Concentration Of Point Defects Research Articles

First Principles Study of Bismuth Vacancy Formation in (111)-Strained BiFeO3

Epitaxial strain is known to significantly influence the structural and functional properties of oxide thin films. However, its impact on point defect concentration has been less explored. Due to the challenges in experimentally measuring thin-film stoichiometry, computational studies become crucial. In this work, we use first-principles calculations based on density functional theory to investigate the formation and stability of Bi vacancies and Bi-O vacancy pairs in BiFeO3 (BFO) under (111) epitaxial strain. Our results demonstrate that compressive strain (−4%) decreases the formation enthalpy of Bi vacancies by 0.88 eV, whereas tensile strain (4%) increases it by 0.39 eV. Out-of-plane (OP) Bi-O vacancy pairs exhibit enhanced stability under both compressive and tensile strain, with formation enthalpy reductions of 1.49 eV and 1.05 eV, respectively. In contrast, in-plane (IP) vacancy pairs are stabilized under compressive strain but are insensitive to tensile strain. Finally, we discuss how these findings influence Bi stoichiometry during thin-film growth and the role of local strain fields in the formation of conducting domain walls.

Energetics of Point Defects in D0a Ag3Sn: First‐Principles Calculations

The Ag3Sn intermetallic compound is commonly found and acts as a strengthening factor in the key lead‐free solders based on Sn‐Ag‐Cu. The Ag3Sn phase exhibits also an asymmetric off‐stoichiometry, which necessitates the existence of constitutional point defects. The presence of point defects can, in general, sensitively affect the plastic deformation of materials and the strengthening role of Ag3Sn in particular. To understand the nature of the point defects and the compositional stability of Ag3Sn, the relaxed structures and the energies of single point defects (vacancies and antisite defects) in all three sublattices of Ag3Sn are calculated at 0 K using ab initio density functional theory (DFT) and the supercell method. The first‐principles‐based calculations predict that the AgSn antisite defect (Ag substitution for Sn) has the smallest enthalpy of formation, thus indicating that the AgSn antisite defect is the dominant point defect in Ag3Sn. The point defect concentrations as a function of Sn content are estimated using the DFT defect energies and the Wagner–Schottky model. The compositional dependence of the point defect concentrations gives new insights on the atomistic mechanisms of formation of nonstoichiometric Ag3Sn.

Enabling defect control or polyiodide formation regimes in halide perovskites

Defect engineering in oxide materials is typically achieved through manipulation of oxygen pressure and temperature, followed by quenching which freezes the concentration of point defects. Unlike oxides, halide perovskites equilibrate with gaseous atmosphere at room temperature. Information on defect engineering in halide perovskites that utilize the concentration of gaseous species is scarce and controversial. In this report we address this controversy by studying the interaction of MAPbI3 with molecular iodine over a wide range of partial pressures and reveal the two regimes of such interaction: defect control regime and polyiodide formation regime switching at ∼20 % of the saturated iodine pressure. In defect control regime the material undergoes reversible changes in semiconductor properties, while in polyiodide formation regime the material undergoes irreversible changes in crystallinity and microstructure. These findings emphasize the manifold role of molecular iodine for this class of materials and provides researchers with the experimental framework that can be utilized to tune stoichiometry and conductivity of halide perovskites to further enhance the performance and stability metrics of the corresponding devices.

Importance of zero cross-point (Cp = 0) control between the vacancy and interstitial Si atom concentration curves to obtain a perfect Si ingot using Si melt growth

The cross-point (Cp), which appears in the vacancy (CV) and interstitial Si atom (CI) concentration curves, is a simple controlling factor for ingot growth and provides a final goal to obtain a defect-free Si ingot using general Si melt growth. The importance of Cp is demonstrated using the noncontact crucible method (NOC), which has a relatively small temperature gradient due to an ingot grown inside the melt. The control of temperature gradient G at a constant growth rate v is simple for the actual ingot growth; thus, the present simulated results are expressed by G at a constant v. The concentration at the Cp point becomes smaller as G becomes smaller and finally becomes zero (Cp = 0), in which CV and CI are practically zero (CV=CI=0). The estimated G and temperature T at Cp = 0 for v = 0.000144 cm s−1 are 6.3, 12.5, and 18.5 K cm−1 and 1216 K (943 °C), 1354 K (1081 °C), and 1371 K (1098 °C), corresponding to each combination. At 1216 K, G should be precisely controlled within 6.3 ± 3 % K cm−1 in the region substantially close to Cp = 0 to maintain the remaining concentration of point defects substantially lower than 1.0 × 1013 cm−3. G should be changed during growth from larger G to smaller G, such as 6.3 K cm−1, to efficiently grow the ingot within the limited time. The changing point, x of G, is an important key parameter for the timing variation, where x denotes the normalized distance from the growing interface. The initial G is large; thus, the changing point of G approaches the growing interface. The growth condition necessary to obtain a defect-free Si ingot can be demonstrated using the Cp = 0 point, which is fully compatible with the perfect critical point where CV and CI are practically zero. The present results are mainly considered using the CV and CI concentration curves. However, these results largely help understand the approximate trend of G and v for the growth of defect-free ingot and the relation between Cp and the commonly used critical point between CV and CI.

First-principles prediction of point defect energies and concentrations in the tantalum and hafnium carbides

First-principles calculations are combined with a statistical–mechanical model to predict the equilibrium point-defect concentrations in the refractory carbides TaC and HfC as a function of temperature and chemical composition. Several different types of point defects (vacancies, interstitials, antisite atoms) and their clusters are treated in a unified manner. The defect concentrations either strictly follow or can be closely approximated by Arrhenius functions with parameters predicted by the model. The model is general and applicable to other carbides, nitrides, borides, or similar chemical compounds. Implications of this work for understanding the diffusion mechanisms in TaC and HfC are discussed.

Unveiling the Effect of Cooling Rate on Grown-in Defects Concentration in Polycrystalline Perovskite Films for Solar Cells with Improved Stability.

Numerous efforts are devoted to reducing the defects at perovskite surface and/or grain boundary; however, the grown-in defects inside grain is rarely studied. Here, the influence of cooling rate on the point defects concentration in polycrystalline perovskite film during heat treatment processing is investigated. With the combination of theoretical and experimental studies, this work reveals that the supersaturated point defects in perovskite films generate during the cooling process and its concentration improves as the cooling rate increases. The supersaturated point defects can be minimized through slowing the cooling rate. As a result, the optimized FAPbI3 polycrystalline films achieve a superior carrier lifetime of up to 12.6 µs and improved stability. The champion device delivers a 25.47% PCE (certified 24.7%) and retain 90% of their initial value after >1100 h of operation at the maximum power point. These results provide a fundamental understanding of the mechanisms of grown-in defects formation in polycrystalline perovskite film.

Sensitivity Analysis and Uncertainty Quantification on Point Defect Kinetics Equations with Perturbation Analysis

The concentration of radiation-induced point defects in general materials under irradiation is commonly described by the point defect kinetics equations based on rate theory. However, the parametric uncertainty in describing the rate constants of competing physical processes, such as recombination and loss to sinks, can lead to a large uncertainty in predicting the time-evolving point defect concentrations. Here, based on perturbation theory, we derive up to the third-order correction to the solution of point defect kinetics equations. This new set of equations enables a full description of continuously changing rate constants and can accurately predict the solution up to 50% deviation in these rate constants. These analyses can also be applied to reveal the sensitivity of the solution to input parameters and aggregated uncertainty from multiple rate constants.

Microstructural evolution and corrosion behavior of deformed GH3536 alloy fabricated by laser metal deposition for bipolar plates in PEMFC

The influences of cold rolling deformation on the microstructures and corrosion behavior of laser metal deposition processed GH3536 alloy were investigated through electron backscattered diffraction and electrochemical tests. The results indicate that the deformed sample within a 15 % of reduction exhibits an excellent corrosion resistance in the simulated PEMFC solution, which can be mainly attributed to a small amount of deformation providing more nucleation sites for Cr to form compact Cr2O3 passive films. In addition, an appropriate compressive residual stress reduces point defect concentrations in passive films and limits interfacial reaction kinetics. In comparison, the corrosion resistance of GH3536 alloy obviously decreases with an increase in deformation reduction from 15 % to 50 %. Apart from a strong increase in activation energy, high-density dislocations after a severe deformation will enhance the surface activity and result in the lattice distortion in the passive film, which deteriorates the corrosion resistance of cold-rolled GH3536 alloy samples.

Atomistic Origins of Various Luminescent Centers and n-Type Conductivity in GaN: Exploring the Point Defects Induced by Cr, Mn, and O through an Ab Initio Thermodynamic Approach.

GaN is a technologically indispensable material for various optoelectronic properties, mainly due to the dopant-induced or native atomic-scale point defects that can create single photon emitters, a range of luminescence bands, and n- or p-type conductivities. Among the various dopants, chromium and manganese-induced defects have been of particular interest over the past few years, because some of them contribute to our present-day light-emitting diode (LED) and spintronic technologies. However, the nature of such atomistic centers in Cr and Mn-doped GaN is yet to be understood. A comprehensive defect thermodynamic analysis of Cr- and Mn-induced defects is essential for their engineering in GaN crystals because by mapping out the defect stabilities as a function of crystal growth parameters, we can maximize the concentration of the target point defects. We therefore investigate chromium and manganese-induced defects in GaN with ab initio methods using the highly accurate exchange-correlation hybrid functionals, and the phase transformations upon excess incorporation of these dopants using the CALPHAD method. We also investigate the impact of oxygen codoping that can be unintentionally incorporated during crystal growth. Our analysis sheds light on the atomistic cause of the unintentional n-type conductivity in GaN, being ON-related. In the case of Cr doping, the formation of CrGa defects is the most dominant, with an E +/0 charge transition at E VBM + 2.19 eV. Increasing nitrogen partial pressure tends to enhance the concentration of CrGa. However, in the case of doping with Mn, several different Mn-related centers can form depending on the growth conditions, with MnGa being the most dominant. MnGa possesses the E 2+/+, E +/0, and E 0/- charge transitions at 0.56, 1.04, and 2.10 eV above the VBM. The incorporation of oxygen tends to cause the formation of the MnGa-VGa center, which explains a series of prior experimental observations in Mn-doped GaN. We provide a powerful tool for point defect engineering in wide band gap binary semiconductors that can be readily used to design optimal crystal growth protocols.

Microstructure, mechanical, and thermal properties of (MoTaTiVW)CX high entropy ceramics with different carbon stoichiometries

In present work, high entropy (MoTaTiVW)CX ceramics with different carbon stoichiometries (X = 3–6) were produced using spark plasma sintering. The microstructure, mechanical properties, and thermal properties of (MoTaTiVW)CX with different carbon stoichiometries were studied. At X = 3, the carbon deficiency resulted in a multiphase structure of the sample, (MoTaTiVW)C3 with a Mo-rich carbide phase. At X = 3.5, the single-phase rock salt structure was formed despite carbon vacancies of up to 30 %. The relative density of (MoTaTiVW)CX gradually decreases as the carbon stoichiometry increases from X = 3 to X = 6. The concentration of carbon vacancies affects the sintering activation energy, which can enhance mass transfer and promote the densification process. The Vickers hardness of (MoTaTiVW)CX shows an overall decreasing trend as the carbon stoichiometry increases from X = 3.5 to X = 6, peaking at 20.4 ± 0.4 GPa at X = 3.5. The fracture toughness increases and then decreases, peaking at 4.4 ± 0.2 MPa m1/2 at X = 4. The thermal conductivity of (MoTaTiVW)CX gradually increases, then decreases and finally increases with the increase of carbon stoichiometry. At room temperature, the maximum value of thermal conductivity is 6.35 ± 0.29 W/m·K of (MoTaTiVW)C5 and the minimum value is 5.32 ± 0.35 W/m·K of (MoTaTiVW)C5.5. At 1000 °C, the thermal conductivity of (MoTaTiVW)CX ranges from 15.94 ± 0.37 W/m·K to 19.56 ± 0.45 W/m·K. As the concentration of carbon vacancies decreases, the decrease in point defect concentration will reduce the degree of lattice distortion, thereby reducing phonon scattering and affecting thermal conductivity. The study suggests that carbon stoichiometry can be used to adjust the microstructure, mechanical properties, and thermal properties of high entropy carbide ceramics.

Improvement of the Thermoelectric Properties of p-Type Mg3Sb2 by Mg-Site Double Substitution.

A P-type Mg3Sb2-based Zintl phase compound has been considered a promising candidate for thermoelectric applications. Alloying, which introduces a high concentration of point defects, is particularly effective in scattering phonons and reducing lattice thermal conductivity. Herein, alloying in p-type Mg2.995Na0.005Sb2 via the introduction of elements like Yb, Eu, Ca, and Ba was realized, and the room-temperature lattice thermal conductivity has been effectively reduced to ∼1.1 W m-1 K-1. To further intensify the phonon scattering, two groups of elements (Eu and Cd, and Yb and Cd) were chosen for heavy alloying at the Mg site, and the lattice thermal conductivity of Mg1.49Eu0.5Cd1Na0.01Sb2 was further reduced to ∼0.45 W m-1 K-1. Eventually, a peak zT as high as ∼1.0 was achieved at 773 K, and the compound outperforms the previously reported p-type Mg3Sb2 compounds.

Defects in Halide Perovskites: Does It Help to Switch from 3D to 2D?

Two-dimensional (2D) organic-inorganic hybrid iodide perovskites have been put forward in recent years as stable alternatives to their three-dimensional (3D) counterparts. Using first-principles calculations, we demonstrate that equilibrium concentrations of point defects in the 2D perovskites PEA2PbI4, BA2PbI4, and PEA2SnI4 (PEA, phenethylammonium; BA, butylammonium) are much lower than in comparable 3D perovskites. Bonding disruptions by defects are more destructive in 2D than in 3D networks, making defect formation energetically more costly. The stability of 2D Sn iodide perovskites can be further enhanced by alloying with Pb. Should, however, point defects emerge in sizable concentrations as a result of nonequilibrium growth conditions, for instance, then those defects likely hamper the optoelectronic performance of the 2D perovskites, as they introduce deep traps. We suggest that trap levels are responsible for the broad sub-bandgap emission in 2D perovskites observed in experiments.

Nickel-hexagonal phase induced in Ni3Si-monoclinic intermetallic phase by ion beam irradiation

A hypereutectic Ni alloy with 22 at. % Si was irradiated with a high-energy nickel ion beam and high ion fluence at 650°C to induce the formation of intrinsic and extrinsic point defects. Under these irradiation conditions, high concentrations of point defects were formed in the irradiated region. The recovery process initiated due to the damage induced by irradiation led to the formation of a nanoparticle population in the irradiated region. The irradiated region was characterized by high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), and transmission electron microscopy (TEM). The experimental evidence obtained permitted the establishment of an event sequence that culminated in nanoparticle population formation. The event sequence had the following stages: (a) Ni atom population implantation within a specific zone of the irradiated region; (b) nucleation and growth of a Nickel-hexagonal phase due to ordering of the implanted nickel atoms; and (c) Ni-hexagonal phase nanoparticle growth within a specific region of the irradiated region. The HRTEM analysis yielded crucial insights into the mechanisms underlying nanoparticle formation. The two most important aspects are as follows: firstly, the nucleation of Nickel-hexagonal phase into an amorphous region, and secondly, the non-equilibrium nature of the Nickel-hexagonal phase of the Nickel metallic system. These experimental findings are important for implantation technology; implanting atomic species into certain materials to create composite materials can lead to the formation of non-equilibrium phases and amorphous regions. Both of these outcomes have the potential to adversely affect the properties of the composite material.

Enhanced Mechanical and Electromechanical Properties of Compositionally Complex Zirconia Zr1-x(Gd1/5Pr1/5Nd1/5Sm1/5Y1/5)xO2-δ Ceramics.

Compositionally complex oxides (CCOs) or high-entropy oxides (HEOs) are new multielement oxides with unexplored physical and functional properties. In this work, we report fluorite structure-derived compositionally complex zirconia with composition Zr1-x(Gd1/5Pr1/5Nd1/5Sm1/5Y1/5)xO2-δ (x = 0.1 and 0.2) synthesized in solid-state reaction route and sintered via hot pressing at 1350 °C. We explore the evolution of these oxides' structural, microstructural, mechanical, electrical, and electromechanical properties regarding phase separation and sintering mechanisms. Highly dense ceramics are achieved by bimodal mass diffusion, composing nanometric tetragonal and micrometric cubic grains microstructure. The material exhibits an anomalously large electrostriction response exceeding the M33 value of 10-17 m2/V2 at room temperature and viscoelastic properties of primary creep in nanoindentation measurement under fast loading. These findings are strikingly similar to those reported for doped ceria and bismuth oxide derivates, highlighting the presence of a large concentration of point defects linked to structural distortion and anelastic behavior, which are characteristics of nonclassical ionic electrostrictors.

One Stone, Two Birds: Using High Electric Fields to Enhance the Mobility and the Concentration of Point Defects in Ion-Conducting Solids.

Improving the ionic conductivity of outstanding, composition-optimized crystalline electrolytes is a major challenge. Achieving increases of orders of magnitude requires, conceivably, highly nonlinear effects. One known possibility is the use of high electric fields to increase point-defect mobility. In this study, we investigate quantitatively a second possibility that high electric fields can increase substantially point-defect concentrations. As a model system, we take a pyrochlore oxide (La2Zr2O7) for its combination of structural vacancies and dominant anti-Frenkel disorder; we perform molecular-dynamics simulations with many-body potentials as a function of temperature and applied electric field. Results within the linear regime yield the activation enthalpies and entropies of oxygen-vacancy and oxygen-interstitial migration, and from three independent methods, the enthalpy and entropy of anti-Frenkel disorder. Transport data for the nonlinear regime are consistent with field-enhanced defect concentrations and defect mobilities. A route for separating the two effects is shown, and an analytical expression for the quantitative prediction of the field-dependent anti-Frenkel equilibrium constant is derived. In summary, we demonstrate that the one stone of a nonlinear driving force can be used to hit two birds of defect behavior.

Influence of Ge to the formation of defects in epitaxial Mg2Sn1−x Ge x thermoelectric thin films

Defect formation in epitaxial Mg2Sn1–x Ge x thermoelectric (TE) thin films grown via MBE was studied. We examined the defect formations and structures using cross-sectional transmission electron microscopy and positron annihilation spectroscopy. The defect formation tends to be influenced by Ge incorporation into the Mg2Sn matrix phase of epitaxial thin films. Mg vacancies (V Mg) were identified as point defects, primarily concentrated in the film’s mid-layer. In films with higher Ge composition, stacking faults were observed. The concentration of vacancy-type point defects decreased as the Ge concentration increased. This implies that the vacancy atoms, which would have otherwise been created by increasing chemical pressure due to the higher Ge content, might have played a role in the formation of stacking faults. The high concentration of vacancy-type defects resulted in the lowest thermal conductivity, demonstrating their significance as effective phonon scattering centers in epitaxial TE films.

Effect of turbulent flow on the oxide properties of carbon steel in alkaline water

The purpose of this study is to investigate the changes in the morphology, chemical state, defect density, and impedance of oxides formed on SA 106 Gr.B carbon steel by turbulent water flow at the micro and atomic levels. A compact magnetite layer composed of multi-faceted particles is formed in stagnant water, while a porous magnetite layer composed of particles without a certain shape is formed in turbulent water. Ferrous ions are preferentially dissolved from the oxide in turbulent water, which increases the vacancies in the oxide lattice. An increase in the concentration of point defects is shown to be comparable to an increase in the corrosion rate of carbon steel. The flow-accelerated corrosion behavior is also well correlated with the electrochemical impedance parameters including the charge transfer resistance and capacitance. Our study provides a further understanding of carbon steel corrosion under turbulent water flow conditions.

Charge-balanced codoping enables exceeding doping limit and ultralow thermal conductivity

Materials with low thermal conductivity are applied extensively in energy management, and breaking the amorphous limits of thermal conductivity to solids has attracted widespread attention from scientists. Doping is a common strategy for achieving low thermal conductivity that can offer abundant scattering centers in which heavier dopants always result in lower phonon group velocities and lower thermal conductivities. However, the amount of equivalent heavy-atom single dopant available is limited. Unfortunately, nonequivalent heavy dopants have finite solubility because of charge imbalance. Here, we propose a charge balance strategy for SnS by substituting Sn<sup>2+</sup> with Ag<sup>+</sup> and heavy Bi<sup>3+</sup>, improving the doping limit of Ag from 2% to 3%. Ag and Bi codoping increases the point defect concentration and introduces abundant boundaries simultaneously, scattering the phonons at both the atomic scale and nanoscale. The thermal conductivity of Ag<sub>0.03</sub>Bi<sub>0.03</sub>Sn<sub>0.94</sub>S decreased to 0.535 W·m<sup>−1</sup>·K<sup>−1</sup> at room temperature and 0.388 W·m<sup>−1</sup>·K<sup>−1</sup> at 275 ℃, which is below the amorphous limit of 0.450 W·m<sup>−1</sup>·K<sup>−1</sup> for SnS. This strategy offers a simple way to enhance the doping limit and achieve ultralow thermal conductivity in solids below the amorphous limit without precise structural modification.

A general scheme for point defect sink strength calculation and related machine-learning-based expressions

Irradiation tends to increase the concentration of point defects (PDs) in crystalline materials, whose consecutive interactions with other types of defects, such as dislocation and void, are recognised highly responsible for the characteristic plastic and damaging behaviours of materials under irradiation. Conventional treatments on evaluating the strength of PD sinks see their limitation with strong regularity requirements over the models used for summarising the key underlying microstructural behaviours, where analytical solutions are bound to be the outcome. The present article serves to introduce a general scheme for PD sink strength evaluation, where constraints on solution analyticity are fully resolved with the use of machine learning. In particular, a neural network representation of the PD sink strength due to void/bubble is derived, where PD transportation tendencies against the hydrostatic pressure gradient surrounding a bubble can be considered in details. The treatment is also applied to analyse PD sink strength due to edge dislocation clusters. For nearly uniformly distributed clusters, upon undertaking a two-scale asymptotic strategy, the corresponding sink strength formulation becomes explicit. For randomly distributed dislocations, the sink strength is found to roughly scale with the onsite dislocation density. But for patterned dislocations, such as dislocation dipoles, their sink strength is suggested to vary with the applied load. The machine-learning-based formulation is also compared well with the results obtained by other multiscale methods.

Spectrum splitting approach based design simulation for multilayer chalcogenide solar cell architecture

We report design simulation on multilayer solar cell architecture aimed at enhancing the absorption efficiency in antimony sulfide (Sb2S3) absorber based cell via spectrum splitting approach. The poor experimental efficiency chalcogenide absorber (say; ∼8% for Sb2S3) based solar cell has been attributed to inadequate rear contact barrier, a high concentration of point defects (both acceptor and donor) within the bulk, low carrier lifetime, and the presence of defects at the absorber/buffer interface. A hetero-structure design modification vis-à-vis experimental report using bandgap tunability of Sb2S3 via point-focusing spectral splitting technique approach has been implemented to upscale the efficiency. The incident solar spectrum has been split into three well defined regimes for a focussed bandgap matching to enable light absorption and minimize transmission and thermalization losses. The adopted point-focusing spectral splitting technique in this work has resulted in an efficiency of 18.0%, which is an advancement by 2.25 times over the highest reported efficiency of 8.0% in the literature for Sb2S3 absorber based solar cells.