Structure Of Point Defects Research Articles

Insight into insulation degradation mechanism of Al2O3 involved with positive and negative defects

Al2O3 with the desired electrical insulating properties and thermal shock resistivity has been extensively applied in the field of solid oxide fuel cells and oxygen sensors. However, degradation of the insulating Al2O3 layer is an intractable issue in practical applications. In this study, different point defect structures of Al2O3 were realized with the substitutional doping effect of ZrO2 and MgO. The MgO dopant provides positively charged oxygen vacancies, whereas the ZrO2 dopant tends to trigger negatively charged vacancy formation at Al3+ sites. The oxygen vacancy concentration of Al2O3 exhibits the following trend: MgO-doped Al2O3 > Al2O3 > ZrO2-doped Al2O3. Furthermore, the densification morphology, insulating properties, and oxygen vacancy migration of Al2O3 have been confirmed to be largely affected by the extrinsic factors. This study indicates that oxygen vacancy migration depends on the applied electric field at high temperatures. As the voltage and temperature increase, oxygen vacancy migration shows obvious electric-field-dependent characteristics, and its aggregation macroscopically shows hole defects. The defect position of Al2O3 is nonstoichiometric Al2O3-x with poor crystallinity. Therefore, it is believed that the oxygen vacancy migration triggered by the second phase directly determines the insulation performance and causes the degradation of Al2O3 materials.

Oxygen Dimerization as a Defect-Driven Process in Bulk LiNiO2.

To explore the possibility of oxygen dimerization-particularly, the formation of molecular oxygen-like species-in the bulk of LiNiO2 lithium ion cathode materials at high states of charge, we conduct a redox-product structure search inspired by recent methodological developments for point-defect structure prediction. We find that (1) delithiated Li1-x NiO2 (x = 1) has good kinetic stability toward decomposition into molecular oxygen and reduced transition-metal oxides but (2) defects can act as nucleation sites for oxygen dimerization. These results help reconcile conflicting reports on the formation of bulk molecular oxygen in LiNiO2 and other nickel-rich cathode materials, highlighting the role of defect chemistry in driving the bulk degradation of these compounds.

Toward an understanding of the role of structural organization and point defects in the formation of functional pure and Tm3+-doped (Ca3-xSrx)(VO4)2 for diode-pumped and SRS lasers

Whitlockite-type polycrystalline and single-crystal (Ca3−xSrx)(VO4)2 solid solutions were successfully obtained by solid-state synthesis and Czochralski method, respectively. Synchrotron powder X-ray diffraction allowed to reveal actual compositions of polycrystalline (Ca3−xSrx)(VO4)2 solid solutions with х = 0.3, 0.54, 0.9, 1.2, 1.35 refined by Rietveld method, which are slightly different from the initial ones. Synchrotron X-ray single-crystal diffraction analysis of Czochralski-grown undoped (Ca1.8Sr1.2)(VO4)2 (CSVO) revealed its actual composition (Ca2.982(11)Sr0.031)(VО4)2. Difference between initial and refined compositions is analyzed and discussed. In the CSVO structure, Sr2+ ions partially occupy monocapped Ca2 and two-capped Ca3 trigonal prismatic sites and Ca2+ ions are in the Ca5 and Ca5A sites, forming two independent strongly distorted tetrahedral Ca5O4 and octahedral Ca5AO6 oxygen environments. Synchrotron X-ray single-crystal diffraction analysis together with X-ray absorption spectroscopic study of (Сa2.4Sr0.6)(VO4)2 doped with 0.5 and 1.0 wt% Tm2O3 (СSVO:0.5Tm and CSVO:1.0Tm) allowed to establish the absence of cations in the Ca5A site, the localization of Sr2+ ions in the Ca2 and Ca3 sites and additionally in octahedral Ca4 site together with Tm3+ ions, forming an individual eight-coordinated environment, in the refined compositions (Ca2.776(7)Sr0.210(4)Tm3+0.008(1))(VO4)2 and (Ca2.855(7)Sr0.140(7)Tm3+0.009(1)□0.022(7))(VO4)2, respectively, with vacancies (marked by a square,□) in the two-capped Ca1 trigonal prismatic site in the CSVO:1.0Tm structure. Additional interstitial oxygen, participating in the formation of the Tm3+ environment, found in the residual electron density, together with vacancies in the Ca1 site provides electroneutrality to CSVO:0.5Tm and CSVO:1.0Tm crystals. Several structural models of the coordination environment of Tm3+ ions were analyzed and the most correct one was proposed.

Charge state-dependent symmetry breaking of atomic defects in transition metal dichalcogenides

The functionality of atomic quantum emitters is intrinsically linked to their host lattice coordination. Structural distortions that spontaneously break the lattice symmetry strongly impact their optical emission properties and spin-photon interface. Here we report on the direct imaging of charge state-dependent symmetry breaking of two prototypical atomic quantum emitters in mono- and bilayer MoS2 by scanning tunneling microscopy (STM) and non-contact atomic force microscopy (nc-AFM). By changing the built-in substrate chemical potential, different charge states of sulfur vacancies (VacS) and substitutional rhenium dopants (ReMo) can be stabilized. VacS−1\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\\mathrm{Vac}}_{{{{{{{{\\rm{S}}}}}}}}}^{-1}$$\\end{document} as well as ReMo0\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${{\\mathrm{Re}}}_{{{{{{{{\\rm{Mo}}}}}}}}}^{0}$$\\end{document} and ReMo−1\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\\mathrm{Re}}_{{\\rm{Mo}}}^{-1}$$\\end{document} exhibit local lattice distortions and symmetry-broken defect orbitals attributed to a Jahn-Teller effect (JTE) and pseudo-JTE, respectively. By mapping the electronic and geometric structure of single point defects, we disentangle the effects of spatial averaging, charge multistability, configurational dynamics, and external perturbations that often mask the presence of local symmetry breaking.

Two-dimensional silicon-based dielectric column photonic crystal point defect microcavity Neural network modelling

In order to solve the problem that it is difficult to predict the microcavity photonic energy bands of point defects in two-dimensional silicon-based dielectric column photonic crystals, this paper proposes a method to predict the microcavity photonic energy bands of point defects in two-dimensional silicon-based photonic crystals by using an artificial neural network model. In this paper, the energy band structure of triangular lattice point defects at different radii is calculated using MPB, and a neural network model is established based on this data and the accuracy of the established model is verified.

Estimation of Some Parameters in the Point Defect Model (PDM) for the Passivity of Metals

In this paper, we justify that the potential drop at the barrier layer/solution (bl/s) interface of the barrier layer of the passive film on a metal, φf/s, is a linear function of the applied voltage V and pH in the case of sufficiently thin barrier layer. Furthermore, we show that a relationship exists between parameters α (the dependence of φf/s on V) and β (the dependence of φf/s on pH), that is, those parameters are not independent, in the general case. It is also shown that some dependence of parameters α and β on temperature can exist. However, this dependence in the practical region (0 °C–100 °C) is weak and, in many cases, it is possible to neglect the dependence of parameters α and β on temperature. Finally, we show that it is possible to estimate, theoretically, the parameter β (and accordingly parameter α) by using models for specific systems. For the system considered in the current report (carbon steel in concrete pore water), the estimated value of parameter β is confirmed experimentally. These findings are discussed in terms of the electronic and point defect structures of the barrier layer.

A first-principles investigation of internal energy and entropy of formation of charged defects in Th1−xUxO2 (x ≤ 0.5)

Mixed thorium/uranium dioxide, (Th,U)O2, is under consideration for advanced nuclear fuel applications. Investigating the point defect structure and energy in this oxide is important for predicting its behavior as fuel. In this work, we use first-principles calculations based on the generalized gradient approximation (GGA)+Hubbard U approach to investigate the internal energy and entropy of the formation of point defects in Th1−xUxO2 at various compositions below x ≤ 0.5. Point defects including O vacancies, O interstitials, Th vacancies, Th interstitials, U vacancies, and U interstitials have all been considered with their charges ranging from neutral to the maximum nominal values. The observed trends have been explained in terms of electronic density of states. The valence band maxima of crystals that contain defects play a crucial role and exhibit variations depending on the U content and the applied charge. The temperature dependence of internal energy and entropy of formation of defects have also been examined. The internal energy of formation of defects was found to exhibit slowly varying or constant values with respect to changes in the U content, except at low values of x and low temperatures. The entropy of formation of defects was observed to decrease with increasing U content. It was additionally observed that the entropy of formation of vacancies increases with temperature, while that of interstitials decreases. This investigation further revealed that at 0 K, the cation vacancies and anion interstitials become increasingly favorable with increasing U content, while cation interstitials and anion vacancies become less favorable.

Intelligent optimization design of large-scale three-dimensional ultrasonic vibration system

Large-scale three-dimensional ultrasonic vibration systems are susceptible to the influence of coupled vibration, resulting in a series of problems such as increased energy loss, small longitudinal displacement amplitude of the radiation surface, and uneven distribution of longitudinal displacement amplitude, which can seriously affect the working efficiency of ultrasonic processing system. How to effectively control the coupled vibration of large-scale three-dimensional ultrasonic transducer systems and optimize their performance has become an urgent problem in the field of power ultrasound. The research has found that some phononic crystal slots and point defect structures can suppress the lateral vibration of large-scale transducer systems, improve the uniformity of system amplitude distribution, and artificially regulate the performance of large-scale three-dimensional ultrasonic vibration systems by changing the configuration parameters of phononic crystal structures. However, excessive design parameters will inevitably increase the complexity of system design, and, currently, the optimization design of large-scale three-dimensional ultrasonic transducer systems relies on empirical trial and error methods which has low design efficiency and low success rate, and cannot guarantee the system performance. Therefore, in the study, homogeneous dislocations and point defect structures are introduced to optimize the design of large-scale three-dimensional ultrasonic vibration systems. Data analysis techniques are used to evaluate the influences of the configuration of homogeneous dislocations and point defect structures on the longitudinal displacement amplitude, amplitude distribution uniformity, radiated sound power, working bandwidth of the system’s radiation surface. And a predictive model for the performance of large-scale ultrasonic transducer system with homogeneous dislocation structure and near periodic defect structure is established, which can achieve intelligent design of large-scale power ultrasonic transducer system, improve design efficiency and success rate, and reduce the design cost.

Photocunductivity spectra of thin solid solution films CdSexS1-x

This paper presents the results of a study on the energy spectra of activation of intrinsic defects in photosensitive films of solid solution CdSexS1-x depending on the conditions of their preparation and thermal treatment in different environments. This study investigates the photoconductivity spectra of thin films composed of the solid solution CdSexS1-x, focusing on the impact of preparation and thermal treatment conditions on the activation energy spectra of intrinsic defects. The films were synthesized using thermal evaporation in a vacuum and subjected to various thermal processes. The results indicate that the photoconductive properties are highly influenced by structural defects and point defects within the crystalline lattice, which create deep levels in the forbidden zone of the semiconductor. These findings advance the understanding of the physical processes in polycrystalline films and highlight the potential of CdSexS1-x films for developing light-emitting diodes and lasers in the infrared and visible spectra.

First-principles calculations of point defect migration mechanisms in InP

As an important second-generation semiconductor material, indium phosphide (InP) possesses excellent advantages such as a wide bandgap, high electron mobility, high photoelectric conversion efficiency, and strong radiation resistance. It is considered an excellent material for electronic devices in aerospace applications. However, point defects generated by space radiation particles in InP electronic devices can cause their electrical performance to degrade severely. In this study, first-principles calculations are employed to investigate the stable structures of point defects in InP and calculate the migration energy values of nearest-neighbor defects. Four stable structures of In vacancies and three stable structures of P vacancies are identified by constructing the stable structures of point defects in different charge states. The migration process of vacancy defects is studied, revealing that the migration energy of P vacancies is higher than that of In vacancies. Moreover, charged vacancy defects exhibit higher migration energy values than neutral vacancies. Regarding the migration process of interstitial defects, it is found that the migration energy of interstitial defects is smaller than that of vacancy defects. In the calculation of In interstitial migration process with different charge states, two different migration processes are found. Besides, during the migration calculations of P interstitial, a special intermediate state is discovered, resulting in multiple paths migrating to the nearest-neighbor position in the migration energy barrier diagram. The research results are helpful to understand the formation mechanism and migration behavior of defects in InP materials, and are important in designing and manufacturing InP devices with long-term stable operation in space environment.

On the Structure of Oxygen Deficient Amorphous Oxide Films.

Understanding defects in amorphous oxide films and heterostructures is vital to improving performance of microelectronic devices, thin-film transistors, and electrocatalysis. However, to what extent the structure and properties of point defects in amorphous solids are similar to those in the crystalline phase are still debated. The validity of this analogy and the experimental and theoretical evidence of the effects of oxygen deficiency in amorphous oxide films are critically discussed. The authors start with the meaning and significance of defect models, such as "oxygen vacancy" in crystalline oxides, and then introduce experimental and computational methods used to study intrinsic defects in amorphous oxides and discuss their limitations and challenges. To test the validity of existing defect models, ab initio molecular dynamics is used with a non-local density functional to model the structure and electronic properties of oxygen-deficient amorphous alumina. Unlike some previous studies, the formation of deep defect states in the bandgap caused by the oxygen deficiency is found. Apart from atomistic structures analogous to crystal vacancies, the formation of more stable defect states characterized by the bond formation between under-coordinated Al ions is shown. The limitations of such defect models and how they may be overcome in simulations are discussed.

Comprehensive Recovery of Point Defect Displacement Field Function in Crystals by Computer X-ray Diffraction Microtomography

In the case of the point defect in a crystal, the inverse Radon’s problem in X-ray diffraction microtomography has been solved. As is known, the crystal-lattice defect displacement field function f(r) = h·u(r) determines phases − (±h)-structure factors incorporated into the Takagi–Taupin equations and provides the 2D image patterns by diffracted and transmitted waves propagating through a crystal (h is the diffraction vector and u(r) is the displacement field crystal-lattice-defects vector). Beyond the semi-kinematical approach for obtaining the analytical problem solution, the difference-equations-scheme of the Takagi–Taupin equations that, in turn, yield numerically controlled-accuracy problem solutions has been first applied and tested. Addressing the inverse Radon’s problem solution, the χ2-target function optimization method using the Nelder–Mead algorithm has been employed and tested in an example of recovering the Coulomb-type point defect structure in a crystal Si(111). As has been shown in the cases of the 2D noise-free fractional and integrated image patterns, based on the Takagi–Taupin solutions in the semi-kinematical and difference-scheme approaches, both procedures provide the χ2-target function global minimum, even if the starting-values of the point-defect vector P1 is chosen rather far away from the reference up to 40% in relative units. In the cases of the 2D Poisson-noise image patterns with noise levels up to 5%, the figures-of-merit values of the optimization procedures by the Nelder–Mead algorithm turn out to be high enough; the lucky trials number is 85%; and in contrast, for the statistically denoised 2D image patterns, they reach 0.1%.

Development of Durable Materials for Cost Effective Water Splitting

Saint-Gobain, a global leader in ceramic and polymer based materials and components has been developing solutions for fuel and electrolysis cells for over 20 years. These solutions include; electrode and electrolyte materials, innovative cell and stack designs, ceramic interconnects, seals (both glass-ceramic and polymer based) and hot box designs. Although high temperature electrolysis promises to be an efficient solution to the production of hydrogen, durability and performance improvements are still required to produce devices that are economically feasible. A promising material family for the air electrode are rare-earth nickelate oxides with the Ruddlesden-Popper structure. These oxides are known to have a point defect structure in which oxygen interstitials play a key role in the oxygen surface exchange and transport through the lattice. Although the performance of the rare-earth nickelates can be high, they unfortunately react and decompose when in contact with rare-earth doped ceria. Ceria is typically added as a second phase from the standpoint of buffering the coefficient of thermal expansion, providing additional oxygen ionic conducting paths, and for forming the buffer layer preventing adverse reactions between the oxygen electrode and the electrolyte which are typically yttrium or scandium doped zirconia.This work focuses on stabilizing the rare-earth nickelate electrodes through compositional modifications while developing cell-design agnostic material solutions using these materials. The driving force for nickelate decomposition was determined to be the high limits for cation solubility within typical ceria-based barrier layers. A solution to this problem is presented. In addition, towards improving the performance of cells the oxygen diffusion mechanism was modeled allowing the calculation of ionic conductivity for a variety of cation substitutions within the nickelate structure. Fundamental material properties such as exchange coefficient, oxygen incorporation into the lattice as a function of partial pressure, and electrode resistance over time were measured. Finally, an innovative processing technique for the simultaneous multilayer coating of highly loaded slurries was developed. This process provides a reduction in the number of processing steps required to produce cells while also allowing for good layer adhesion as well as thickness control at the 2.5 micron range.

Li2s-PI3 Cathode for High-Energy-Density All-Solid-State Lithium-Sulfur Batteries

1.Introduction All-solid-state lithium-sulfur batteries (ASSLSBs) are one of the most promising next-generation large scale energy storage devices due to their remarkably high theoretical energy density, which is generated by high capacity of both cathodes, like element S or Li2S and Li metal anode. However, due to insufficient electronic and/or ionic conductivities of element S and Li2S, the low sulfur utilization and correspondingly unsatisfied practical energy density hinder the application of ASSLSBs largely. By heterovalent doping, vacancies in Li2S could be created, leading to higher ionic conductivity [1-2]. In this study, we developed different proportion of PI3-doping Li2S as active material to improve the sulfur utilization. Mixing with CNovel as electronic additive, Li2S-PI3-CNovel as cathode material shows good electrochemical performance. In order to clarify the effect of doping PI3, a detailed analysis of the point defect structure was performed using pair distribution function analysis using high-energy X-ray diffraction, synchrotron X-ray diffraction measurements, and X-ray absorption measurements to correlate with the electrochemical properties. 2. Experimental Li2S-PI3 as active material was synthesized by mixing Li2S and PI3 as raw materials with ball milling method and the proportion of raw materials has been optimized. The characterization of the prepared Li2S-PI3 was conducted by Synchrotron XRD coupled with pair Distribution Function analysis. The ionic conductivities were measured by AC impedance. The cathode materials were prepared based on active materials (90 wt%) and CNovel (10 wt%) as electronic conductor. The batteries composed of Li2S-PI3-CNovel as cathode, Li3PS4 as SSE and Li-In alloy as anode were assembled in the glove box filled with Ar atmosphere. The charge-discharge curves were obtained by galvanostatic measurement. The electronic structure and morphology of the Li2S-PI3-CNovel after electrochemical measurements were examined by X-ray Absorption Spectroscopy (XAS) for S K-edge, P K-edge, and I K-edge. 3.Results and Discussion Pair distribution function (PDF) analysis revealed that with PI3 doping, iodine atoms would occupy sulfur sites and phosphorous atoms would occupy lithium sites, creating lithium vacancies in the antifluorite structure. Figure 1 shows the charge/discharge curves of the Li2S-PI3-CNovel as cathode. The Li2S-PI3-CNovel cathode shows a charge capacity of 440 mAh g-1 and a discharge capacity of 494 mAh g-1 in the first cycle. And the capacities increase to 538 mAh g-1 during the subsequent cycles, with an average voltage of 1.81 V (vs Li/Li+). Even at 1 C (1 C=626 mAh g-1), the cathode without solid-state electrolyte could deliver 207 mAh g-1, corresponding to 38 % capacity retention of that at 0.05 C, which demonstrates good rate performance (Figure 2). The charge compensation is attributed to S, suggesting the conversion reaction between Li2S and element S, which was confirmed by XAS for S K-edge and P K-edge. References H Gamo.et al., Adv. 2022, 3, 2488-2494.NHH Phuc. et al., Energy Res., 2021, 8, 606023. Acknowledgement This research was financially supported by JST ALCA-SPRING Project. Figure 1

The effect of room‐temperature plastic deformation in darkness on the photoluminescence properties of ZnS

AbstractInorganic semiconductors have been considered to be brittle at room temperature generally, but recently zinc sulfide (ZnS), a II–VI compound semiconductor, was found to exhibit extraordinarily large plasticity even at room temperature if it was deformed in darkness. Room‐temperature plastic deformation can achieve high density of glide dislocations in the crystal without significantly changing the point defect structure, and these dislocations themselves have a potential to provide unique functional properties different from those of the bulk. In this study, therefore, undoped ZnS crystals were plastically deformed at room temperature in darkness to generate only a large number of dislocations, and the changes in luminescence properties resulting from this process were investigated for the first time. As a result, we found that ZnS deformed in darkness exhibits characteristic photoluminescence and persistent luminescence emissions with a visible green color. SEM‐CL analyses also identified the emissions from the dislocations. Theoretical calculations indicated that individual dislocations in ZnS have the ability to trap photo‐excited carriers. Such changes in luminescence properties due to room temperature plastic deformation in darkness can be considered to originate from dislocations rather than point defects. In other words, the dislocations themselves serve as the significant recombination centers, realizing visible light emission.

Effect of ion migration on lead halide perovskite on visible light communication system

Benefiting from the high modulation bandwidth (BW), low energy consumption and excellent optical performance, lead halide perovskite has attracted wide attention in visible light communication (VLC). However, the ion migration which results in mobile point defects in perovskite structures is recognized as a crucial key factor inducing the performance degradation. Here, the influence of ion migration in perovskite devices on the performance of VLC was systematically studied. The ion migration process is realized by mixing CsPbBr3 and CsPbI3 quantum dots, during which, the performance of the VLC system is reduced, but it can return to its initial state after stabilization. The on-off keying (OOK) modulation scheme of the perovskite light-emitting diode (LED) device was carried out, achieving a data rate of 90 Mbps.

Theoretical investigation of electronic structure and thermoelectric properties of CN point defects in GaN

GaN bulk with CN point defects has been theoretically calculated using Density Functional Theory and Boltzmann transport theory. Pure GaN and GaN with two CN of the nearest neighbor, the second-nearest neighbor, and the third-nearest neighbor were carried out to investigate the energy band, density of states, and thermoelectric properties. Compared to pure GaN, it was found that impurity levels appear, which lead to the moving down of the Fermi level and then the moving up of top valence bands in GaN with CN defects. Combining with total density of states (TDOS) and partial density of states (PDOS), we found C(p) makes the main contribution to the moving down of the Fermi level. Then, the highest value of figure-of-merit (ZT) was calculated to be 2.66 of GaN with two CN of the nearest neighbor, while it is only 0.94 of pure GaN at 900 K for p-type. ZT of pure GaN and GaN with CN defects are almost the same at room temperature. In short, impurity levels that appeared in GaN in the energy band were related to CN point defects, which are useful for the improvement of thermoelectric properties on GaN at high temperatures. The research is useful for the application of GaN-based semiconductors.

Transformation of defects in semiconductor structures under action of magnetic fields stimulated by drift phenomena

The phenomenon of directed motion of mobile charged point defects in semiconductor structures under action of magnetic fields has been discussed. The features of defect drift in sign-changing magnetic fields have been studied. The effect of directional movement of charged defects under the combined action of constant and alternating magnetic fields has been analyzed. Analytical relations have been presented for the drift rate of defects in semiconductor structures under given impacts.

Identifying native point defect configurations in α-alumina

Intimately intertwined atomic and electronic structures of point defects govern diffusion-limited corrosion and underpin the operation of optoelectronic devices. For some materials, complex energy landscapes containing metastable defect configurations challenge first-principles modeling efforts. Here, we thoroughly reevaluate native point defect geometries for the illustrative case of α-Al2O3 by comparing three methods for sampling candidate geometries in density functional theory calculations: displacing atoms near a naively placed defect, initializing interstitials at high-symmetry points of a Voronoi decomposition, and Bayesian optimization. We find symmetry-breaking distortions for oxygen vacancies in some charge states, and we identify several distinct oxygen split-interstitial geometries that help explain literature discrepancies involving this defect. We also report a surprising and, to our knowledge, previously unknown trigonal geometry favored by aluminum interstitials in some charge states. These new configurations may have transformative impacts on our understanding of defect migration pathways in aluminum-oxide scales protecting metal alloys from corrosion. Overall, the Voronoi scheme appears most effective for sampling candidate interstitial sites because it always succeeded in finding the lowest-energy geometry identified in this study, although no approach found every metastable configuration. Finally, we show that the position of defect levels within the band gap can depend strongly on the defect geometry, underscoring the need to conduct careful searches for ground-state geometries in defect calculations.

Intrinsic point defects and the n -type dopability of Bi2MoO6 with higher photocatalytic performance: A hybrid functional study

Intrinsic point defects play a vital role in regulating the electronic structure and electron carrier concentration (${n}_{0}$) of ${\mathrm{Bi}}_{2}\mathrm{Mo}{\mathrm{O}}_{6}$, which has been demonstrated as a promising photocatalyst. Unfortunately, the source of $n$-type conductivity for its intrinsic defects has proved challenging. Using first-principles hybrid density functional calculations, we investigate the formation energies and electronic structure of intrinsic point defects in ${\mathrm{Bi}}_{2}\mathrm{Mo}{\mathrm{O}}_{6}$. The self-consistent Fermi energies and equilibrium carrier and defect concentrations are calculated using the sc-fermi code based on thermodynamic simulation. It is found that the easy formation of the +2 charged O vacancy (${V}_{\mathrm{O}}^{2+}$) is responsible for its intrinsic $n$-type conductivity under Bi-rich/O-poor conditions, and thus, it can have a very high density (reaching up to ${10}^{19} \mathrm{c}{\mathrm{m}}^{\ensuremath{-}3}$), making it the dominant defect in ${\mathrm{Bi}}_{2}\mathrm{Mo}{\mathrm{O}}_{6}$. Under O-rich conditions, only adopting both ${\mathrm{D}}^{+}$ doping and quenching methods in ${\mathrm{Bi}}_{2}\mathrm{Mo}{\mathrm{O}}_{6}$ can reach a higher carrier density $(>{10}^{17}\phantom{\rule{0.16em}{0ex}}\mathrm{c}{\mathrm{m}}^{\ensuremath{-}3})$. Moreover, under the broad range of chemical potentials of $\ensuremath{-}2.50\phantom{\rule{0.16em}{0ex}}\mathrm{eV}<\mathrm{\ensuremath{\Delta}}{\ensuremath{\mu}}_{\mathrm{Bi}}<0, \ensuremath{-}6.32\phantom{\rule{0.16em}{0ex}}\mathrm{eV}<\mathrm{\ensuremath{\Delta}}{\ensuremath{\mu}}_{\mathrm{Mo}}<\ensuremath{-}1.48\phantom{\rule{0.16em}{0ex}}\mathrm{eV}$, and $\ensuremath{-}2.19\phantom{\rule{0.16em}{0ex}}\mathrm{eV}<\mathrm{\ensuremath{\Delta}}{\ensuremath{\mu}}_{\mathrm{O}}<\ensuremath{-}0.65\phantom{\rule{0.16em}{0ex}}\mathrm{eV}$, after quenching from 700 to 300 K, ${\mathrm{Bi}}_{2}\mathrm{Mo}{\mathrm{O}}_{6}$ can be effectively donor doped without significant compensation, and ${n}_{0}$ increases as $\mathrm{\ensuremath{\Delta}}{\ensuremath{\mu}}_{\mathrm{O}}$ decreases or temperature increases. Our results can give a guide in selecting optimum growth and quenching conditions to achieve high $n$-type doping and suppress compensation.