Distribution Of Point Defects Research Articles

Point defect distributions in ultrafast laser-induced periodic surface structures on β-Ga2O3

β-Ga2O3 has received widespread attention due to its ultrawide bandgap, which potentially permits applications in extreme conditions. Ultrafast laser irradiation of β-Ga2O3 provides a means for exploring the response of the material under such conditions, which could result in the generation of point defects as well as a localized modification of structural features that could yield properties that differ from the pristine surface. However, an understanding of defects generated by femtosecond laser irradiation in the vicinity of laser-induced periodic surface structures (LIPSS) remains to be explored. We correlate topographic features with optical and electronic properties by combining near-nm scale resolution cathodoluminescence with Kelvin probe force microscopy. Defects are found to correlate with crystalline order and near-surface morphology, as well as changes in work function. They are also suggested to be closely related to the formation of high spatial frequency LIPSS. These results suggest a need for precise tuning of laser irradiation conditions as well as possible post-processing to control defects in future Ga2O3 devices.

Heterogeneity in Point Defect Distribution and Mobility in Solid Ion Conductors.

Alkali metal anodes paired with solid ion conductors offer promising avenues for enhancing battery energy density and safety. To facilitate rapid ion transport crucial for fast charging and discharging of batteries, it is essential to understand the behavior of point defects in these conductors. In this study, we investigate the heterogeneity of defect distribution in two prototypical solid ion conductors, Li3OCl and Li2PO2N (LiPON), by quantifying the defect formation energy (DFE) as a function of distance from the surface and interface through first-principles simulations. To simulate defects at the electrode-electrolyte interface, we perform calculations of Li+ vacancy in Li3OCl near its interface with lithium metal. Our results reveal a significant difference between the bulk and surface/interface DFE which could lead to defect aggregation/depletion near the surface/interface. Interestingly, while Li3OCl has a lower surface DFE than the bulk in most cases, LiPON follows the opposite trend with a higher surface DFE compared to the bulk. Due to this difference between bulk and surface DFE, the defect density can be up to 14 orders of magnitude higher at surfaces compared to the bulk. Further, we reveal that the DFE transition from surface/interface to bulk is precisely characterized by an exponentially decaying function. By incorporating this exponential trend, we develop a revised model for the average behavior of defects in solid ion conductors that offers a more accurate description of the influence of grain sizes. Surface effects dominate for grain sizes ≲1 μm, highlighting the importance of surface defect engineering and the DFE function for accurately capturing ion transport in devices. We further explore the kinetics of defect redistribution by calculating the migration barriers for defect movement between bulk and surfaces. We find a highly asymmetric energy landscape for the lithium vacancies, exhibiting lower migration barriers for movement toward the surface compared to the bulk, while interstitial defects exhibit comparable kinetics between surface and bulk regions. These insights highlight the importance of considering both thermodynamic and kinetic factors in designing solid ion conductors for improved ion transport at surfaces and interfaces.

Microstructure and hardness of two-step reverse-polarity flash sintered high-purity Al2O3 ceramics

In this work, high-purity alumina ceramics were prepared by using two-step reverse polarity flash sintering (PR-FS). The effects of the time distribution between the first flash and the second flash on microstructure and hardness were studied. The results show that compared to the conventional DC flash sintered alumina, the RP–FS–ed samples exhibited more uniform-microstructure, finer grains, higher relative density, and higher hardness. The underlying mechanism for such more homogeneous microstructure was related to uniform distribution of point defects under effect of reverse polarity. Two-step reverse polarity flash sintering method offers a great potential in obtaining highly densified alumina ceramics with homogeneous microstructure.

Advancing piezoelectric properties of barium titanate ceramic through AC + DC field poling over Curie temperature

The significance of increased domain nucleation sites from smaller grain size (GS) of barium titanate (BT) ceramics on piezoelectric properties was analyzed for different types of poling, including conventional DC poling, modified DC poling, and AC plus DC poling, conducted at different poling temperatures. The AC plus DC poling conducted at 1.5 °C above the Curie temperature (T C) showed the highest piezoelectric constant (d 33) of 528 pC/N, with an average domain size of 100 nm observed after poling. The d 33 improvement was attributed to smaller domain size formation from field-induced phase transitions and homogenous distribution of point defects achieved by the AC field. Comparative analysis with larger grain BT ceramics under AC plus DC poling suggests that defects and volume fraction of grain boundaries in BT ceramics could have an effect on domain sizes.

Dislocation loop and irradiation-induced synergistic-competitive mechanism in Cu-rich precipitates: a phase-field study

Both irradiation and dislocations have been proposed as routes to rationally manipulate spatial distribution and micromorphology of precipitate. An interesting effect emerges in Fe–10at.%Cu–3at.%Mn–1.5at.%Ni–1.5at.%Al alloy due to the synergistic-competitive roles of dislocation loop and irradiation. Base on cascade mixing, vacancy-interstitial atoms and dislocation stress field model, we examine nucleation and growth dynamics of Cu-rich precipitates, where both dislocation loop and irradiation act in conjunction. Analytical treatments identify regimes, where the distribution of elements and point defects due to irradiation and dislocations are specific to the Cu-rich precipitates. Simulation results reveal that density, size and distribution of Cu-rich precipitates are a manifestation of the competing effects of the dislocation loop and the irradiation rate. More specifically, the dislocation loop preferentially assists the formation of precipitates and new dislocations at lower irradiation rates. Only the irradiation induces the formation of Cu-rich precipitates with the irradiation rate continues to increase. Equipped with molecular dynamics, where reproduces major interaction features of the solutes with point defects under displacement cascade, can verify multi-component morphologies of Cu-rich precipitates. This modeling framework provides an avenue to explore the role of dislocation loop and irradiation on the microstructural evolution of Cu-rich precipitates.

Tuning grain boundary cation segregation with oxygen deficiency and atomic structure in a perovskite compositionally complex oxide thin film

Compositionally complex oxides (CCOs) are an emerging class of materials encompassing high entropy and entropy stabilized oxides. These promising advanced materials leverage tunable chemical bond structure, lattice distortion, and chemical disorder for unprecedented properties. Grain boundary (GB) and point defect segregation to GBs are relatively understudied in CCOs even though they can govern macroscopic material properties. For example, GB segregation can govern local chemical (dis)order and point defect distribution, playing a critical role in electrochemical reaction kinetics, and charge and mass transport in solid electrolytes. However, compared with conventional oxides, GBs in multi-cation CCO systems are expected to exhibit more complex segregation phenomena and, thus, prove more difficult to tune through GB design strategies. Here, GB segregation was studied in a model perovskite CCO LaFe0.7Ni0.1Co0.1Cu0.05Pd0.05O3−x textured thin film by (sub-)atomic-resolution scanning transmission electron microscopy imaging and spectroscopy. It is found that GB segregation is correlated with cation reducibility—predicted by an Ellingham diagram—as Pd and Cu segregate to GBs rich in oxygen vacancies (VO··). Furthermore, Pd and Cu segregation is highly sensitive to the concentration and spatial distribution of VO·· along the GB plane, as well as fluctuations in atomic structure and elastic strain induced by GB local disorder, such as dislocations. This work offers a perspective of controlling segregation concentration of CCO cations to GBs by tuning reducibility of CCO cations and oxygen deficiency, which is expected to guide GB design in CCOs.

Atomistic Probing of Defect-Engineered 2H-MoTe2 Monolayers.

Point defects dictate various physical, chemical, and optoelectronic properties of two-dimensional (2D) materials, and therefore, a rudimentary understanding of the formation and spatial distribution of point defects is a key to advancement in 2D material-based nanotechnology. In this work, we performed the demonstration to directly probe the point defects in 2H-MoTe2 monolayers that are tactically exposed to (i) 200 °C-vacuum-annealing and (ii) 532 nm-laser-illumination; and accordingly, we utilize a deep learning algorithm to classify and quantify the generated point defects. We discovered that tellurium-related defects are mainly generated in both 2H-MoTe2 samples; but interestingly, 200 °C-vacuum-annealing and 532 nm-laser-illumination modulate a strong n-type and strong p-type 2H-MoTe2, respectively. While 200 °C-vacuum-annealing generates tellurium vacancies or tellurium adatoms, 532 nm-laser-illumination prompts oxygen atoms to be adsorbed/chemisorbed at tellurium vacancies, giving rise to the p-type characteristic. This work significantly advances the current understanding of point defect engineering in 2H-MoTe2 monolayers and other 2D materials, which is critical for developing nanoscale devices with desired functionality.

Molecular dynamics simulations of displacement damage in SiGe alloys induced by single and binary primary knock-on atoms under different temperatures

The defect evolution of primary radiation damage in SiGe alloys induced by single (Si or Ge) and binary (Si and Ge) primary knock-on atoms (PKAs) under different temperatures was investigated and evaluated by molecular dynamics simulations. The interatomic potential function was established by combining Stillinger−Weber potential with Ziegler–Biersack–Littmark potential, and it was validated by the lattice parameter, melting point, and thermal conductivity. The spatiotemporal distributions of point defects (Frenkel defects and antisites) and the lattice temperature showed a distinct difference to the kinetic energy (1 keV and 10 keV), PKA type (Si and/or Ge), and temperature of the SiGe alloy (100, 300, and 500 K). The radiation tolerance of the SiGe alloy to specific radiation environments was deduced based on the simulation results of displacement damage in this work.

Molecular dynamics simulation for radiation response of Nb bicrystal having Σ 13, Σ 29, and Σ 85 grain boundary

Nb is considered a promising candidate as a refractory element due to its high-temperature endurance, excellent thermal conductivity, and compatibility with liquid-metallic coolants in nuclear reactors. In the present study, radiation-based molecular dynamics numerical simulations were conducted in Σ 13, Σ 29, and Σ 85 symmetric tilt grain boundary models for pure Nb specimens. The stochastic high-energy collisions were modeled via large-scale atomic/molecular parallel simulator code to accurately investigate the radiation-induced defects generated in the order of picoseconds at the atomic level. The long-range embedded atom method potential and coulombic repulsive Ziegler–Biersack–Littmark potentials were smoothly overlaid for precise force-field interactions among Nb atoms. To investigate the ability to arrest the radiation-induced damage, the bi-crystal Nb specimens were irradiated at varying magnitudes of primary-knock-on atom (PKA) energies EPKA = 10 20, and 30 keV at temperature regimes 300, 600, and 900 K, respectively. The Frenkel pairs, complex linear defects, distribution of point defects as clusters, rate of defect annihilation, and temperature fluctuations within the displacement cascades of irradiated Nb specimens were comprehensively studied and reported. Here, the Nb-Σ 29 GB model survived with the lowest number of residual defects. Also, the recombination rate of the irradiated Nb specimens increases with the increase in temperature and PKA energy magnitude due to enhanced atomic mobility of the dislodged atoms. Hence, the bi-crystal Nb specimen can be favored for a radiation-tolerant material as structural components in next-generation reactors.

СИНТЕЗ И ЛЮМИНЕСЦЕНТНЫЕ СВОЙСТВА КУБИЧЕСКОЙ КЕРАМИКИ ZrO2-Y2O3-Eu2O3 И HfO2-Y2O3-Eu2O3

In this work samples of ZrO2-Y2O3-Eu2O3 and HfO2-Y2O3-Eu2O3. ceramics are synthesized. Cathodoluminescent studies were carried out. It is shown that, under the chosen synthesis regimes, the ZrO2-Y2O3-Eu2O3 ceramic is stabilized in the cubic phase and is single-phase. The HfO2-Y2O3-Eu2O3ceramic is also stabilized in the cubic phase with small amount of inclusions of the tetragonal phase. Also, in the HfO2-Y2O3-Eu2O3 sample, an inhomogeneous distribution of point defects associated with oxygen deficiency is observed.

A model for redistribution of oppositely charged point defects under the stress field of dislocations in nonstoichiometric ionic solids: Implications in doped ceria

Point defect distribution in the vicinity of discontinuities plays important role in the transport properties of nonstoichiometric ionic solids. Here, considering dopants and oxygen vacancies as the major point defects in doped ceria, we develop a Monte Carlo model to examine how the stress field of edge dislocations affect point defect distribution in their surroundings. Point defects are considered to interact with the elastic stress field of dislocations due to their misfit volume, and the electrostatic interaction between the point defects is also taken into account. In contrast with a prevalent theory of chemo-mechanical equilibrium in solid solutions, the model developed here is consistent with classical elasticity in that the point defects do not interact through their self-stress fields. Stress effects both on the defect distribution, and on the electric potential, are examined for a single dislocation as well as a periodic array of like dislocations. In agreement with previous atomistic simulations, the model predicts that electrostatic interactions drive enrichment or depletion of defects of both types on either the compressive or tensile side of edge dislocations depending on the ionic radius of the dopant. The stress field of an array of like dislocations periodic in the direction of the Burgers vector is shown to result in different bulk defect concentrations and bulk electric potentials on the opposite sides of the array, whereas for an array with repeat direction normal to the Burgers vector, defect enrichment and depletion emerge in alternate regions limited to the vicinity of the dislocations.

Predicting defect stability and annealing kinetics in two-dimensional PtSe2 using steepest entropy ascent quantum thermodynamics

The steepest-entropy-ascent quantum thermodynamic (SEAQT) framework was used to calculate the stability of a collection of point defects in 2D PtSe2 and predict the kinetics with which defects rearrange during thermal annealing. The framework provides a non-equilibrium, ensemble-based framework with a self-consistent link between mechanics (both quantum and classical) and thermodynamics. It employs an equation of motion derived from the principle of steepest entropy ascent (maximum entropy production) to predict the time evolution of a set of occupation probabilities that define the states of a system undergoing a non-equilibrium process. The system is described by a degenerate energy landscape of eigenvalues, and the entropy is found from the occupation probabilities and the eigenlevel degeneracies. Scanning tunneling microscopy was used to identify the structure and distribution of point defects observed experimentally in a 2D PtSe2 film. A catalog of observed defects includes six unique point defects (vacancies and anti-site defects on Pt and Se sublattices) and twenty combinations of multiple point defects in close proximity. The defect energies were estimated with density functional theory, while the degeneracies, or density of states, for the 2D film with all possible combinations or arrangements of cataloged defects was constructed using a non-Markovian Monte-Carlo approach (i.e. the Replica–Exchange–Wang–Landau algorithm (Vogel et al 2013 Phys. Rev. Lett. 110 210603)) with a q-state Potts model. The energy landscape and associated degeneracies were determined for a 2D PtSe2 film two molecules thick and unit cells in area (total of 5400 atoms). The SEAQT equation of motion was applied to the energy landscape to determine how an arbitrary density and arrangement of the six defect types evolve during annealing. Two annealing processes were modeled: heating from 77 K (−196 C) to 523 K (250 ∘C) and isothermal annealing at 523 K. The SEAQT framework predicted defect configurations, which were consistent with experimental STM images.

Interface effect of Fe and Fe2O3 on the distributions of ion induced defects

The stability of structural materials in extreme nuclear reactor environments—with high temperature, high radiation, and corrosive media—directly affects the lifespan of the reactor. In such extreme environments, an oxide layer on the metal surface acts as a passive layer protecting the metal underneath from corrosion. To predict the irradiation effect on the metal layer in these metal/oxide bilayers, nondestructive depth-resolved positron annihilation lifetime spectroscopy (PALS) and complementary transmission electron microscopy (TEM) were used to investigate small-scale defects created by ion irradiation in an epitaxially grown (100) Fe film capped with a 50 nm Fe2O3 oxide layer. In this study, the evolution of induced vacancies was monitored, from individual vacancy formation at low doses—10−5 dpa—to larger vacancy cluster formation at increasing doses, showing the sensitivity of positron annihilation spectroscopy technique. Furthermore, PALS measurements reveal how the presence of a metal–oxide interface modifies the distribution of point defects induced by irradiation. TEM measurements show that irradiation induced dislocations at the interface is the mechanism behind the redistribution of point defects causing their accumulation close to the interface. This work demonstrates that the passive oxide layers formed during corrosion impact the distribution and accumulation of radiation induced defects in the metal underneath and emphasizes that the synergistic impact of radiation and corrosion will differ from their individual impacts.

Probing oxygen vacancy distribution in oxide heterostructures by deep Learning-based spectral analysis of current noise

Exploiting oxygen vacancies has emerged as a versatile tool to tune the electronic and optoelectronic properties of complex oxide heterostructures. For the precise manipulation of the oxygen vacancies, the capability of directly probing the defect distribution in nanoscale is essential, but still lacking. Here we estimate the spatial distribution of oxygen vacancies in LaAlO3/SrTiO3 (LAO/STO) heterostructures by deep learning-based spectral analysis of current noise. The Monte-Carlo simulation and the specifically-designed deep learning model allow us to evaluate the defect distribution from current noise signals, measured through two-dimensional electron gas at the LAO/STO interface. We show that the oxygen vacancies are uniformly distributed over ∼ 100 nm from the interface in the as-grown LAO/STO heterostructure, while they can be migrated and confined to the interface within ∼ 14 nm by a vertical electric field at room temperature. These results introduce a powerful strategy to quantitatively probe the spatial distribution of point defects in oxide heterostructures with nm-scale precision.

Numerical investigation of impact of crystal diameter fluctuations on intrinsic point defects distribution in Si crystal grown by Czochralski method

Intrinsic point defects distribution is primarily controlled by the crystal pulling rate and temperature gradient directly at growth interface in silicon crystals grown using the Czochralski (Cz) method. The fluctuation in crystal diameter during the Cz process is one of the primary features associated with the temporal variation in growth process parameters, such as the pulling rate and heater power in the growth system, and which is expected to affect the thermal stress, defects, and dopant incorporation in a growing crystal. In this study, we numerically investigated the effect of temporal variation in crystal diameter on the intrinsic point defects distribution in a silicon crystal grown using the Cz method. The point defect dynamics in the crystal were numerically evaluated within a two-dimensional axisymmetric unsteady global heat and mass transport model for dynamically pulled silicon crystals, considering the shape of the crystal and diameter variation. Unsteady numerical simulations showed that the distribution of intrinsic point defects near crystal side surface in a growing silicon crystal significantly depends on the temporal variation in the crystal diameter.

Luminescence features of bulk crystals β-(Ga-=SUB=-x-=/SUB=-Al-=SUB=-1-x-=/SUB=-)-=SUB=-2-=/SUB=-O-=SUB=-3-=/SUB=-

This work is devoted to the study of the luminescence inhomogeneity nature of bulk (GaxAl1-x)2O3 samples grown by the Czochralski method. In the study of sample cleavages by the local cathodoluminescence method, regions with different luminescence were observed. To determine the cathodoluminescence contrast nature, we studied the uniformity of the aluminum distribution, the surface topography, and compared the luminescence spectra and the kinetics of emission bands for different regions of the sample. Also, to determine the luminescence bands nature, the crystal was annealed in air at 1000oC. This made it possible to observe the change in luminescence for the same region of the sample. Based on the studies performed, it was concluded that inhomogeneous luminescence is associated with the distribution of point defects. Upon annealing in air, the transformation of nonradiative recombination centers into luminescent centers was observed. Keywords: gallium oxide, luminescence, point defects.

Insight of displacement cascade evolution in gallium arsenide through molecular dynamics simulations

Displacement damage induced by space radiation is still a considerable challenge of expanding application of GaAs-based devices (e.g. solar cell, et al.) in space missions. In the current work, molecular dynamics (MD) simulations are applied to investigate displacement cascades evolution in GaAs at room temperature. A set of displacement events initiated by different energies (up to 50 keV) of primary knock-on atom (PKA) were simulated. An improved Wigner-Seitz (W-S) cell method was developed by introducing a simple criterion for more accurate identification of interstitials and antisites. Based on the present defect analysis method, the generation, evolution and distribution of point defects were discussed at first. Then, the mechanisms of both vacancy and interstitial cluster evolutions along simulation time were presented. The results indicate that both Ga and As type defects play the same crucial role among interstitials, antisites and vacancies. As the energy of PKA increases, the start points of heat spike phase postpone slightly. Moreover, the non-linear increase of surviving defects accompanied with the rise of the energy of PKA is considered as contribution of directly amorphous pockets. During the stage Ⅰ of cascade, as time progresses, different size clusters show up in succession from small size (i.e., between 2 and 5) to larger size. The medium and large vacancy clusters virtually only exist in the middle of cascades, and the majority of vacancies belong to the categorizes of single vacancy and small clusters, especially at the end of cascades. However, the medium and large interstitial clusters incline to hold up or grow continually at the MD time scale once they build up. Meanwhile, interstitials in larger clusters (30 ∼ ) account for more fraction as the energy of particles increases.

Direct Visualization of Large-Scale Intrinsic Atomic Lattice Structure and Its Collective Anisotropy in Air-Sensitive Monolayer 1T'- WTe2.

Probing large‐scale intrinsic structure of air‐sensitive 2D materials with atomic resolution is so far challenging due to their rapid oxidization and contamination. Here, by keeping the whole experiment including growth, transfer, and characterizations in an interconnected atmosphere‐control environment, the large‐scale intact lattice structure of air‐sensitive monolayer 1T’‐WTe2 is directly visualized by atom‐resolved scanning transmission electron microscopy. Benefit from the large‐scale atomic mapping, collective lattice distortions are further unveiled due to the presence of anisotropic rippling, which propagates perpendicular to only one of the preferential lattice planes in the same WTe2 monolayer. Such anisotropic lattice rippling modulates the intrinsic point defect (Te vacancy) distribution, in which they aggregate at the constrictive inner side of the undulating structure, presumably due to the ripple‐induced asymmetric strain as elaborated by density functional theory. The results pave the way for atomic characterizations and defect engineering of air‐sensitive 2D layered materials.

A Review of Grain Boundary and Heterointerface Characterization in Polycrystalline Oxides by (Scanning) Transmission Electron Microscopy

Interfaces such as grain boundaries (GBs) and heterointerfaces (HIs) are known to play a crucial role in structure-property relationships of polycrystalline materials. While several methods have been used to characterize such interfaces, advanced transmission electron microscopy (TEM) and scanning TEM (STEM) techniques have proven to be uniquely powerful tools, enabling quantification of atomic structure, electronic structure, chemistry, order/disorder, and point defect distributions below the atomic scale. This review focuses on recent progress in characterization of polycrystalline oxide interfaces using S/TEM techniques including imaging, analytical spectroscopies such as energy dispersive X-ray spectroscopy (EDXS) and electron energy-loss spectroscopy (EELS) and scanning diffraction methods such as precession electron nano diffraction (PEND) and 4D-STEM. First, a brief introduction to interfaces, GBs, HIs, and relevant techniques is given. Then, experimental studies which directly correlate GB/HI S/TEM characterization with measured properties of polycrystalline oxides are presented to both strengthen our understanding of these interfaces, and to demonstrate the instrumental capabilities available in the S/TEM. Finally, existing challenges and future development opportunities are discussed. In summary, this article is prepared as a guide for scientists and engineers interested in learning about, and/or using advanced S/TEM techniques to characterize interfaces in polycrystalline materials, particularly ceramic oxides.

Direct measurements of space-charge-regions in individual nanometer-scale crystals of Al2O3-rich magnesium-aluminate-spinel using off-axis electron holography and electron energy-loss spectroscopy

Space charge regions (SCR) in ionic solids, a result of an uneven distribution of point defects, alter their thermodynamic, transport, mechanical, and optical properties.We examine the formation of SCR in nanometer-scale sized crystals of magnesium-aluminate-spinel with excess Al2O3, MgO·1.27Al2O3. For this composition, the expected dominant point defects are anti-sites and cation vacancies.We determine the types, distribution and formation energies of charged point defects that form the SCR. Off-axis electron holography and electron energy-loss spectroscopy enabled to measure the electrostatic potential and distribution of Al·Mg anti-site charged point defects, respectively in individual crystals.We extract the width of the SCR, LSCR, between 1.7 and 2.1 nm. We measured the formation energy of charged vacancies following two extreme states, only aluminum or magnesium vacancies resulting in EfV″′Al=1.09±0.16eV and EfV″Mg=1.04±0.19eV, respectively.For crystals considerably larger than LSCR, V'''Al and VʺMg cation vacancies are the majority species at the particle core resulting in a negative charge density. When approaching the surface of the crystal, the space charge region is richer in Al·Mg defects.Finally, we examine the SCR as the crystal size is reduced, approaching LSCR. Measurements at particle cores of these crystals results in a positive charge due to the overlap of the SCR.