to analyse individual strained quantum dots. Our approach uses continuous-wave broadband radiofrequency excitation with a specially designed spectral pattern and can probe individual strained nanostructures containing only 1 × 10(5) quadrupole nuclear spins. With this technique, we are able to measure the strain distribution and chemical composition of quantum dots in the volume occupied by the single confined electron. The approach could also be used to address problems in quantum information processing such as the precise control of nuclear spins in the presence of strong quadrupole effects.

Low voltage STEM imaging of multi-walled carbon nanotubes.

We present high magnification STEM images of multi-walled carbon nanotubes recorded with a 5 keV electron beam using a Helios Dual Beam microscope and a dedicated multi-segment transmission (STEM) detector. Images of carbon nanotubes recorded with bright-field (BF), annular dark-field (ADF) and high angle annular dark-field (HAADF) signals all show high contrast features, with internal structures 1-2 nm in width clearly revealed in the STEM images. Thicker regions of the nanotubes appear to show an unusual contrast reversal when comparing ADF and HAADF images. An understanding of the image contrast, and its dependence on thickness, is obtained by computing simulations of the ADF and HAADF images using Monte-Carlo software taking into account electron scattering in the nanotube.

Accurate ultra-low-energy secondary ion mass spectrometry analysis of wide bandgap GaN/In(x)Ga(1-x)N structures using optical conductivity enhancement.

Ultra-low-energy secondary ion mass spectrometry has been used to undertake a structural analysis of GaN-In(x)Ga(1-x)N (x approximately 0.25) quantum wells used in optoelectronic devices. The high resistivity of intrinsic GaN-In(x)Ga(1-x)N restricts the necessary electrical path between the analyzed area and the instrument ground potential resulting in surface charge accumulation. Consequently, unstable and unrepresentative depth profiles tend to be produced. A technique known as optical conductivity enhancement (OCE) has been used during depth profiling to reduce the material resistivity. This creates an electrical path between the sample and holder, eliminating charge build up and resulting in accurate depth profiles.

Blocking of indium incorporation by antimony in III-V-Sb nanostructures.

The addition of antimony to III-V nanostructures is expected to give greater freedom in bandgap engineering for device applications. One of the main challenges to overcome is the effect of indium and antimony surface segregation. Using several very high resolution analysis techniques we clearly demonstrate blocking of indium incorporation by antimony. Furthermore, indium incorporation resumes when the antimony concentration drops below a critical level. This leads to major differences between nominal and actual structures.

Electron tomography of III-V quantum dots using dark field 002 imaging conditions.

We present an evaluation of electron tomography of buried InAs quantum dots using dark field 002 imaging conditions. The compositional sensitivity of this imaging condition gives strong contrast among III-V materials of differing compositions and, in principle, should allow an accurate 3D model of the buried structures to be produced. The large extinction distance allows specimens several hundred nanometres in thickness to be examined and reduces the effect of strain contrast in the images, with the advantage that it can be performed using conventional transmission electron microscopy techniques. A two-beam condition must be maintained for all images, and the presence of other strong diffraction effects at certain specimen orientation results reduces the number of orientations available for tomography by approximately 10%. The data presented here are limited due to a lack of angular range in the data set but we find that an acceptable 3D model of a buried quantum dot may be produced by imposing cylindrical symmetry on the data set.

An approach to the systematic distortion correction in aberration-corrected HAADF images.

Systematic distortion has been analysed in high-angle annular dark-field (HAADF) images which may be caused by electrical interference. Strain mapping techniques have been applied to a strain-free GaAs substrate in order to provide a broad analysis of the influence of this distortion on the determination of local strain in the heterostructure. We have developed a methodology for estimating the systematic distortion, and we correct the original images by using an algorithm that removes this systematic distortion.

Dark field transmission electron microscope images of III-V quantum dot structures.

Multi-layer quantum dot structures are becoming increasingly common in order to improve the efficiency of quantum dot lasers. Each layer of dots may be influenced by the preceding dot layer, and the dot density can vary from layer to layer. Characterization of such structures relies on the reliable determination of the shape, size and density of dots in each layer. Dark field transmission electron microscopy (TEM) images using the 002 diffraction condition are frequently used, viewing the layers edge-on in a cross-section sample. A simple model is used to describe the contrast as a function of dot size and shape, specimen thickness, and the composition of the dot and surrounding materials. Good agreement with experimental results is obtained. It is found that the dot size is not accurately related to the bright region seen in such images. While 002 images can be used to determine the size and shape of dots, a density per unit area cannot be calculated in the cross section geometry without either measuring--or assuming--the specimen thickness. In multilayer structures, plan-view TEM images show the layers as overlapping, losing the information from individual layers. By tilting a cross-section specimen to allow imaging with the dark field 113 diffraction condition, the density in individual layers can be measured. Additional information, such as wetting layer thickness variations and alignment of dots due to surface roughness or substrate offcut, can also be obtained.