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Results for “native point defects”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Low-frequency lattice phonons in halide perovskites explain high defect tolerance toward electron-hole recombination

Low-cost solution-based synthesis of metal halide perovskites (MHPs) invariably introduces defects in the system, which could form Shockley-Read-Hall (SRH) electron-hole recombination centers detrimental to solar conversion efficiency. Here, we investigate the nonradiative recombination processes due to native point defects in methylammonium lead halide (MAPbI 3 ) perovskites using ab initio nonadiabatic molecular dynamics within surface-hopping framework. Regardless of whether the defects introduce a shallow or deep band state, we find that charge recombination in MAPbI 3 is not enhanced, contrary to predictions from SRH theory. We demonstrate that this strong tolerance against defects, and hence the breakdown of SRH, arises because the photogenerated carriers are only coupled with low-frequency phonons and electron and hole states overlap weakly. Both factors appreciably decrease the nonadiabatic coupling. We argue that the soft nature of the inorganic lattice with small bulk modulus is key for defect tolerance, and hence, the findings are general to other MHPs.

Science & Technology - Other Topics↗
DOE OSTI2020

Soft Lattice and Defect Covalency Rationalize Tolerance of β‐CsPbI 3 Perovskite Solar Cells to Native Defects

Abstract Although all‐inorganic metal halide perovskites (MHPs) have shown tremendous improvement, they are still inferior to the hybrid organic–inorganic MHPs in efficiency. Recently, a conceptually new β‐CsPbI 3 perovskite reached 18.4 % efficiency combined with good thermodynamic stability at ambient conditions. We use ab initio non‐adiabatic molecular dynamics to show that native point defects in β‐CsPbI 3 are generally benign for nonradiative charge recombination, regardless of whether they introduce shallow or deep trap states. These results indicate that MHPs do not follow the simple models used to explain defect‐mediated charge recombination in the conventional semiconductors. The strong tolerance is due to the softness of the perovskite lattice, which permits separation of electrons and holes upon defect formation, and only allows carriers to couple to the low‐frequency vibrations. Both factors decrease notably the non‐adiabatic coupling and slow down the dissipation of energy to heat.

Chu, Weibin↗
DOE OSTI2023

Trap characterization of high-growth-rate laser-assisted MOCVD GaN

A detailed study comparing defect incorporation between laser-assisted metal-organic chemical vapor deposition (MOCVD)-grown GaN and conventional low- and high-growth-rate MOCVD GaN was conducted. Using deep-level transient and optical spectroscopy, traps throughout the bandgap were characterized where traps were found at EC-0.25 eV, EC-0.57 eV, EC-0.72 eV, EC-0.9 eV, EC-1.35 eV, EC-2.6 eV, and EC-3.28 eV in all three samples. This indicates no new traps were observed in the laser-assisted MOCVD GaN sample. Overall, the trap concentrations in the laser-assisted MOCVD sample were ∼2× higher than the optimal low-growth-rate sample, but this is primarily due to the increase in gallium vacancy EC-2.6 eV and carbon-related EC-3.28 eV trap concentrations. The EC-0.9 eV trap concentration was ∼2× higher in the laser-assisted sample, so proton irradiation experiments were conducted to identify the physical source of this level. The results indicated this was a native point defect likely related to gallium interstitials. Overall, this study shows that the laser-assisted MOCVD growth method is promising for future thick, high-quality GaN epilayers after further growth optimizations.

Physics↗
DOE OSTI2024

Impact of metal diffusion, lattice distortions, native defects, and ambient on dielectric breakdown in Ni–Ga 2 O 3 Schottky diodes

Ga 2 O 3 unipolar devices are of high interest due to their ~8 MV/cm predicted breakdown fields, which have not yet been achieved due to premature device failure. Pre- and post-failure defect analysis of Ni–Ga 2 O 3 Schottky diodes in ultrahigh vacuum (UHV) and air were performed using depth-resolved cathodoluminescence, high angle annular dark field scanning transmission electron microscopy, and energy dispersive x-ray analysis to understand the physical mechanisms that precede premature breakdown. The breakdown voltage in UHV was dramatically reduced by nearly 40% compared with the breakdown in air. This reduction in the breakdown voltage correlated with post-breakdown differences in Ni distribution, indicating that the coordination and bonding of Ni contribute strongly to electrical behavior in Ni–Ga 2 O 3 Schottky diodes. Breakdown studies in UHV revealed that Ni diffuses away more from the metal–semiconductor interface than with air breakdown, where Ni localizes more near the interface, indicative of the preferential formation of a Ni oxide under O-poor conditions. These measurements also identified the formation of divacancy-interstitial complexes and their characteristic luminescence signature ~150 nm from the interface, the densities of which correlated with breakdown fields. These findings show that electric-field-induced degradation occurs via the rearrangement of native point defects, which act as an additional precursor to device failure. Macroscopically, they show the impact of both vacuum conditions and metal reactivity on Ga 2 O 3 device fabrication.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Accelerated screening of functional atomic impurities in halide perovskites using high-throughput computations and machine learning

The pressing need for novel materials that can serve rising demands in solar cell and optoelectronic technologies makes the nexus of halide perovskites, high-throughput computations, and machine learning, very promising. Ever increasing amounts of data on the structure, fundamental properties, and device performance of halide perovskites provide opportunities for learning chemical rules and design principles that make these materials attractive, and applying them across wide chemical spaces. In this work, we show that impurity properties of halide perovskites computed using density functional theory (DFT) can be combined with machine learning (ML) to deliver predictive models and quick identification of optoelectronically active impurity atoms. Our computation lead to the largest reported dataset of the formation energies and charge transition levels of Pb-site impurities in methylammonium lead halide (MAPbX 3 ) perovskites. Descriptors are defined to uniquely represent any impurity atom in any MAPbX 3 compound and mapped to the computed impurity properties using regression techniques such as Gaussian process regression, neural networks, and random forests. We use the best optimized predictive models to make predictions for hundreds of impurities across 9 MAPbX 3 compounds and create lists of dominating impurities, that is, impurities that can shift the equilibrium Fermi level in the perovskite as determined by native point defects. Finally, this accelerated screening powered by computations and machine learning can guide the identification of problematic impurities that may cause undesired recombination of charge carriers, as well as impurities that can be deliberately introduced to tune the perovskite conductivity and resulting photovoltaic absorption.

36 MATERIALS SCIENCE↗
NASA NTRS1995

The control of stoichiometry in Epitaxial semiconductor structures. Interfacial Chemistry: Property relations. A workshop review

A workshop on the control of stoichiometry in epitaxial semiconductor structures was held on August 21-26, 1995 in the hotel Stutenhaus at Vesser in Germany. The secluded location of the workshop in the forest of Thuringia and its informal style stimulated extensive private discussions among the participants and promoted new contacts between young scientists from Eastern and Western Europe and the USA. Topics addressed by the presentations were interactions of precursors to heteroepitaxy and doping with the substrate surface, the control of interfacial properties under the conditions of heteroepitaxy for selected materials systems, methods of characterization of interfaces and native point defects in semiconductor heterostructures and an in depth evaluation of the present status of the control and characterization of the point defect chemistry for one specific semiconductor (ZnGeP2), including studies of both heterostructures and bulk single crystals. The selected examples of presentations and comments given here represent individual choices - made by the author to highlight major points of the discussions.

Bachmann, Klaus J.↗
DOE OSTI2022

Native and radiation induced point defects in AlN and Sc-doped AlN

Herein, we have performed first-principles calculations to investigate the electronic structure, configurations, formation, and binding energies of native and radiation induced point defects in pristine and Sc-doped wurtzite AlN. For the native defects, the nitrogen vacancy has the lowest formation energy in p-type material while the aluminum vacancy has the lowest formation energy in n-type material which is consistent with the previous studies. Several interstitial defect structures were modeled for Al, N, and Sc atoms. The effects of charge state on their relative stability were investigated. The binding energy of Sc with point defects was calculated and found to be dependent strongly on the defect type and charge state. The results obtained are discussed in light of the possible Sc effects on the radiation damage evolution in AlN. Thus the attraction of Sc atom to N vacancy and both Al and N interstitials reduces their mobility and increases Frenkel pair recombination distance.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Defect Chemistry and Hydrogen Transport in La/Sr-Based Oxyhydrides

Oxyhydrides in the series La 2 – y Sr y LiH 1 + y O 3 – y are attractive materials for solid-state hydride electrolytes. However, their chemical stability is poor, and thus far only La 2 LiHO 3 (y = 0) has been demonstrated in a working fuel cell. Using a first-principles approach to study defect chemistry and stability, we find that La 2 LiHO 3 can be stabilized over a range of H-rich, O-poor chemical conditions, while Sr 2 LiH 3 O has low stability. Here, defects are critical for ionic transport and for stability, particularly in Sr 2 LiH 3 O, in which anion antisites and H vacancies readily form. In fact, we show that the ground-state structure of Sr 2 LiH 3 O is inherently disordered. La 2 LiHO 3 has low conductivity, which we connect to the high formation energy of defects such as VO and OH that are necessary for hydride conduction. When Sr 2 LiH 3 O is grown under carefully selected conditions, V H + defects can be made prevalent; these defects give rise to much higher ionic conductivity than can be obtained in La 2 LiHO 3 . In general, we show that the choice of synthesis conditions is vital when seeking to optimize the stability and ionic conductivity of these oxyhydrides, thereby tailoring them for use in solid-state hydrogen fuel cells.

08 HYDROGEN↗
DOE OSTI2022

Unusual electronic transport in (1 - x )Cu 2 Se-( x )CuInSe 2 hierarchical composites

The ability to control the relative density of electronic point defects as well as their energy distribution in semiconductors could afford a systematic modulation of their electronic, optical, and optoelectronic properties. Using a model binary hybrid system Cu 2 Se–CuInSe 2 , we have investigated the correlation between phase composition, microstructure, and electronic transport behavior in the synthesized composites. We found that both Cu 2 Se and CuInSe 2 phases coexist at multiple length scales, ranging from sub-ten nanometer to several micrometers, leading to the formation of a hybrid hierarchical microstructure. Astonishingly, the electronic phase diagram of the (1 - x)Cu 2 Se–(x)CuInSe 2 (15% ≤ x ≤ 100%) hierarchical composites remarkably deviates from the trend normally expected for composites between a heavily doped semiconductor (Cu 2 Se) and a poorly conducting phase (CuInSe 2 ). A sudden 3-fold increase in the electrical conductivity and carrier concentration along with a marginal increase in the carrier mobility is observed for composites at the vicinity of equimolar composition (48% ≤ x ≤ 52%). The carrier concentration increases from ~1.5 × 10 20 cm -3 for the composites with x ≤ 45% to 5.0 × 10 20 cm -3 for x = 50%, and remains constant at 4.5 × 10 20 cm -3 with x value in the range of 52% < x ≤ 90%, then quickly drops to 8 × 10 18 cm -3 for pristine CuInSe 2 phase (x = 100%). The atypical electronic behavior was rationalized in the light of the formation of an inter-band (IB) within the band gap, which arises from the hybridization of native electronic point defects from both Cu 2 Se and CuInSe 2 phases in the resulting hierarchical composites. The result points to a new strategy to modulate the electronic structure of semiconductor composites to maximize interaction and coupling between two fundamentally contrasting properties enabling access to electronic hybrid systems with potential applications as interactive and stimuli-responsive multifunctional materials.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Accurate point defect energy levels from non-empirical screened range-separated hybrid functionals: The case of native vacancies in ZnO

We use density functional theory (DFT) with non-empirically tuned screened range-separated hybrid (SRSH) functionals to calculate the electronic properties of native zinc and oxygen vacancy point defects in ZnO, and we predict their defect levels for thermal and optical transitions in excellent agreement with available experiments and prior calculations that use empirical hybrid functionals. Furthermore, the ability of this non-empirical first-principles framework to accurately predict quantities of relevance to both bulk- and defect-level spectroscopy enables high-accuracy DFT calculations with non-empirical hybrid functionals for defect physics, at a reduced computational cost.

Defects↗
DOE OSTI2026

Point defects and impurities in fluorite PuO 2

The native surface oxide of plutonium plays a critical role in ensuring the stability and safe storage of the underlying metal; consequently, understanding the role of defects and impurities in determining the properties of the oxide layer is critical. Here, in this study, we use hybrid density-functional theory calculations to evaluate the electronic structure and defect chemistry of PuO 2 , the most stable of the native oxide phases, including both native and extrinsic defects. We find that oxygen vacancies (𝑉 O ) form readily in PuO 2 , as do polarons. Electron polarons (𝜂 − ) are the lowest-energy acceptor species in PuO 2 , while the charge compensating donor species will shift from 𝑉 O under O-poor conditions to hole polarons (𝜂 + ) under O-rich conditions. Nitrogen and fluorine can substitute readily for oxygen atoms under O-poor conditions, while fluorine can also incorporate in an interstitial configuration (F$^−_i$) under more O-rich conditions. Carbon and chlorine incorporation in PuO 2 will be very limited. We also evaluate the kinetic barriers for oxygen-related defects, which we find to diffuse readily when present. Our results provide valuable insights into the critical role and variable chemistry of point defects and impurities in PuO 2 , which in turn have important implications for the safe storage of the underlying metal layer. In short, exposure of freshly prepared plutonium to reactive nitrogen- and fluorine-containing contaminants should be avoided, while carbon- or chlorine-containing contaminants are less likely to incorporate readily into the oxide.

Materials science↗
NASA NTRS1981

A thermochemical model of radiation damage and annealing applied to GaAs solar cells

Calculations of the equilibrium conditions for continuous radiation damage and thermal annealing are reported. The calculations are based on a thermochemical model developed to analyze the incorporation of point imperfections in GaAs, and modified by introducing the radiation to produce native lattice defects rather than high-temperature and arsenic atmospheric pressure. The concentration of a set of defects, including vacancies, divacancies, and impurity vacancy complexes, are calculated as a function of temperature. Minority carrier lifetimes, short circuit current, and efficiency are deduced for a range of equilibrium temperatures. The results indicate that GaAs solar cells could have a mission life which is not greatly limited by radiation damage.

Conway, E. J.↗
DOE OSTI2025

First principles investigation of dopants and defect complexes in CdSe$_x$Te$_{1-x}$

Se alloying is a common approach to improve the performance of CdTe solar cells by tuning the bandgap, defect levels, and carrier density. A fundamental understanding of these improvements, specifically the effect of Se alloying on the behavior of defects and dopants in CdTe, remains unclear. Here, in this work, we present a density functional theory (DFT) study of point defect energetics in CdTe and CdSe x Te 1-x with x = 0.25, leading to a comparison of how native defects, dopants (As and Cu), impurities (Cl and O), and related defect complexes behave in CdTe vs CdSe x Te 1-x . Our calculations, performed by combining semi-local and nonlocal hybrid functionals, show a general lowering of the formation energies of native defects as well as substitutional defects formed by As and Cl upon Se addition. For successful p-type doping with As, destabilizing Cl-based defects in the CdSeTe lattice would be essential. We find evidence for some low-energy defect complexes of As, Cl, and O in CdSe 0.25 Te 0.75 . The computed defect formation energies further enable estimates of temperature-dependent defect concentrations and self-consistent Fermi levels. A comparison of defect energetics with the energies of impurity phases reveals that As, Cu, Cl, and O overwhelmingly prefer being segregated to unwanted As 2 O 5 , AsCl 3 , Cd 2 AsCl 2 , and CuO x phases rather than remain at defect sites, but such segregation is less likely to happen in CdSe 0.25 Te 0.75 than in CdTe. Overall, our work presents a list of likely defects and complexes in CdTe and Se-incorporated CdTe, paving the way to explain and mitigate limited dopant activation in experimental observations.

CdTe↗
DOE OSTI2021

Radiative properties of quantum emitters in boron nitride from excited state calculations and Bayesian analysis

Abstract Point defects in hexagonal boron nitride (hBN) have attracted growing attention as bright single-photon emitters. However, understanding of their atomic structure and radiative properties remains incomplete. Here we study the excited states and radiative lifetimes of over 20 native defects and carbon or oxygen impurities in hBN using ab initio density functional theory and GW plus Bethe-Salpeter equation calculations, generating a large data set of their emission energy, polarization and lifetime. We find a wide variability across quantum emitters, with exciton energies ranging from 0.3 to 4 eV and radiative lifetimes from ns to ms for different defect structures. Through a Bayesian statistical analysis, we identify various high-likelihood charge-neutral defect emitters, among which the native V N N B defect is predicted to possess emission energy and radiative lifetime in agreement with experiments. Our work advances the microscopic understanding of hBN single-photon emitters and introduces a computational framework to characterize and identify quantum emitters in 2D materials.

Chemistry↗
DOE OSTI2021

Identification of dislocation-related and point-defects in III-As layers for silicon photonics applications

Abstract The aim of this paper is to identify, analyze and compare the defects present in III-As, as a function of dislocation density, and as a function of the presence/absence of quantum dots (QDs). Such materials are of fundamental importance for the development of lasers and photodiodes for silicon photonics. The study is based on an extensive deep-level transient spectroscopy investigation, carried out on GaAs pin diodes grown on Si and on GaAs (that differ in the dislocation density), with and without embedded QDs. The original results described in this paper demonstrate that: (a) we were able to identify four different defects within the device grown on Si (three electron and one hole traps) and one defect (hole trap) in the device on GaAs, common to both samples; (b) all the majority carrier traps identified are located near midgap, i.e. are efficient non-radiative recombination centers; (c) such defects are absent (or non-detectable) in the sample grown on GaAs substrate, having a very low dislocation density; (d) the presence of QDs does not result in additional defects within the semiconductor material; (e) the analysis of the capture kinetics revealed that two of the identified traps are related to point defects, whereas the other two traps can be associated with point defects located near a dislocation; (f) a comparison with previous reports indicate that the detected traps are related to native III-As defects, or to oxygen-related complexes.

Physics↗
DOE OSTI2022

Effects of Selenium Doping in Zinc Telluride from First Principles

We report point defects and compensation in zinc telluride have been subjects of study for several decades due to the compound’s scientific/technological applications. Despite this, there remains some disagreement in the literature as to the fine details of its defect chemistry. Recently, it has also come under renewed interest due to the emerging Cd( 1–x )Zn x Te( 1–y )Se y material family, used in nuclear radiation detector applications. In this article, we use state-of-the-art computational tools to re-examine the native defect chemistry of ZnTe and explore how it changes upon addition of selenium using density functional theory with screened hybrid exchange–correlation functionals, thermochemical models of the equilibration environment, and statistical mechanics models of the point defect ensemble.

II-VI semiconductors↗
DOE OSTI2022

Efficient microwave absorption with V n+1 C n T x MXenes

The availability of MXenes and other two-dimensional conductive nanomaterials with tunable surface chemistry has reshaped the field of electromagnetic protection. However, the high electrical conductivity and low dielectric loss of titanium-based MXenes lead to strong reflection of electromagnetic waves, even when combined with polymers to form composites. Here, we report on the ability of vanadium-based MXenes to provide broadband microwave absorption. Polyurethane composites with ~2 wt % V n+1 C n T x can absorb 90% of electromagnetic waves covering the entire X band. In addition, pure V n+1 C n T x films of submicrometer thickness can provide effective electromagnetic interference shielding. The free electron transport, surface terminations, native defects, and layers arrangement in composites have profound effects on electronic and dielectric properties of V n+1 C n T x MXenes. This study points toward a new frontier for development of thin and highly absorbing MXene-based electromagnetic protection materials.

77 NANOSCIENCE AND NANOTECHNOLOGY↗