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At least 775 records · Page 43

Anomalous Defect Dependence of Thermal Conductivity in Epitaxial WO 3 Thin Films

Lattice defects typically reduce lattice thermal conductivity, which has been widely exploited in applications such as thermoelectric energy conversion. Here, an anomalous dependence of the lattice thermal conductivity on point defects is demonstrated in epitaxial WO 3 thin films. Depending on the substrate, the lattice of epitaxial WO 3 expands or contracts as protons are intercalated by electrolyte gating or oxygen vacancies are introduced by adjusting growth conditions. Surprisingly, the observed lattice volume, instead of the defect concentration, plays the dominant role in determining the thermal conductivity. In particular, the thermal conductivity increases significantly with proton intercalation, which is contrary to the expectation that point defects typically lower the lattice thermal conductivity. The thermal conductivity can be dynamically varied by a factor of ≈1.7 via electrolyte gating, and tuned over a larger range, from 7.8 to 1.1 W m -1 K -1 , by adjusting the oxygen pressure during film growth. The electrolyte-gating-induced changes in thermal conductivity and lattice dimensions are reversible through multiple cycles. These findings not only expand the basic understanding of thermal transport in complex oxides, but also provide a path to dynamically control the thermal conductivity.

36 MATERIALS SCIENCE↗

Engineering Electrical Transport by Implantation‐Induced Defects in CrN Films Without Affecting Thermal Conductivity

The transport properties of CrN thin films deposited on sapphire have been tailored through structural modifications induced by cumulative argon implantation. As-grown samples experience the typical structural transition in CrN films from orthorhombic at low temperature to cubic above the Néel temperature (≈280 K) and exhibit a metallic-like conduction in both phases. With increasing implantation dose, the conduction mode shifts to a semiconductor-like behavior in both phases, albeit at different damage levels. Analysis of the results suggests that hopping conduction becomes dominant beyond a given damage threshold. The results highlight a promising correlation between defect engineering and conduction mechanisms, offering valuable insights into the versatile electrical properties of CrN films. These implantation-induced defects scatter carriers, leading to a decrease in their mobility. As the implantation dose increases, the defect landscape evolves, modifying the density of states. However, up to a dose of 0.050 dpa, no significant influence on phonon scattering is observed. This approach demonstrates that ion implantation enables precise tuning of CrN's electrical properties without affecting thermal conductivity, offering valuable insights into defect engineering in transition metal nitrides and underscoring its potential for transport properties decorrelation.

defects↗

Light–Induced Frenkel Defect Pair Formation Can Lead to Phase–Segregation of Otherwise Miscible Halide Perovskite Alloys

Alloys of ABX 3 halide perovskites (HP) exhibit unique phase behavior compared to traditional III-V and II-VI semiconductor alloys used in solar cells. While the latter typically have good mutual miscibility when their mixed components are size matched, and phase-segregate when size mismatched, HP alloys show good miscibility in the dark but can phase-segregate under light. Quantum mechanical calculations described herein reveal light-induced defect formation and migration hold the key. Specifically, the interaction between a halogen vacancy V X with halogen interstitial X i forming together a Frenkel-pair defect emerges as the enabler for phase-segregation in HP alloys. At a threshold bromine composition in the Br-I alloys, the photogenerated holes in the valence band localize, creating thereby a doubly-charged iodine Frenkel-pair (V I + I i ) 2+ . Faster migration of iodine over bromine interstitial into the vacant iodine V I site leads to the formation of iodine-rich and iodine-depleted regions, establishing phase-segregation. Removal of the mobile defects–the agent of segregation–by dark thermal annealing, supplies the opposing force, leading to reversal of phase-segregation. Furthermore, this atomistic understanding can enable some control of the phase-segregation by selecting substituting elements on the B site–such as replacing some Pb by Sn–that are unable to form stable Frenkel defects.

14 SOLAR ENERGY↗

Enhanced Sb 2 Se 3 solar cell performance through theory-guided defect control: Enhanced Sb 2 Se 3 solar cell performance

Defects present in the absorber layer largely dictate photovoltaic device performance. Recently, a binary photovoltaic material, Sb 2 Se 3 , has drawn much attention due to its low-cost and nontoxic constituents and rapid performance promotion. So far, however, the intrinsic defects of Sb 2 Se 3 remain elusive. Here in this work, through a combined theoretical and experimental investigation, we revealed that shallow acceptors, SeSb antisites, are the dominant defects in Sb 2 Se 3 produced in an Se-rich environment, where deep donors, SbSe and VSe, dominate in Sb 2 Se 3 produced in an Se-poor environment. We further constructed a superstrate CdS/Sb 2 Se 3 thin-film solar cell achieving 5.76% efficiency through in situ Se compensation during Sb 2 Se 3 evaporation and through careful optimization of absorber layer thickness. In conclusion, the understanding of intrinsic defects in Sb 2 Se 3 film and the demonstrated success of in situ Se compensation strategy pave the way for further efficiency improvement of this very promising photovoltaic technology.

14 SOLAR ENERGY↗

Multichannel filter application of a magnetized cold plasma defect in periodic structure of ZnS/TiO{sub 2} materials

In this article, transmission spectra of multilayer structure of zinc sulfide (ZnS) and titanium dioxide (TiO{sub 2}) with defect of magnetized cold plasma (MCP) have been calculated theoretically by using characteristics transfer matrix method. The transmission spectra versus frequency have been analyzed for symmetric and asymmetric structure. Due to have a multiple band gaps in the asymmetric structure, we have taken the asymmetric structure for analysis with the parameters of MCP and the thicknesses of the dielectric materials. It is well known that magnetized cold plasma is an abnormal material because the permittivity changes with applied external magnetic field, and shows tunable photonic band gap for permittivity of the MCP. Now, the transmission spectra of the asymmetric structure versus frequency by inserting one or two magnetized cold plasma layer were analyzed with the variation of incident angles, the parameters of MCP, and the thicknesses of ZnS and TiO{sub 2} material. The analyzed transmission spectra of asymmetric structure with the variation of electron density, thicknesses of dielectric materials were obtained better results with defect of two plasma layers as compare to the defect of one layer of plasma. These obtained results reveal that the defect of two magnetized cold plasma layers of one dimensional asymmetric structure of ZnS, TiO{sub 2} may be used for the tunable multichannel filter at microwave region.

36 MATERIALS SCIENCE↗

Structural-Phase Features of Low-Stability Pre-Transitional States of BCC-Alloys with Complexes of Planar Defects (Antiphase Boundaries)

Using the Monte Carlo method, the influence of the complexes of antiphase boundaries (APBs) (a pair of shear APBs and a pair of thermal APBs) on the low-stability, pre-transitional states of BCC-alloys is considered by the example of a conventional copper alloy CuZn and an intermetallic compound NiAl. It is shown that in the region of low-stability structural-phase states the energy of formation of a complex of thermal APBs is higher than that of shear APBs. The contribution of APBs into disordering is appreciable up to the structural-phase transition temperature. The most significant factor in terms of the long-range order is the formation of the defect itself; the differences in the APB type or the plane of their occurrence do not so much affect the longrange order behavior with the temperature variation. The type of APBs however appreciably affects the structural-energy characteristics of the system at the temperatures below the phase transformation temperature. Logically, a system with structural defects is less ordered than a defect-free system. The presence of a defect favors the onset of disordering at lower temperatures: it starts at lower temperatures in the case of thermal APBs (TAPBs) compared to shear APBs (TAPBs). In a BCC-system with a complex of TAPBs the first signs of disordering invariably appear near the phase boundary in the neighborhood of large atoms (Zn–Zn in the CuZn alloy or Al–Al in the NiAl intermetallide). In the alloy with a complex of shear APBs the distortion of ordering at low temperatures is observed in the regions where the boundaries cross. The presence of antiphase boundaries affects the alloy stability under heating. It is shown that disordering is accompanied by smearing of the boundaries and their faceting. It follows from a comparative analysis of the peculiarities of disordering in the BCC-system under study (classical alloy CuZn and intermetallide NiAl) under conditions of higher temperatures in the region of low-stability, pre-transitional states that the order – disorder phase transition in the CuZn alloy takes place as a result of disordering of the system, while in the intermetallide NiAl the change of long-range order results from the structural-phase transition.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Entropy-defect synergy for dual luminescence mechanism in spinel: Time-resolved anti-counterfeiting and fingerprint visualization

Multimodal luminescent materials, while promising for anti-counterfeiting, often lack dynamic time-dependent responses and controllable spatial distribution, limiting their encryption capabilities in the spatiotemporal dimension. Here, this work presents a coordinated control strategy based on entropy and defect engineering, and uses a backpropagation (BP) neural network for material screening to successfully prepare spinel Mg 0.8 (Fe 0.04 Co 0.04 Ni 0.04 Cu 0.04 Zn 0.04 )Cr 2 O 4 (MgA 5 CO) phosphors with time-dependent dynamic luminescence behavior. This phosphor simultaneously activated the d-d transition luminescence (∼618 nm) derived from Co 2+ /Cr 3+ and the defect luminescence (∼398 nm) related to zinc vacancies (V Zn ) in a single-phase solid solution. The phosphor exhibits a time-dependent color evolution from pink to purple under fixed-wavelength excitation, due to the different excited-state dynamics and decay lifetimes associated with the d-d transition and defect luminescence. Structural characterization and spectral analysis confirmed the existence of V Zn and its significant role in defect luminescence process. The fluorescent and dynamic luminescent properties of entropy-based spinel oxide enable its use in advanced anti-counterfeiting applications like fingerprint recognition and color-changing dedicated anti-counterfeiting mark, showing promise in high-end and time-dynamic anti-counterfeiting fields. This research not only developed a new type of fluorescent dynamic anti-counterfeiting material, but also provided a new idea for constructing advanced optical functional materials with multiple luminescence mechanisms.

Defect project↗

Atomistically-informed modeling of point defect clustering and evolution in irradiated ThO 2

A cluster dynamics (CD) model has been developed to investigate the nucleation and growth of point defect clusters, i.e., interstitial prismatic loops and nanoscale and sub-nanoscale voids, in ThO 2 during irradiation by energetic particles. The model considers cluster off-stoichiometry due to the asymmetry of point defect generation on the O and Th sublattices under irradiation, as well as the point defect diffusivities and the defect binding energies to clusters. The energies were established using detailed molecular dynamics simulations considering the statistical variability of cluster configuration. A high-order adaptive time-integration has been used to solve the model. The predicted loop density and their average size is in good agreement with reported experimental observations for proton irradiated ThO 2 at 600°C. In conclusion, the model did not predict void evolution due to the sluggish kinetics of cation vacancies, explaining the absence of voids in proton irradiated ThO 2 (and other oxides) at relatively low temperatures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A computational framework for automation of point defect calculations

We have developed a complete and rigorously validated open-source Python framework to automate point defect calculations using density functional theory. Furthermore, the framework provides an effective and efficient method for defect structure generation, and creation of simple yet customizable workflows to analyze defect calculations. This package provides the capability to compute widely-accepted correction schemes to overcome finite-size effects, including (1) potential alignment, (2) image-charge correction, and (3) band filling correction to shallow defects. Using Si, ZnO and In2O3 as test examples, we demonstrate the package capabilities and validate the methodology.

97 MATHEMATICS AND COMPUTING↗

VTAnDeM: A python toolkit for simultaneously visualizing phase stability, defect energetics, and carrier concentrations of materials

Phase stability, defect formation energies, and carrier concentrations are closely interrelated features of semiconductors. Due to their joint dependence on the multidimensional chemical potential space, it is challenging to quantitatively establish patterns between these quantities in a given semiconductor, especially when the semiconductor is comprised of multiple elements. To enable synchronous visualization and analysis of these complementary material properties and their interdependence, we developed the Visualization Toolkit for Analyzing Defects in Materials (VTAnDeM). This python-based toolkit allows users to interactively explore how defect formation energies and carrier concentrations vary across the composition and chemical potential spaces of multicomponent semiconductors. Here, we illustrate the computational workflow that employs VTAnDeM as a post-processing tool for first-principles calculations and describe the data organization and theory underlying the visualization scheme. Furthermore, we believe that this software will serve as a useful tool for simultaneously visualizing the often complex and non-intuitive chemical potential – defect – carrier concentration phase space of semiconductors.

36 MATERIALS SCIENCE↗

Probing lattice defects in crystalline battery cathode using hard X-ray nanoprobe with data-driven modeling

Lattice defects, e.g., dislocations and grain boundaries, critically impact the properties of crystalline battery cathode materials. A longstanding challenge is to probe the meso–scale heterogeneity and evolution of lattice defects with sensitivity to atomic-scale details. Herein, we tackle this issue with a unique combination of X-ray nanoprobe diffractive imaging and advanced machine learning techniques. The domains with different lattice defect configuration within a single-crystalline LiCoO2 cathode particle are faithfully revealed using our approach. We further visualize the rearrangement of grain boundaries and local crystallinity upon mild thermal annealing. Furthermore, these results pave a direct way to the understanding of crystalline battery materials’ response under external stimuli with high fidelity, which provides valuable empirical guidance to defect-engineering strategies for improving the cathode materials against aggressive battery operation.

36 MATERIALS SCIENCE↗

Recent advances in rational design of defect-engineered photocatalysts toward sustainable NH 3 synthesis as H 2 carrier: From fundamental and development to machine-learning

In this study, we provide a detailed overview of the fundamental mechanisms underpinning photocatalytic N 2 reduction. We also discuss advances in catalyst design for the synthesis of NH 3 . Particular emphasis is placed on the role of surface defect engineering, which includes the creation of surface defects to enhance the performance of semiconducting photocatalysts for efficient N 2 reduction. In addition, the application of a machine learning-based computational modeling approach is discussed as an important driving force for predicting and regulating NH 3 synthesis efficiency based on catalyst features and reaction conditions. Finally, existing challenges and future perspectives for improving the performance of defect-engineered photocatalysts are outlined to contribute to the ongoing discourse on sustainable ammonia generation. This review aims to clarify recent progress in the rational design of defect-containing photocatalysts for the synthesis of NH 3 and encourages innovative approaches to catalyst optimization rather than solely focusing on new materials.

08 HYDROGEN↗

Multi-physics melt pool modeling and process optimization for laser direct energy deposition of Nb-based refractory C103: Defect formation, geometric precision, and process mapping

Recent developments in additive manufacturing (AM) technology have reignited interest in the fabrication of the Nb-based refractory C103 alloy offering solutions to the challenges posed by traditional manufacturing methods. However, the limited numerical and experimental studies on laser direct energy deposition (DED) of C103 have hindered the understanding of the relationships between process parameters and build quality. This has made it challenging to consistently produce parts with the desired quality and microstructure suitable for critical applications. In this study, we focus on optimizing the laser DED process for C103 by employing a hybrid approach that combines experimental techniques and computational fluid dynamics (CFD). This approach facilitates the development of process maps for defect detection and geometric precision. To achieve this, multi-layer C103 samples were fabricated using laser DED under various process parameters, enabling the creation of a process map for defect detection. Additionally, a multi-physics, multiphase simulation framework was developed within a high-performance computing (HPC) environment to establish process maps for geometric precision. Using these process maps, printability windows were identified for achieving both the desired geometric accuracy and defect-free prints. It was observed that prints with a power-to-velocity (P/V) ratio close to unity resulted in defect-free outcomes. This study provides a foundation for reducing design lead time and rejected parts, ultimately optimizing the laser DED process for C103.

Defect formation and geometric precision↗

Defect evolution in Ni and NiCoCr by in situ 2.8 MeV Au irradiation

The evolution of radiation-induced defects in Ni and the single-phase concentrated solid solution alloy, NiCoCr, were investigated during in situ 2.8 MeV Au ion irradiation and post-irradiation analysis using transmission electron microscopy. Compared to Ni, both the size and area density of defect clusters decreased in NiCoCr under the same irradiation conditions, suggesting that the chemical complexity, i.e., randomness of lattice site occupations, of NiCoCr suppressed radiation-induced damage. One-dimensional glide of defect clusters was observed in Ni but not in the NiCoCr alloy. The structural nature of small defect clusters in NiCoCr were further investigated using high-angle annular dark field scanning transmission electron microscopy.

36 MATERIALS SCIENCE↗

Role of chemical disorder on radiation-induced defect production and damage evolution in NiFeCoCr

Understanding chemical disorder in many concentrated solid solution alloys (CSAs) at the levels of electrons and atoms has attracted increasing attention as a path forward to reveal and identify underlying mechanisms for extraordinary mechanical properties and improved radiation tolerance. Single-phase NiFeCoCr CSA is a common base for many high-entropy alloys (HEAs) that have shown improved mechanical strength and radiation tolerance. In this study, defect production and damage evolution in NiFeCoCr under ion irradiation at room temperature to dose over 20 dpa are determined using ion channeling technique along both <100> and <110> directions utilizing multiple probing beam energies. The results obtained from the multi-axial and multi-energy channeling analysis are compared with those previously obtained for Ni crystals irradiated under similar conditions. The influence of chemical complexity on defect production and clustering at early-stage under room temperature irradiation up to dose of 1 dpa is discussed based on positron annihilation spectroscopy results. Defect structure evaluation in Ni and NiFeCoCr is also discussed based on transmission electron microscopy results over a prolonged irradiation at both room and elevated temperatures. Compared with chemically complex NiFeCoCr, larger dislocation loops thus less lattice strain are expected to form in pure Ni. Moreover, the role of chemical disorder in this CSA is also investigated based on ab initio calculations using large supercells. Finally, to understand the impact of chemical complexity effect on defect structure evolution, this integrated research effort attempts to link the relatively large charge redistribution due to difference in valence electron counts resulting from alloying different 3d transition metal elements, moderate lattice distortion arising from similar adaptable atomic size, and notable suppressed or delayed damage evolution in NiFeCoCr.

36 MATERIALS SCIENCE↗

Phonon modal analysis of thermal transport in ThO 2 with point defects using equilibrium molecular dynamics

Defects can significantly degrade the thermal conductivity of ThO 2 , an advanced nuclear fuel material as well as a surrogate for other fluorite-structured materials. Here, we investigate how point defects in ThO 2 impact phonon mode-resolved thermal transport. By incorporating phonon modes from lattice dynamics, we decompose the trajectory and heat flux to phonon normal mode space and extract key phonon properties, including phonon relaxation times and their contributions to thermal conductivity. We implement two methods. The first method is based on the Green Kubo formalism to resolve the contribution of each phonon mode to thermal conductivity. The second resolves the lifetime of individual phonon modes and the thermal conductivity is calculated using the Boltzmann transport equation within relaxation time approximation. Notably, a lower contribution of acoustic modes is revealed compared to perturbative approaches considering only three-phonon scattering processes. The effects of four types of point defects are evaluated. The strongest impact on a reduction in thermal conductivity is from Th interstitials, followed by Th vacancies. O interstitials/vacancies have a similar impact, albeit smaller than defects on the thorium sublattice. These observations are consistent with previous studies.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Impact of chemical ordering on thermodynamic properties of point defects and Xe substitutional in U-10Mo

The accurate knowledge of defect energetics is critical to understanding the aging and irradiation behavior of U-10Mo nuclear fuel, which is selected as the fuel type for conversion of the United States High-Performance Research Reactors (HPRRs). Furthermore, using hybrid molecular dynamics and Monte Carlo (MDMC) simulation, we studied the impact of chemical ordering on the formation energies of vacancies, interstitials, and the solution energy of the Xe substitutionals. Instead of forming a random solid solution (RSS), substantial short-range-order (SRO) develops in U-10Mo, particularly at low temperatures. Mo atoms are found to repel each other and prefer U-rich local atomic environments within the 1st nearest neighbor (1NN) cutoff. Compared to the case of a RSS, the state with equilibrated Mo ordering shifts the distributions of vacancy and interstitial formation energies due to the dependence of defect energies on the local atomic environment, without a clear effect on Xe solution energy. In the operation temperature range (100–250 °C) of U-Mo fuels, neglecting SRO can lead to an inaccurate estimate of thermal equilibrium point defect concentrations by over an order of magnitude and incorrectly predict the preference among different types of dumbbells, highlighting the critical importance of accounting for the impact of chemical ordering for accurate atomistic calculations of defect properties.

Molecular dynamics and Monte Carlo (MDMC)↗

Bethe-Salpeter Equation calculations of nitrogen-vacancy defects in diamond

Doped diamonds are of significant fundamental, technological, and commercial interest. For example, boron doping leads to a blue coloration at low concentration and superconductivity at high concentration. Similarly nitrogen doping can cause a variety of colors in diamond. Nitrogen-vacancy defects are also promising as quantum-computing qubits. Theoretical Bethe-Salpeter Equation (BSE) simulations of boron-doped diamonds have been found to give optical absorption spectra in good agreement with their observed blue coloration. In contrast, nitrogen defects are more complex, due in part to a plethora of possible N-defect conformations. Here, in this study, we present a theoretical study of several neutral, isolated, N-defect conformations that combines ab initio DFT calculations for relaxed 64-atom unit cells together with first principles GW/BSE calculations of their optical spectra. Spectral results are compared with available experimental data, and the effects of absorption are simulated for realistic rendered diamonds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗