Extended Defects Research Articles

Defect Structure and Luminescence of κ‐Ga2O3 Micro‐Monocrystals

Wide bandgap orthorhombic polymorph of gallium oxide (κ‐Ga2O3) possessing a high spontaneous polarization grown on wurtzite‐type semiconducting substrates is considered to create a high mobility electron channel suitable for applications. Such κ‐Ga2O3 layers are composed of hexagon microprisms whose properties affect the lateral electric conductance. In this work, the structure and recombination properties of extended defects in individual “suspended” thin microprisms are investigated with transmission and scanning electron microscopy techniques (STEM, HR‐TEM) including cathodoluminescence (CL‐SEM). It is established that the microprism is composed of six equisized orthorhombic domains bounded by twin domain boundaries (TDBs) along the directions <110>. Twin domain contains a parallel array of antiphase boundaries (APB) of a high density stretched in the [010] direction. APBs possess steps or interruption and can form double oppositely shifted spatially separated layers (APB dipoles). TDBs on majority of their length are incoherent and serve as the border for the APB terminations. Panchromatic CL maps reveal either enhanced or reduced intensity of APB without noticeable spectral changes. CL intensity enhancement is proposed to be due to enhanced electron–hole generation caused by excess scattering of primary electron beam by APBs in thin films while, in fact, APB exhibits enhanced nonradiative recombination activity.

Anisotropy of radiation-induced defects in Yb-implanted β-Ga2O3

RE-doped β-Ga2O3 seems attractive for future high-power LEDs operating in high irradiation environments. In this work, we pay special attention to the issue of radiation-induced defect anisotropy in β-Ga2O3, which is crucial for device manufacturing. Using the RBS/c technique, we have carefully studied the structural changes caused by implantation and post-implantation annealing in two of the most commonly used crystallographic orientations of β-Ga2O3, namely the (-201) and (010). The analysis was supported by advanced computer simulations using the McChasy code. Our studies reveal a strong dependence of the structural damage induced by Yb-ion implantation on the crystal orientation, with a significantly higher level of extended defects observed in the (-201) direction than for the (010). In contrast, the concentration and behavior of simple defects seem similar for both oriented crystals, although their evolution suggests the co-existence of two different types of defects in the implanted zone with their different sensitivity to both, radiation and annealing. It has also been found that Yb ions mostly occupy the interstitial positions in β-Ga2O3 crystals that remain unchanged after annealing. The location is independent of the crystal orientations. We believe that these studies noticeably extend the knowledge of the radiation-induced defect structure, because they dispel doubts about the differences in the damage level depending on crystal orientation, and are important for further practical applications.

In-Situ TEM study of microstructural evolution in proton irradiated single crystal UO2 under high-temperature annealing

Understanding microstructural changes in nuclear fuels under different irradiation conditions is important as it directly affects thermal, oxidation and mechanical properties and thereby reactor safety and longevity. This work focuses on the effect of temperature on the evolution of extended defects in uranium dioxide. In-situ transmission electron microscopy (TEM) annealing of proton irradiated UO2 was performed at different temperatures: 900 °C, 1100 °C and 1300 °C, 1 hour for each temperature. Microstructural evolution in terms of dislocation loops and voids were captured using in-situ TEM during annealing at different temperatures. Post-annealing at each temperature, detailed characterization using rel-rod dark field, bright field, and underfocus-overfocus imaging in TEM were used to identify faulted loops, perfect dislocation loops, and voids, respectively. Dislocation loops showed migration, disappearance, coalescence and loop-line interactions which significantly contributed to the recovery process during annealing at temperatures of 1100 °C and 1300 °C. Small voids were observed at 900 °C (diameter ∼ 0.5–1.5 nm) and grew rapidly during 1300 °C annealing (diameter ∼ 1–3 nm). Void growth was attributed to vacancy absorption, Ostwald ripening and void coalescence mechanisms. Extensive void growth was unique to in-situ TEM annealing due to free surface effect as ex-situ annealing confirmed negligible TEM resolvable (> 0.5 nm) voids at 1300 °C. The dislocation loops and voids behavior during in-situ TEM annealing were compared with rate theory and cluster dynamics predictions.

Laparoscopic ureteroplasty of a transplanted kidney using a healthy native ureter

Introduction. Ureteral strictures are a common urological complication of kidney transplantation. For short narrowings of the ureter, endoscopic operations are used; for extended defects the Boari operation is often performed. An alternative method may be to use a native ureter.Purpose of the study. To study the results of such operations in four patients.Materials & methods. We observed four patients with extended ureteral strictures of a transplanted kidney. Among them were three women and one man. Previously, all patients had undergone a cadaveric kidney transplant; the time from the operation itself to the development of stricture ranged from 3 months to 13 years. Initially, all patients underwent percutaneous drainage of the pyelocaliceal system of the transplanted kidney. After stabilization of creatinine values, the pelvis or pyeloureteral segment of the transplanted kidney was isolated using a transperitoneal approach. Further, the lower third of the ipsilateral native ureter was crossed at the level of the iliac vessels. Its upper end was clipped and anastomosis with the pelvis or ureteropelvic junction of the graft was performed.Results. The procedures were successful in all patients. In three patients the operation was completed using a laparoscopic approach. In one patient in whom extensive ureteral obliteration developed 3 months after transplantation against the background of incompetent ureterocystoneoastomosis and urinary leakage, when the pelvis was isolated, which was covered by the external iliac vein, the latter was injured with bleeding. This required conversion to open access, suturing of the iliac vein defect, further excision of the pelvis and anastomosis with the native ureter. In the post-operative period, the patient developed thrombosis of the iliac and femoral veins below the suturing area, and successful thrombolytic therapy was performed. Nephrostomy drain was removed before discharge and the stent was removed on an outpatient visit 4 to 6 weeks after surgery. Currently the condition of all patients is stable, the graft is functioning, and their diuresis is unchanged, serum creatinine ranges from 106 to 180 μmol/l.Conclusion. The use of a healthy native ureter is an adequate method of replacement of extended ureteral strictures of the transplanted kidney.

Crystal Originated Defect Monitoring and Reduction in Production Grade SmartSiC™ Engineered Substrates

Power devices electronics based on Silicon Carbide (SiC) are emerging as a breakthrough technology for various applications. The link between the quality of SiC substrates and device performance has been widely discussed [1]. Smart Cut™ technology offers the opportunity to integrate a high quality SiC layer on a low resistivity handle wafer. Moreover the crystal quality of a single donor wafer can be replicated multiple times to provide an epitaxy-ready substrate in high volume [2]. Nevertheless, some extended grown-in defects of SiC starting material, like micro-pipes or bulk inclusions, may generate surface defects called "Crystal Originated Defects" (COD) on transferred layers. This paper explains how SmartSiC™ defect density can be reduced by limiting the number of extended defects on donor wafers. Specific inspection recipes were developed to monitor the starting material and the replicated engineered substrate: COD root-causes and effects were analyzed. We demonstrated how a well-suited quality control of donor wafers plays a major role to guarantee defect-free SmartSiC™ wafers.

TEM Investigation on High Dose Al Implanted 4H-SiC Epitaxial Layer

Within this work, the effect of high dose Al ion implantation on 4H-SiC epitaxial layer is displayed. Through TEM investigation it is demonstrated that the implanted surface is suitable as seed for subsequent epitaxial regrowth generating a crystal free of extended defects. In order to assess the defects within the projected range of the ion implanted area, High Angle Annular Dark Field STEM (HAADF-STEM) analyses were performed demonstrating the atomic arrangement of the lattice in correspondence of the dislocation loop and the deviation of the crystallographic planes of 4H-SiC, driven by stress relaxation, that determine the staircase configuration of the implant pattern. Further emphasis is given to the detailed analysis of the precipitates atomic structure, whose preferential localization is ascertained. Using Energy-Dispersive X-ray spectroscopy (EDS) analysis, the precipitate is finally established as Al crystal with an FCC structure.

Characterization of extended defects in 2D materials using aperture-based dark-field STEM in SEM

Quantitative diffraction contrast analysis with defined diffraction vectors is a well-established method in TEM for studying defects in crystalline materials. A comparable transmission technique is however not available in the more widely used SEM platforms. In this work, we transfer the aperture-based dark-field imaging method from the TEM to the SEM, thus enabling quantitative diffraction contrast studies at lower voltages in SEM. This is achieved in STEM mode by inserting a custom-made aperture between the sample and the STEM detector and centering the hole on a desired reflection. To select individual reflections for dark-field imaging, we use our Low Energy Nanodiffraction (LEND) setup [Schweizer et al., Ultramicroscopy 213, 112956 (2020)], which captures transmission diffraction patterns from a fluorescent screen positioned below the sample. The aperture-based dark-field STEM method is particularly useful for studying extended defects in 2D materials, where (i) stronger diffraction at the lower voltages used in SEM is advantageous, but (ii) two-beam conditions cannot be established, making quantitative diffraction contrast analysis with standard bright-field and annular dark-field detectors impossible. We demonstrate the method by studying basal plane dislocations in bilayer graphene, which have attracted considerable research interest due to their exceptional structural and electronic properties. Direct comparison of results obtained on identical dislocations by the established TEM method and by the new aperture-based dark-field STEM method in SEM shows that a reliable Burgers vector analysis is possible by applying the well-known g·b=0 invisibility criterion. We further use the LEND setup to acquire 4D-STEM data and show that the virtual dark-field images match well with those in aperture-based dark-field STEM images for reliable Burgers vector analysis.

(Invited) Advanced Electronic Characterization of Wide Band Gap Semiconductor Defects at the Nanoscale

Wide bandgap materials such as gallium nitride (GaN) and gallium oxide (Ga2O3) are currently under development for realizing next-generation high power electronic devices beyond silicon. Vertical structures produced through homoepitaxial growth are preferred for scaling high-voltage devices, which places strict demands on the quality of bulk substrates. In particular, extended defects can propagate during epitaxial growth into the active areas of devices. Therefore, there is a need for identifying defects and determining their electronic properties at relevant nano- to micro- scale dimensions in order to disentangle their combined effects on macroscopic devices. Here, we use a combination of laser-based photoemission electron microscopy (PEEM) and electrical atomic force microscopy (AFM) methodologies to investigate the local electronic properties of surface defects in epitaxially grown GaN and β-Ga2O3. PEEM is a non-scanning electron microscopy technique where photoelectrons emitted by a surface illuminated by deep-ultraviolet light are imaged with nanometer-scale spatial resolution. The emitted photoelectrons are sensitive to the local electronic structure, making PEEM a powerful tool for evaluating electronic changes at length scales relevant for devices, and provides valuable information for identifying “killer” defects which must be minimized during device growth and processing.The difficulty in producing large, low dislocation density bulk GaN substrates has led to longstanding issues with leakage current in diodes and transistor devices. We identify surface defects with different electronic properties in GaN epitaxy on different substrates using PEEM. We observe star-shaped defects on strain-patterned GaN substrates and elongated dark patches on growth ridges on ammonothermally grown GaN substrates. In both cases, the observed electronic changes in PEEM correlate directly with local electrical AFM measurements, revealing that local changes in the electronic structure at these defects results in altered electrical conduction.In contrast, the development of large bulk Ga2O3 substrates has been more successful, yet the identification and influence of various defects on device performance is still largely unknown at this point. The topography of β-Ga2O3 epitaxy varies widely between growth methods and substrate orientations. For example, β-Ga2O3 by hydride vapor physical epitaxy lacks fine structure, yet has surface defects that regularly appear in parallel orientations. In β-Ga2O3 grown on different substrate orientations, we observe variations in the surface electronic properties using PEEM. For certain substrate orientations and growths, we find nanoscale variations in doping, while other orientations display micron-scale electronic inhomogeneity and defects. Our results demonstrate that laser-based PEEM can be a powerful tool for detecting electrically active defects, as well as evaluating the nanoscale electronic homogeneity of wide bandgap semiconductors.

Understanding Atomic-Scale Dynamics of Defects in Complex Oxides for Memristive Devices

The exceptional resistive switching characteristics of complex oxides make them promising for use in memristors to mimic biological synapses in neuromorphic computing architectures in an energy-efficient manner. Specifically, the electrical conductance of complex oxides can be controllable switched across multiple orders of magnitude by either (a) electroforming a conduction channel (e.g., in tungsten oxide), or (b) inducing Mott-Hubbard transition (e.g., in rare-earth nickelates)– both via controlled migration of defects (such as oxygen vacancies) under applied bias. However, development of accurate neuromorphic computers (i.e., low variability) remains extremely challenging due to a lack of fundamental understanding of the atomic-scale processes that underlie migration and spatiotemporal evolution of oxygen vacancies (and other extended defects) over nano-to-mesoscopic length/timescales under applied electric field. Here, we demonstrate that a synergistic integration of density functional theory (DFT) calculation, ab initio/classical molecular dynamics (AIMD/CMD) simulations, precision synthesis, and multi-modal X-ray imaging experiments provides an effective route to address this knowledge gap. First, we use a combination of multi-modal X-ray imaging (with chemical/structural sensitivity) and CMD simulations to show that the intrinsic randomness of electroforming process in tungsten-oxide memristors can be minimized by careful introduction of sharp protrusions in the electrode gap. We find that sharp protrusions confine the electric field, which yields a reproducible distribution of oxygen vacancies over several switching cycles; and reliably form conduction channel in a specific location in the memristor. Next, we employed a large dataset of data from DFT calculations and short AIMD trajectories to develop deep neural network (DNN) models to accurately capture energetics, atomic forces, atomic charges, and maximally localized Wannier centers in rare-earth nickelates (RNO). CMD simulations based on these newly developed DNNs show that metal-insulator transition (MIT) in RNO occurs via a local structural distortion in the extended nickel structure, which facilitates the electronic instability and causes a sharp concomitant Ni-O bond and Ni-charge disproportion with decreasing temperature; this MIT is also strongly influenced by applied pressure and rare-earth ion. Furthermore, DFT calculations reveal the correlations the oxygen stoichiometry, OV distribution (including different NiOx motifs), OV transport, and electron-lattice coupling in perovskite nickelates. These results will be discussed in the context of controlling defect-induced transitions to design accurate and reliable memristive devices for neuromorphic computing platforms that are vital for artificial intelligence technologies.

Biological conduits based on spider silk for reconstruction of extended nerve defects.

The availability of appropriate conduits remains an obstacle for successful reconstruction of long-distance nerve defects. In previous sheep trials, we were able to bridge 6 cm nerve gaps with nerve conduits based on spider silk fibers with full functional outcomes. Here, we describe the first application of spider silk for nerve repair inhumans. Four patients with extended nerve defects (>20 cm) underwent nerve reconstruction by interposition of conduits that were composed of spider silk fibers contained in autologous veins. The longitudinal luminal fibers (approx.2500 fibers per graft) consisted of drag line silkfrom Trichonephila spiders. All patients were evaluated between 2and 10 years postreconstruction, clinically, and byneurography. In all patients, primary wound healing and no adverse reactions to the implanted spider silk material wereobserved. Patients regained the following relevant functions: protective sensibility, full flexor function with near-normal grasp and powerful function after microvascular gracilis muscle transfer, and key grip function and gross finger flexion after additional tenodesis. One patient with sciatic nerve reconstruction developed protective sensibility of the lower leg, foot, and gait, enabling normal walking and jogging. No neuroma formation or neuropathic or chronic pain occurred in any of the patients. For patients with extended peripheral nerve defects in the extremities, use of conduits based on spider silk fibers offers the possibility of restoring sensory function and protection from neuroma. This kind of nerve bridges provides new perspectives for the reconstruction of complex and long-distance nerve defects.

Loss of Tet hydroxymethylase activity causes mouse embryonic stem cell differentiation bias and developmental defects.

The TET family is well known for active DNA demethylation and plays important roles in regulating transcription, the epigenome and development. Nevertheless, previous studies using knockdown (KD) or knockout (KO) models to investigate the function of TET have faced challenges in distinguishing its enzymatic and nonenzymatic roles, as well as compensatory effects among TET family members, which has made the understanding of the enzymatic role of TET not accurate enough. To solve this problem, we successfully generated mice catalytically inactive for specific Tet members (Tetm/m). We observed that, compared with the reported KO mice, mutant mice exhibited distinct developmental defects, including growth retardation, sex imbalance, infertility, and perinatal lethality. Notably, Tetm/m mouse embryonic stem cells (mESCs) were successfully established but entered an impaired developmental program, demonstrating extended pluripotency and defects in ectodermal differentiation caused by abnormal DNA methylation. Intriguingly, Tet3, traditionally considered less critical for mESCs due to its lower expression level, had a significant impact on the global hydroxymethylation, gene expression, and differentiation potential of mESCs. Notably, there were common regulatory regions between Tet1 and Tet3 in pluripotency regulation. In summary, our study provides a more accurate reference for the functional mechanism of Tet hydroxymethylase activity in mouse development and ESC pluripotency regulation.

Tunnel bone grafting for the reconstruction of an extended end defect of the alveolar bone of the lower jaw: a clinical case

Tunnel bone grafting for the reconstruction of an extended end defect of the alveolar bone of the lower jaw: a clinical case

Electron levels of defects in In(Ga)As/(In)GaAs nanostructures: A review

The data on electron levels induced by defects in In(Ga)As/(In)GaAs nanostructures, their localization, activation energy and identification have been systematically reviewed. Point defects inherent to GaAs and found in the (In)GaAs-based nanostructures have been listed, and their classification has been clarified, including EB3, EL2, EL3, EL4 (M4), EL5, EL6 (M3), EL7, EL8, EL9 (M2), EL10 (M1), EL11 (M0) and M00. The effect of the interfaces on the formation of different types of extended defects has been described. All the levels of electron traps found in heterostructures with quantum wells, wires and dots by deep level spectroscopies have been collected in a table with indication of the detection technique, object, location in the structure and their origin assumed. This overview can be useful as a reference material for researchers who study these nanostructures.

A Processing Route to Chalcogenide Perovskites Alloys with Tunable Band Gap via Anion Exchange

AbstractThe synthesis of BaZr(S,Se)3 chalcogenide perovskite alloys is demonstrated by selenization of BaZrS3 thin films. The anion‐exchange process produces films with tunable composition and band gap without changing the orthorhombic perovskite crystal structure or the film microstructure. The direct band gap is tunable between 1.5 and 1.9 eV. The alloy films made in this way feature one‐hundred‐times stronger photoconductive response and a lower density of extended defects, compared to alloy films made by direct growth. The perovskite structure is stable in high‐selenium‐content thin films with and without epitaxy. The manufacturing‐compatible process of selenization in H2Se gas may spur the development of chalcogenide perovskite solar cell technology.

Formation of an extended defect cluster in cuprous oxide

Intrinsic defects and defect clusters play an important role in the room-temperature transport of cuprous oxide. Neutralization of these defects by doping and/or modifying the synthesis process is essential to improve the room-temperature hole mobility in cuprous oxide. Toward this end, we annealed polycrystalline cuprous oxide under Cu-rich conditions, which led to the neutralization of the intrinsic acceptor defect. The concentration of both the acceptor defects ( VCu and VCusplit ) that are already present, reduces by four to five orders of magnitude. This is in accordance with the amount of possible Cu incorporation under different annealing conditions, indicating the backfilling of a large fraction of the Cu vacancies. Unforeseeably, the experimental conditions lead to the creation of yet another higher-order extended defect (3 VCu + 2Cu i ) with a defect level at ≈0.5 eV above the valence band. The formation of such a defect is also indirectly suggested by the analysis of carrier concentration vs. temperature data and first-principles calculations. Such singly ionized higher-order defects with a possibly higher capture cross-section act as more effective traps resulting in reduced hole mobility.

ScN/GaN(11̅00): A New Platform for the Epitaxy of Twin-Free Metal-Semiconductor Heterostructures.

We study the molecular beam epitaxy of rock-salt ScN on the wurtzite GaN(11̅00) surface. To this end, ScN is grown on freestanding GaN(11̅00) substrates and self-assembled GaN nanowires exhibiting (11̅00) sidewalls. On both substrates, ScN crystallizes twin-free thanks to a specific epitaxial relationship, namely ScN(110)[001]∥GaN(11̅00)[0001], providing a congruent, low-symmetry interface. The 13.1% uniaxial lattice mismatch occurring in this orientation mostly relaxes within the first few monolayers of growth by forming a near-coincidence site lattice, where 7 GaN planes coincide with 8 ScN planes, leaving the ScN surface nearly free of extended defects. Overgrowth of the ScN with GaN leads to a kinetic stabilization of the zinc blende phase, that rapidly develops wurtzite inclusions nucleating on {111} nanofacets, commonly observed during zinc blende GaN growth. Our ScN/GaN(11̅00) platform opens a new route for the epitaxy of twin-free metal-semiconductor heterostructures including closely lattice-matched GaN, ScN, HfN, and ZrN compounds.

Laser‐Annealed SiO2/Si1−xGex Scaffolds for Nanoscaled Devices, Synergy of Experiment, and Computation

Laser‐Annealed SiO₂/Si_1−<i>x</i>Ge_<i>x</i> Scaffolds for Nanoscaled Devices, Synergy of Experiment, and Computation

Irregular network of extended defects in graphene and a new criterion of the crystal lattice melting

Investigation of graphite defects has long and rich history. However, it turned out, that most point defects in graphene, such as vacancies or topological Stone-Wales defect, have high formation energies, preventing them from formation in large quantities. Recently, we have proposed a new type of extended defects in graphene, with formation energy per atom only slightly above the melting temperature. This means, that these planar defects may occur near the melting temperature in sufficient quantities to influence the thermodynamic properties of graphene. Still, there is discrepancy between thermodynamic properties of these defects and their topology, which can be successfully resolved by proposition of a new defects' type – irregular network of extended defects, which will be described in this paper. The study of network stability from these defects enables us to formulate a new criterion of crystal lattice melting, which supersedes the Lindemann/Born criteria.

Effects of boron doping on the surface modification and defect evolution of silicon induced by proton implantation and annealing

Ultra-thin silicons can be obtained using SMART CUT technology, but there is a lack of systematic research on the effect of boron doping. This paper reports the effects of boron doping on surface modification and defect evolution. Monocrystalline silicon samples with different concentrations of boron doping were implanted to 3.5 × 1017H+/cm2 using a 1.52 MeV High Intensity Proton Implanter (HIPI) and annealed at 300, 400, and 550 ℃. The annealed samples were analyzed by non-contact optical profilometry, Raman spectroscopy, SEM, and TEM. The results show that appropriate boron doping can reduce the surface roughness of the exfoliated samples; excessive boron doping leads to a significant increase in surface roughness (∼525 nm) and produces a step-like morphology. Boron doping leads to changes in the type, concentration and dissociation temperature of hydrogenated defects during implantation. These changes result in the width of damage band changes vary with doping concentration. The density and diameter of the hydrogenated extended defects also changed, which results in the surface modification of samples, such as the change of the surface morphology and substrate roughness. In the end of the paper, the paper discusses the correlation between surface morphology and internal damage for different concentrations of boron doping.

Bipolar pulse anodizing of aluminum: Understanding the fundamental electrochemical mechanisms

Anodic aluminum oxides (AAO) with attractive morphological properties might be obtained by pulse anodizing via controlled hydrogen release during the cathodic step. In order to enhance such processes currently relying on empirical studies, the present paper aims to investigate basically the AAO formation on pure aluminum in sulfuric acid during a bipolar pulse anodizing process, by combining in situ electrochemical measurements and cross-section scanning electron microscopy. Results show that the hydrogen evolution at the metal/oxide interface during the cathodic step can be easily managed by current control. Actually, under cathodic galvanostatic conditions, successive mechanisms occur, depending on both the duration and the current density: a first stage corresponds to the reorganization of the electric charges and the migration of H+ through the AAO barrier layer and is followed by hydrogen evolution at the metal/oxide interface, which induces the formation of local or more extended defects at the metal/oxide interface until the detachment of the AAO layer.