Isolated Point Defects Research Articles

Impact of Fe doping on the reactivity of γ-dicalcium silicate: Insights from DFT calculations

This study investigates the impact of Fe doping on the reactivity of γ-dicalcium silicate (γ-C2S) using density functional theory (DFT) calculations. We examined isolated point defects and defect complexes in various charge states to assess substitution tendencies. The results reveal that substituting Si with Fe is energetically more favorable than substituting Ca, due to smaller distortions and minimal impact on Fe-O bonds compared to Ca-O bonds. We systematically analyzed the impact of Fe impurities on γ-C2S reactivity through atomic charges, chemical bonds, and ab initio molecular dynamics (AIMD) simulations. On the one hand, Fe strengthens nearby Ca-O bonds, reducing the effective charge of oxygen atoms and inhibiting reactivity. On the other hand, hydroxylation of Fe-O groups, followed by dehydroxylation, decreases the coordination number of certain surface Ca ions, enhancing reactivity. The overall reactivity of Fe-doped γ-C2S balances inhibition and enhancement, depending on the reacting molecules. In pure H2O systems, the inhibitory effect prevails, while in the presence of H2CO3, the enhancement effect dominates. Experimental observations corroborate these findings. This study provides insights into impurity doping mechanisms in calcium silicate minerals.

Controlled creation of point defects in three-dimensional colloidal crystals.

Crystal defects crucially influence the properties of crystalline materials and have been extensively studied. Even for the simplest type of defect-the point defect-however, basic properties such as their diffusive behavior, and their interactions, remain elusive on the atomic scale. Here, we demonstrate in situ control over the creation of isolated point defects in a three-dimensional (3D) colloidal crystal allowing insight on a single-particle level. Our system consists of thermoresponsive microgel particles embedded in a crystal of nonresponsive colloids. Heating this mixed-particle system triggers the shrinking of the embedded microgels, which then vacate their lattice positions, creating vacancy-interstitial pairs. We use temperature-controlled confocal laser scanning microscopy to verify and visualize the formation of the point defects. In addition, by reswelling the microgels we quantify the local lattice distortion around an interstitial defect. Our experimental model system provides a unique opportunity to shed light on the interplay between point defects, on the mechanisms of their diffusion, on their interactions, and on collective dynamics.

Defect Analysis in a Long-Wave Infrared HgCdTe Auger-Suppressed Photodiode.

Deep defects in the long-wave infrared (LWIR) HgCdTe heterostructure photodiode were measured via deep-level transient spectroscopy (DLTS) and photoluminescence (PL). The n+-P+-π-N+ photodiode structure was grown by following the metal-organic chemical vapor deposition (MOCVD) technique on a GaAs substrate. DLTS has revealed two defects: one electron trap with an activation energy value of 252 meV below the conduction band edge, located in the low n-type-doped transient layer at the π-N+ interface, and a second hole trap with an activation energy value of 89 meV above the valence band edge, located in the π absorber. The latter was interpreted as an isolated point defect, most probably associated with mercury vacancies (VHg). Numerical calculations applied to the experimental data showed that this VHg hole trap is the main cause of increased dark currents in the LWIR photodiode. The determined specific parameters of this trap were the capture cross-section for the holes of σp = 10-16-4 × 10-15 cm2 and the trap concentration of NT = 3-4 × 1014 cm-3. PL measurements confirmed that the trap lies approximately 83-89 meV above the valence band edge and its location.

Zircon-to-reidite phase transition enhanced by minor radiation damage: Implications for hypervelocity impacts

Reidite, a high-pressure phase of zircon, is increasingly identified at terrestrial impact sites. Despite its growing recognition, the potential applications for estimating minimum impact pressure face impediments due to existing discrepancies in the condition of zircon-reidite transformation, controversial models governing the transformation mechanism, and unclear effects of pre-existing radiation damage on reidite formation. Here, we show enhanced reidite formation by synchrotron X-ray diffraction, Raman spectroscopy, and transmission electron microscopy analyses of zircon grains that have experienced different alpha-decay doses from U and Th impurities and subsequent pressurization in diamond anvil cells. Below ∼1 × 1018 α-decay events/g, the α-decay-induced isolated point defects in the still crystalline zircon facilitate the minor atomic readjustments required for reidite formation. However, above this dose, the loss of long-range periodicity in severely damaged or even metamict zircon inhibits the transformation. The enhanced reidite formation by minor radiation damage coincides with the more common occurrence of reidite at impact sites for which the precursor zircon has a relatively lower alpha-decay-event dose before the impact event. In addition, the detailed atomic-scale structures of twinned reidite provide unambiguous evidence for a characteristic internal stress-induced martensitic transition. These findings have important implications for interpreting the formation conditions of natural reidite due to the convergence of pressure from the static, shockwave, and natural reidite samples.

The Effect of Point Defects on Young’s Modulus of the Off-Stoichiometric Al3X (X = Li, Sc, and Zr) Phases: A First-Principles Study

L12-Al3X (X = Li, Sc, and Zr) precipitates are the main strengthened phases of high-strength aluminum alloys and are critical for aerospace structural materials. Point defects and substitutional ternary elements change the mechanical properties of Al3X. In this paper, the effect of point defects, including vacancy, antisite, and substitutional element addition defects on the elastic modulus of the off-stoichiometric Al3X (X = Li, Sc, and Zr) phase were investigated by using first-principle calculations. The formation enthalpies of the defective Al3X alloy and isolated point defects in Al3X were calculated, and the results showed that the defects have an effect on the structure and elasticity of the off-stoichiometric Al3X phases. The lattice distortion, elastic constants, and elastic moduli were further investigated. It was found that the point defects increased the Young’s modulus for Al3Zr, and the doping of Er improved the Young’s modulus for off-stoichiometric Al3Li and Al3Sc. Adjusting the position of vacancies can improve the elastic modulus. In addition, the doping of substitutional elements (especially Sc, Ti, Zr, Hf, Ta, Mn, Ir, and Cf) can greatly increase the Young’s modulus of off-stoichiometric Al3Li.

Comparative studies of interatomic potentials for modeling point defects in wurtzite GaN

In this paper, a new version of the Stillinger–Weber (SW) potential for wurtzite GaN is presented, by which we systematically explore the structural and thermodynamical properties of native point defects and their complexes. In parallel, the semi-empirical Modified Embedded-Atom Method (MEAM) potential is selected for comparison. The SW and MEAM potentials are assessed by the reproduction of the fundamental properties of wurtzite GaN and by the ability to describe the inversion domain boundaries and the wurtzite–rocksalt phase transition. Then the structural search of native point defects and their complexes in GaN is implemented using both SW and MEAM potentials with the benchmark of Density Functional Theory (DFT) calculations. Besides vacancies and antisites, four N and five Ga interstitials are confirmed by refining the DFT calculations, among which two N split interstitials N+−N⟨21̄1̄0⟩ and N+−Ga⟨011̄0⟩, and two Ga split interstitials, Ga+−Ga⟨011̄0⟩−g and Ga+−N⟨011̄0⟩, are observed for the first time. The SW potential correctly predicts the octahedral occupation GaOct to be the most stable Ga interstitial, while the MEAM potential predicts the ground state of the N+−N⟨011̄0⟩ split interstitial (N+−N⟨011̄0⟩−g) as the most stable N interstitial. However, neither of the two potentials could simultaneously generate the most stable configurations of N and Ga interstitials. The investigations of point defect complexes reveal that N octahedral Frenkel [FrenkelOct(N)] and paired antisite (NGaGaN) defects are unstable and get converted into VN⊕N+−N⟨011̄0⟩−g configurations with different separations between VN and N+−N⟨011̄0⟩−g point defects based on the DFT calculations. The formation energies calculated by the DFT and SW potential demonstrate that Schottky, Ga octahedral Frenkel [FrenkelOct(Ga)], and VN⊕N+−N⟨011̄0⟩−g point defect complexes are energetically feasible and that they should not dissociate into two isolated point defects. In contrast, the MEAM potential predicts the dissociation to be exothermic for Schottky and VN⊕N+−N⟨011̄0⟩−g. Overall, the structural features concerned with N–N or Ga–Ga bonds relaxed by the SW potential are more consistent with DFT calculations than the MEAM counterpart.

Photoluminescence microscopy as a noninvasive characterization method for defects in gallium oxide and aluminum gallium oxide epitaxial films

Herein we utilize polarized photoluminescence (PL) microscopy and spectral analysis to locate and characterize many different types of µm-scale extended defects present in melt-grown bulk crystals and metal-organic vapor-phase epitaxy (MOVPE)-grown epitaxial thin films of β-Ga2O3 and β-(Al,Ga)2O3. These include pits, divots, mounds, scratches, rotation domain boundaries, stacking faults, cracks, and other defect categories. Some types of µm-scale defects simply decrease overall PL yield, while others emit different spectra than single crystal regions. We combine PL microscopy with atomic force microscopy (AFM) and scanning electron microscopy (SEM) to provide detailed characteristics of these different types of features which can arise from both bulk crystal growth, surface preparation, and epitaxial growth processes. We show that sample quality (in terms of extended defects) can be determined by using PL and that attributing spectral features to isolated point defects is invalid unless the sample is proven to not contain extended defects.

Kinetic Model of Acid Gas Induced Defect Propagation in Zeolitic Imidazolate Frameworks

Understanding the degradation of nanoporous materials under exposure to common acid gas contaminants (e.g., SO2, CO2, NO2, and H2S) is essential to elongate their lifetime and thus enable their practical applications in separations and catalysis. Previous theoretical investigations have focused on the formation of isolated point defects, which are insufficient to provide direct insights into the long-term evolution of the bulk properties of materials such as zeolitic imidazolate frameworks (ZIFs) under sustained acid gas exposure. To bridge this divide in both length and time scales, we developed a first-principles lattice-based kinetic model to simulate the defect propagation and bulk material breakdown in ZIFs. This model closely reproduces the experimentally measured macroscopic evolution of the time-dependent bulk materials proprieties and also yields important new insights regarding the autocatalytic nature of ZIF degradation and the spatial distribution of defects. Our results suggest new experimental directions to identify nascent defect clusters in degraded ZIFs and avenues to mitigate degradation under challenging conditions of acid gas exposure.

Effect of phosphorus ion implantation on electrical conductivity and local lattice distortions in diamond

In this work, phosphorus ions have been implanted with various doses at an energy 100 keV on single crystal (100) diamond. We try to understand the local lattice distortions (disorder) induced in the implanted layer post annealing (at 850 °C) as a result of ion impact with the help of out-of-plane as well as in-plane XRD techniques and its corresponding effect on the electrical conductivity in diamond crystal. While a low dose of 1014cm−2 increases the lattice parameter along the out-of-plane direction and leads to formation of isolated point defects (mostly interstitials) in the lattice without introducing much disorder, a moderate dose of 1015cm−2 initiates the process of clustering of these defects in the implanted/defected layer. An out-of-plane tensile strain that is present in low dose case is eventually released with moderate dose implantations. With high doses of phosphorus in diamond, the crystallinity in the implanted layer drops, the damage propagates to the extent that it forms small amorphous pockets within this defected layer; although the lattice is not completely amorphous as it still retains the long range order as confirmed from X-ray absorption results. Our data indicate that the electrical transport in diamond is mainly due to substitutional phosphorus when implanted at low dose of 1014cm−2 and also highlights that damage or ‘localized amorphization’ takes place at a critical implantation dose of 1016cm−2 and therefore the critical phosphorus ion dose of 1015cm−2 (in 100 keV energy regime) i.e. a damage threshold of 8 × 1021vacancies/cm3 is the limit beyond which chances of amorphization is prevalent and the electronic properties in diamond are solely due to sp3 bond breakage.

Electronic Properties of Defective Janus MoSSe Monolayer.

Two-dimensional (2D) transition-metal dichalcogenides (TMDCs) hold great promise in electronics and optoelectronics due to their novel electronic and optical properties. In TMDCs, structural defects are inevitable and might play a decisive role in device performance. In this work, point defects, line vacancies, and 60° grain boundaries (GBs) are explored in 2D Janus MoSSe, a new member to the family of TMDCs, by means of the first-principles calculations. S and Se vacancies are found to be the most favorable point defects, and they tend to aggregate along the zigzag direction to form line vacancies. Comparing with isolated point defects, line vacancies induced in-gap states are more dispersive. In particular, 60° GBs behave as one-dimensional metallic quantum wires, as a consequence of the polar discontinuity. Thus, effectively controlling the formation of defects at nanoscale brings new electronic characteristics, providing new opportunities to broaden the applications of 2D TMDCs.

Spectral quadrature for the first principles study of crystal defects: Application to magnesium

We present an accurate and efficient finite-difference formulation and parallel implementation of Kohn-Sham Density (Operator) Functional Theory (DFT) for non periodic systems embedded in a bulk environment. Specifically, employing non-local pseudopotentials, local reformulation of electrostatics, and truncation of the spatial Kohn-Sham Hamiltonian, and the Linear Scaling Spectral Quadrature method to solve for the pointwise electronic fields in real-space and the non-local component of the atomic force, we develop a parallel finite difference framework suitable for distributed memory computing architectures to simulate non-periodic systems embedded in a bulk environment. Choosing examples from magnesium-aluminum alloys, we first demonstrate the convergence of energies and forces with respect to spectral quadrature polynomial order, and the width of the spatially truncated Hamiltonian. Next, we demonstrate the parallel scaling of our framework, and show that the computation time and memory scale linearly with respect to the number of atoms. Next, we use the developed framework to simulate isolated point defects and their interactions in magnesium-aluminum alloys. Our findings conclude that the binding energies of divacancies, Al solute-vacancy and two Al solute atoms are anisotropic and are dependent on cell size. Furthermore, the binding is favorable in all three cases.

Vacancy Defects in Ga2O3: First-Principles Calculations of Electronic Structure.

First-principles density functional theory (DFT) is employed to study the electronic structure of oxygen and gallium vacancies in monoclinic bulk β-Ga2O3 crystals. Hybrid exchange–correlation functional B3LYP within the density functional theory and supercell approach were successfully used to simulate isolated point defects in β-Ga2O3. Based on the results of our calculations, we predict that an oxygen vacancy in β-Ga2O3 is a deep donor defect which cannot be an effective source of electrons and, thus, is not responsible for n-type conductivity in β-Ga2O3. On the other hand, all types of charge states of gallium vacancies are sufficiently deep acceptors with transition levels more than 1.5 eV above the valence band of the crystal. Due to high formation energy of above 10 eV, they cannot be considered as a source of p-type conductivity in β-Ga2O3.

Healing of nanocracks by collision cascades in nickel

We use molecular dynamics simulations to investigate the interaction between collision cascades and pre-existing nanocracks in nickel (Ni). We find that collision cascades cause the cracks to heal whenever a cascade initiates a thermal spike whose core overlaps with the crack. Moreover, crack healing affects the distribution of radiation-induced defects generated during a collision cascade: defect clusters, such as dislocations and stacking fault tetrahedra, dominate in the presence of crack healing, while isolated point defects dominate in its absence. This work indicates that irradiation may reduce the number of pre-existing crack-like flaws in metallic components, potentially improving their mechanical resilience.

Self-diffusion mechanisms based defect complexes in MoSi2

MoSi2 is widely concerned due to excellent electrical conductivity, oxidation resistance as a typical transition metal silicide. The high-temperature diffusion behavior is one of the important factors for the degradation of MoSi2 coatings. However, the diffusion mechanism in MoSi2 is still unclear. Prior theoretical work mostly focused on defect formation energy, but these are not consistent with the self-diffusion experiments because the migration behaviors were not considered. Therefore, the purpose of this work was to investigate the microscopic diffusion mechanisms of Mo and Si atoms in MoSi2 using density functional theory and the CI-NEB method. We confirmed that the temperature-dependent vibrational contribution has a significant impact on the defect formation free energy. The isolated point defects in MoSi2 will tend to aggregate to form defect complexes, which participate in the atomic diffusion as mediators. The defect migration behaviors of atoms for vacancy mediated, vacancy complex mediated, and antisite assisted jumps were obtained based on electronic structures analysis. The results show that Si diffusion is mediated by intrasublattice jumps of the nearest neighbor Si vacancies. Moreover, the destroyed covalent Mo–Si bonds by Si vacancies and the non-directional weak metal bonds formed by the Mo antisites and Mo atoms could improve the mobility of the Mo atom which results in the low migration barrier. The agreement between our calculations and the reported experimental results indicates that the dominant diffusion mechanism for Mo atoms is mediated by vacancy complex mediated jumps and antisite assisted jumps. It is concluded that the Si vacancy-based defect complexes are likely the diffusion mediators for Mo atom self-diffusion in MoSi2. This work provides a deeper insight into the connection between the atomic mechanism and the macroscopic behavior for the diffusion in the MoSi2, and establishes the basis for further optimizing high-temperature coating materials.

Vibrational and vibronic structure of isolated point defects: The nitrogen-vacancy center in diamond

We present a theoretical study of vibrational and vibronic properties of a point defect in the dilute limit by means of first-principles density functional theory calculations. As an exemplar we choose the negatively charged nitrogen-vacancy center, a solid-state system that has served as a testbed for many protocols of quantum technology. We achieve low effective concentrations of defects by constructing dynamical matrices of large supercells containing tens of thousands of atoms. The main goal of the paper is to calculate luminescence and absorption lineshapes due to coupling to vibrational degrees of freedom. The coupling to symmetric $a_1$ modes is computed via the Huang-Rhys theory. Importantly, to include a nontrivial contribution of $e$ modes we develop an effective methodology to solve the multi-mode $E \otimes e$ Jahn-Teller problem. Our results show that for NV centers in diamond a proper treatment of $e$ modes is particularly important for absorption. We obtain good agreement with experiment for both luminescence and absorption. Finally, the remaining shortcomings of the theoretical approach are critically reviewed. The presented theoretical approach will benefit identification and future studies of point defects in solids.

The influence of temperature and energy on defect evolution and clustering during cascade in GaAs

Molecular dynamics (MD) is used to simulate cascade collision in gallium arsenide (GaAs) under different temperatures (300–900 K). During the entire simulation, the primary knock-on atom (PKA) is incident at a special angle, and its energy (EPKA) is within 10 keV. The simulation results are found to be reasonable based on the NRT equation and show that high EPKA causes direct damage, thereby increasing all evolution parameters such as the peak time (tp), steady time (ts), peak (Np) number, and steady (Ns) number of defects. Compared to EPKA, high temperatures reduce Ns of Frenkel pairs and increase the threshold displacement energy (Ed), during which Ga defects occupy the main part. It is also found that the difference between Ga and As vacancy-interstitial pairs on the amount makes tp of GaAs defects longer than AsGa defects, leading to a significant delay in antisite defects as temperature increases. Regarding clusters, high temperatures can promote the transformation of large clusters to isolated point defects for the vacancies, while only the transformation of large and small clusters is observed in the interstitials.

Determination of Thermal Expansion, Defect Formation Energy, and Defect-Induced Strain of α-U Via ab Initio Molecular Dynamics

Uranium (U) is often alloyed with molybdenum (Mo) or zirconium (Zr) in order to stabilize its high-temperature body-centered cubic phase for use in nuclear reactors. However, in all metallic fuel forms, the α phase of U remains in some fraction. This phase decomposition due to temperature or compositional variance can play an outsized role on fuel performance and microstructural evolution. Relatively little is known about fundamental point defect properties in α-U at non-zero temperatures, from either computational or experimental studies. This work performs the first thorough evaluation of the α phase of U via ab initio molecular dynamics (AIMD). A number of thermophysical properties are calculated as a function of temperature, including equilibrium lattice parameters, thermal expansion, and heat capacity. These results indicate a two-region behavior, with the transition at 400 K. The thermal expansion/contraction in the a/b direction occurs rapidly from 100 up to 400 K, after which a more linear and gradual change in the lattice constant takes place. The volumetric expansion matches experiments quantitatively, but the individual lattice constant expansion only matches experiments qualitatively. Point defect formation energies and induced lattice strains are also determined as a function of temperature, providing insight on defect populations and the fundamentals of irradiation growth in α-U. Interstitials induce significantly more strain than vacancies, and the nature of that strain is highly dependent on the individual lattice directions. The direction of point defect-induced lattice strain is contrary to the irradiation growth behavior of α-U. This work shows that isolated point defects cannot be the primary driving force responsible for the significant irradiation-induced growth of α-U observed experimentally.

Evolutionary computing and machine learning for discovering of low-energy defect configurations

Density functional theory (DFT) has become a standard tool for the study of point defects in materials. However, finding the most stable defective structures remains a very challenging task as it involves the solution of a multimodal optimization problem with a high-dimensional objective function. Hitherto, the approaches most commonly used to tackle this problem have been mostly empirical, heuristic, and/or based on domain knowledge. In this contribution, we describe an approach for exploring the potential energy surface (PES) based on the covariance matrix adaptation evolution strategy (CMA-ES) and supervised and unsupervised machine learning models. The resulting algorithm depends only on a limited set of physically interpretable hyperparameters and the approach offers a systematic way for finding low-energy configurations of isolated point defects in solids. We demonstrate its applicability on different systems and show its ability to find known low-energy structures and discover additional ones as well.

A single silicon colour centre resolved

Isolated point defects in silicon that emit light at telecom wavelengths could help accelerate the development of quantum information technologies using commercial platforms.

Structure and role of carbon-related defects in yttrium aluminum garnet

This paper presents ab-initio calculations of composition and energy structure of carbon-related defects in carbon-doped yttrium aluminum garnet, Y3Al5O12. Defect formation energies are considered for isolated point defects and their combinations in case of O-poor atmosphere, which is inherent to crystal growth under Ar + CO gas conditions, and O-rich atmosphere used at post-growth annealing. The point CAl and complex carbon-related defects, such as Ci-VAl, and CAl-VO with lower formation energies should play a role of electron acceptors that compete with oxygen vacancies for electron capture. These results are discussed in conjunction with specific properties of carbon-doped garnets, in particular, no F-type center formation in annealed crystals, even under high irradiation doses.