Several approaches have been used to investigate the impact of Nitrogen (N) on the electronic structure of GaAs$_{1-x}$N$_{x}$ alloys, however, there is no agreement between theory and experiments about the importance of the different N interstitial defects in these alloys, and their nature is still unknown. Here we analyze the impact of five different N defects on the electronic structure of GaAs$_{1-x}$N$_{x}$ alloys, using density-functional methods: we calculate electronic states, formation energies and charge transition levels. The studied defects include N$_{As}$, As$_{Ga}$, As$_{Ga}$-N$_{As}$ substitutional defects, and (N-N)$_{As}$, (N-As)$_{As}$ split-interstitial complex defects. Our calculated defect formation energies agree with those reported by S.B. Zhang et al. [Phys. Rev. Lett. 86, 1789 (2001)], who predicted these defects. Among the interstitial defects, we found that (N-As)$_{As}$ emerges as the lowest energy configuration in comparison with (N-N)$_{As}$, agreeing with recent experiments [T. Jen, et al., Appl. Phys. Lett. 107, 221904 (2015)]. We also calculated the levels induced in the electronic structure due to each of these defects: defect states may occur as deep levels in the gap, shallow levels close to the band edges, and as levels between bulk states. We find that the largest changes in the band structure are produced by an isolated N atom in GaAs, which is resonant with the conduction band, exhibiting a strong hybridization between N and GaAs states. Deeper levels in the bandgap are obtained with (N-N)$_{As}$ split-interstitial defects. Our results confirm the formation of highly localized states around the N sites, which is convenient for photovoltaics and photoluminescence applications.
The remarkable mechanical properties of high entropy alloys can be further improved by interstitial alloying. In this work we employ density functional theory calculations to study the solution energies of dilute carbon interstitial atoms in tetrahedral and octahedral sites in bcc HfNbTiVZr. Our results indicate that carbon interstitials in tetrahedral sites are unstable, and the preferred octahedral sites present a large spread in the energy of solution. The inclusion of carbon interstitials induces large structural relaxations with long-range effects. The effect of local chemical environment…
Due to their high strength and advantageous high-temperature properties, tungsten-based alloys are being considered as plasma-facing candidate materials in fusion devices. Under neutron irradiation, rhenium, which is produced by nuclear transmutation, has been found to precipitate in elongated precipitates forming thermodynamic intermetallic phases at concentrations well below the solubility limit. Recent measurements have shown that Re precipitation can lead to substantial hardening, which may have a detrimental effect on the fracture toughness of W alloys. This puzzle of sub-solubility preci…
Determinants of Self-Interstitial Energetics in Refractory High-Entropy Alloys
Key Laboratory of Automobile Materials (Jilin University), Ministry of Education, Department of Materials Science and Engineering, Jilin University（吉林大学汽车材料教育部重点实验室，材料科学与工程学院）
High-throughput density functional calculations are used to investigate the effect of interstitial B, C and N atoms on 21 alloys reported to crystallize in the cubic Cu$_3$Au structure. It is shown that the interstitials can have a significant impact on the magneto-crystalline anisotropy energy (MAE), the thermodynamic stability and the magnetic ground state structure, making these alloys interesting for hard magnetic, magnetocaloric and other applications. For 29 alloy/interstitial combinations the formation of stable alloys with interstitial concentrations above 5\% is expected. In Ni$_3$Mn …
Based on high-throughput density functional theory calculations, we investigated the effects of light interstitial H, B, C, and N atoms on the magnetic properties of cubic Heusler alloys, with the aim to design new rare-earth free permanent magnets. It is observed that the interstitial atoms induce significant tetragonal distortions, leading to 32 candidates with large ($>$ 0.4 MJ/m$^3$) uniaxial magneto-crystalline anisotropy energies (MAEs) and 10 cases with large in-plane MAEs. Detailed analysis following the the perturbation theory and chemical bonding reveals the strong MAE originates fro…
Neutron irradiation tends to promote disorder in ordered alloys through the action of the thermal spikes that it generates, while simultaneously introducing point defects and defect clusters. As they migrate, these point defects will promote reordering of the alloys, acting against irradiation-induced disordering. In this study, classical molecular dynamics and a highly parallel accelerated sampling method are used to study the reordering kinetics of Ni$_3$Al under the diffusion of self-interstitial atoms (SIA). By monitoring the order parameter and potential energy from atomistic simulations,…
Impurity diffusion in Zr is potentially important for many applications of Zr alloys, and in particular for their use of nuclear reactor cladding. However, significant uncertainty presently exists about which elements are vacancy vs. interstitial diffusers, which can inhibit understanding and prediction of their behavior under different temperature, irradiation, and alloying conditions. Therefore, first-principles calculations based on density functional theory (DFT) have been employed to predict the temperature-dependent dilute impurity diffusion coefficients for 14 substitutional alloying el…
Solute clusters in long period stacking order (LPSO) alloys play a key role in their idiosyncratic plastic behavior, for example kink formation and kink strengthening. Identifying atomistic details of cluster structures is a prerequisite for atomistic modeling of LPSO alloys and is crucial for improving their strength and ductility; however, there is much uncertainty regarding interstitial atoms in the cluster. Although density functional theory calculations have shown that the inclusion of Mg interstitial atoms is energetically most favorable in majority of LPSO alloys, solute elements have a…
Tracer diffusion of the substitutional components in (CoCrFeNiMn)$_{1-x}$C$_x$ high-entropy alloys with x = 0.002, 0.005 and 0.008 (in at. fractions) is measured at elevated temperatures from 1173 to 1373 K. Two different characteristic effects of interstitial carbon addition on substitutional diffusion in these FCC alloys are distinguished. At the highest temperature of 1373 K, alloying by C with relatively low concentrations (x = 0.002) retards diffusion of the substitutional elements with respect to those in the C-free alloy. At lower temperatures and/or higher C concentrations (x > 0.005),…
Interstitial Fe-Cr alloys: Tuning of magnetism by nanoscale structural control and by implantation of nonmagnetic atoms
使用密度泛函理论，我们进行了一个完整的原子弛豫的散装铁氧体与12.5%的浓度的单原子间隙Cr周期性地位于bcc Fe $_α$细胞的边缘。我们表明，在这种人工设计的合金结构弛豫导致显着的原子位移，并在形成新的高度稳定的配置与平行链的八面体排列的铁的结果。这种类型的合金的低对称金属状态下的增强的磁极化可以通过额外包含诸如氮的非金属杂质来外部控制。我们讨论了生成的间隙合金在自旋电子器件中的可能应用，并建议将其作为新型耐用不锈钢的基础。
We derive an Ising Hamiltonian for kinetic simulations involving interstitial and vacancy defects in binary alloys. Our model, which we term `ABVI', incorporates solute transport by both interstitial defects and vacancies into a mathematically-consistent framework , and thus represents a generalization to the widely-used ABV model for alloy evolution simulations. The Hamiltonian captures the three possible interstitial configurations in a binary alloy: A-A, A-B, and B-B, which makes it particularly useful for irradiation damage simulations. All the constants of the Hamiltonian are expressed in…
We use an $sp^3d^5s^* $ tight-binding model to investigate the electronic and optical properties of realistic site-controlled (111)-oriented InGaAs/GaAs quantum dots. Special attention is paid to the impact of random alloy fluctuations on key factors that determine the fine-structure splitting in these systems. Using a pure InAs/GaAs quantum dot as a reference system, we show that the combination of spin-orbit coupling and biaxial strain effects can lead to sizeable spin-splitting effects in these systems. Then, a realistic alloyed InGaAs/GaAs quantum dot with 25\% InAs content is studied. Our…
High-entropy alloys (HEAs) composed of multiple principal elements have been shown to offer improved radiation resistance over their elemental or dilute-solution counterparts. Using NiCoFeCrMn HEA as a model, here we introduce carbon and nitrogen interstitial alloying elements to impart chemical heterogeneities in the form of the local chemical order (LCO) and associated compositional variations. Density functional theory simulations predict chemical short-range order (CSRO) (nearest neighbors and the next couple of atomic shells) surrounding C and N, due to the chemical affinity of C with (Co…
Impact of interstitial carbon on local lattice distortions in CoCrFeMnNi high-entropy alloys
Helmholtz-Zentrum Berlin für Materialien und Energie (HZB)（柏林亥姆霍兹材料能源中心）；Institute of Solid State Physics, University of Latvia（拉脱维亚大学固体物理研究所）；Department of Metallurgical and Materials Engineering, Indian Institute of Technology Patna（巴特那印度理工学院冶金与材料工程系）；Deutsches Elektronen-Synchrotron DESY（德国电子同步辐射中心）；Interdisciplinary Centre for Advanced Materials Simulation, Ruhr-Universität Bochum（鲁尔大学波鸿跨学科先进材料模拟中心）；Department of Computational Materials Design, Max-Planck-Institute for Sustainable Materials（马普可持续材料研究所计算材料设计系）；Institute for Materials Science, University of Stuttgart（斯图加特大学材料科学研究所）；Institute of Materials Physics, University of Münster（明斯特大学材料物理研究所）
Significant efficiency droop is a major concern for light-emitting diodes and laser diodes operating at high current density. Recent study has suggested that heavily Bi-alloyed GaAs can decrease the non-radiative Auger recombination and therefore alleviate the efficiency droop. Using density functional theory, we studied a newly fabricated quaternary alloy, GaAs1-x-yPyBix, which can host significant amounts of Bi, through calculations of its band gap, spin-orbit splitting, and band offsets with GaAs. We found that the band gap changes of GaAs1-x-yPyBix relative to GaAs are determined mainly by…
The high solubility of oxygen in Ti, Zr and Hf makes it difficult to stabilize the protective oxide scales on their surfaces as the subsurface regions can serve as boundless sinks that continuously dissolve oxygen. Alloying elements are crucial to reduce the oxygen solubility and diffusivity within early transition metals. Past studies have shown that substitutional alloying additions to titanium repel interstitial oxygen. Here we use first-principles calculations to show that this repulsion is short ranged and identify a variety of factors that are likely responsible for the repulsive interac…
Dislocations can climb out of their glide plane by absorbing (or emitting) point defects (vacancies and self-interstitial atoms (SIAs)). In contrast with conservative glide motion, climb relies on the point defects' thermal diffusion and hence operates on much longer timescales, leading to some forms of creep. Whilst equilibrium point defect concentrations allow dislocations to climb to relieve non-glide stresses, point defect supersaturations also lead to osmotic forces, driving dislocation motion even in the absence of external stresses. Self-interstitial atoms typically have significantly h…
12-band $\textbf{k}\cdot\textbf{p}$ model for dilute bismide alloys of (In)GaAs derived from supercell calculations
在（In）GaAs中掺入微量铋（Bi）已被证明会产生独特的电子性质，原则上可以用于设计高效率的电信激光器。这激发了这些稀铋化物合金的电子结构的简单模型的发展，其可用于评估其作为光学应用的候选材料系统的潜力。在这里，我们开始使用详细的计算的基础上的$sp^{3}s^{*}$紧束缚模型的（In）GaBi $_{x}$ As $_{1-x}$，以验证在这些合金中的价带-反交叉相互作用的存在。基于紧束缚模型，导出了稀二酰二亚胺合金的12带$\textbf{k}\cdot\textbf{p}$哈密顿量。我们表明，从12带模型得到的能带结构是在良好的协议与全紧束缚超原胞计算。最后，我们将12带模型应用于In $_{0.53}$ Ga $_{0.47}$ Bi $_{x}$ As $_{1-x}$，并将计算的带隙和自旋轨道分裂的变化与在一系列MBE生长的In $_{0.53}$ Ga $_{0.47}$ Bi $_{x}$ As $_{1-x}$ /InP层上进行的各种光谱测量进行比较。
We develop a fast and accurate machine-learned interatomic potential for the Mo-Nb-Ta-V-W quinary system and use it to study segregation and defects in the body-centred cubic refractory high-entropy alloy MoNbTaVW. In the bulk alloy, we observe clear ordering of mainly Mo-Ta and V-W binaries at low temperatures. In damaged crystals, our simulations reveal clear segregation of vanadium, the smallest atom in the alloy, to compressed interstitial-rich regions like radiation-induced dislocation loops. Vanadium also dominates the population of single self-interstitial atoms. In contrast, due to its…
Technological applications of novel metastable materials are frequently inhibited by abundant defects residing in these materials. Using first-principles methods we investigate the point defect thermodynamics and phase segregation in the technologically-important metastable alloy GaAsBi. Our calculations predict defect energy levels in good agreement with abundant previous experiments and clarify the defect structures giving rise to these levels. We find that vacancies in some charge states become metastable or unstable with respect to antisite formation, and this instability is a general char…
Si$_x$Ge$_{1-x-y}$Sn$_y$ ternary alloys are a candidate material system for use in solar cells and other optoelectronic devices. We report on the direct transition energies and structural properties of Ge-rich Si$_x$Ge$_{1-x-y}$Sn$_y$ alloys with six different compositions up to 10 % Si and 3 % Sn, lattice-matched to Ge or GaAs substrates. The direct transitions occurring between 0.9 and 5.0 eV were investigated using spectroscopic ellipsometry (SE), and the resulting data was used to obtain the dielectric functions of the Si$_x$Ge$_{1-x-y}$Sn$_y$n layer by fitting a multi-layer model. Values …
Part of developing new strategies for fabrications of nanowire structures involves in many cases the aid of metal nanoparticles (NPs). It is highly beneficial if one can define both diameter and position of the initial NPs and make well-defined nanowire arrays. This sets additional requirement on the NPs with respect to being able to withstand a pre-growth annealing process (i.e. de- oxidation of the III-V semiconductor surface) in an epitaxy system. Recently, it has been demonstrated that Ag may be an alternative to using Au NPs as seeds for particle-seeded nanowire fabrication. This work bri…
Evidence of valence band perturbations in GaAsN/GaAs(001): A combined variable-angle spectroscopic ellipsometry and modulated photoreflectance investigation
Anion substitution with bismuth (Bi) in III-V semiconductors is an effective method for experimental engineering of the band gap Eg at low Bi concentrations, in particular in gallium arsenide (GaAs). The inverse Bi-concentration dependence of Eg has been found to be linear at low concentrations x and dominated by a valence band-defect level anticrossing between As and Bi occupied p levels. This dependence breaks down at high concentrations where empirical models accounting only for the As-Bi interaction are not applicable. Predictive models for the valence band hybridization require a first-pr…
We present a systematic investigation of the effect of H, B, C, and N interstitials on the electronic, lattice and magnetic properties of La(Fe,Si)$_{13}$ using density functional theory. The parent LaSiFe$_{12}$ alloy has a shallow, double-well free energy function that is the basis of itinerant metamagnetism. On increasing the dopant concentration, the resulting lattice expansion causes an initial increase in magnetisation for all interstitials that is only maintained at higher levels of doping in the case of hydrogen. Strong s-p band hybridisation occurs at high B,C and N concentrations. We…
Sluggish and Chemically-Biased Interstitial Diffusion in Concentrated Solid Solution Alloys: Mechanisms and Methods
City University of Hong Kong（香港城市大学）；City University of Hong Kong Shenzhen Research Institute（香港城市大学深圳研究院）；Hong Kong Institute for Advanced Study, City University of Hong Kong（香港城市大学香港高等研究院）
Plasticity in body centered cubic (bcc) refractory metals are largely due to the stress tensor induced either by solute or thermal activation. The mechanism of the solute atom(s) residence causes instability in such metals. Earlier research have considered the mechanism of oxygen (O) or carbon (C) in tungsten (W), even though the major component of the environment is nitrogen (N). In this article, the density functional theory (DFT) was employed to investigate the thermodynamic stable site for an interstitial solute (N or O) in the bcc refractory metals (Mo and Nb) by calculating the equilibri…
