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At least 937 records · Page 52
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Observation of Single-Electron Transport and Charging on Individual Point Defects in Atomically Thin WSe 2

Defects significantly impact the properties of 2D semiconductors, providing in-gap quantum states that can serve as a natural platform for single-electron operations, localization sites for excitons to serve as single-photon sources, and potentially quantum spin memories. To date, however, a microscopic observation of such a single-electron transport (SET) behavior has been rarely reported on single defects of 2D semiconductors. In this study, we report a SET and charge-state transition on individual point-defect states buried in the bilayer WSe 2 using scanning tunneling microscopy. SET characteristics of their states is evidenced by both the Coulomb staircase and the saturation behavior of the transport current, consistent with the SET model. Furthermore, we demonstrate that, through the local field of a scanning tunneling microscope tip, it is possible to successively charge the defects by single electrons, suggested by both the ring structures and charging peaks in dI/dV measurements. Our results provide new insights into the quantum nature of these defect-bound states, as well as the possibility of using their single-electron behavior and response for applications in quantum information and local-field sensing.

2D semiconductor↗
DOE OSTI2018

Boron Doping and Defect Engineering of Graphene Aerogels for Ultrasensitive NO 2 Detection

In this study, boron-doped and defect-engineered graphene aerogels are prepared using triphenyl boron as a boron precursor and subsequent heat treatments. The boron chemistry and concentration in the graphene lattice are found to be highly dependent on the temperature used to activate boron. At 1500 °C, boron is incorporated at 3.2 atom % through a combination of B–C, B–N, and B–O bonds. At 1750 °C, the boron concentration decreases to 0.7 atom % and is predominantly incorporated through B–N bonding. Higher temperatures result in complete expulsion of boron from the lattice, leaving behind defects that are found to be beneficial for NO 2 gas detection. The gas sensing properties are explored to gain insight into the impact of boron chemistry on the sensing performance. A highly sensitive and selective conductometric NO 2 sensor is fabricated on a low-power microheater. Defect-engineered graphene aerogels with no boron remaining have superior gas detection properties. At an optimum sensing temperature of 240 °C, the defect-engineered aerogel has a theoretical detection limit of 7 ppb for NO 2 and response and recovery times of 100 and 300 s, respectively, with excellent selectivity over ammonia and hydrogen. Lastly, the superior gas sensing performance of defect-engineered graphene aerogels has remarkable implications for their performance in catalysis and energy storage applications.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Comparative Study of the Effect of Defects on Selective Adsorption of Butanol from Butanol/Water Binary Vapor Mixtures in Silicalite-1 Films

A promising route for sustainable 1-butanol (butanol) production is ABE (acetone, butanol, ethanol) fermentation. However, recovery of the products is challenging because of the low concentrations obtained in the aqueous solution, thus hampering large-scale production of biobutanol. Membrane and adsorbent-based technologies using hydrophobic zeolites are interesting alternatives to traditional separation techniques (e.g., distillation) for energy-efficient separation of butanol from aqueous mixtures. To maximize the butanol over water selectivity of the material, it is important to reduce the number of hydrophilic adsorption sites. This can, for instance, be achieved by reducing the density of lattice defect sites where polar silanol groups are found. The density of silanol defects can be reduced by preparing the zeolite at neutral pH instead of using traditional synthesis solutions with high pH. In this work, binary adsorption of butanol and water in two silicalite-1 films was studied using in situ attenuated total reflectance–Fourier transform infrared (ATR-FTIR) spectroscopy under equal experimental conditions. One of the films was prepared in fluoride medium, whereas the other one was prepared at high pH using traditional synthesis conditions. The amounts of water and butanol adsorbed from binary vapor mixtures of varying composition were determined at 35 and 50 °C, and the corresponding adsorption selectivities were also obtained. Both samples showed very high selectivities (100–23 000) toward butanol under the conditions studied. The sample having low density of defects, in general, showed ca. a factor 10 times higher butanol selectivity than the sample having a higher density of defects at the same experimental conditions. This difference was due to a much lower adsorption of water in the sample with low density of internal defects. Analysis of molecular simulation trajectories provides insights on the local selectivities in the zeolite channel network and at the film surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Radiative Electronic Bound States in the Continuum from Defects in Semiconductors

Continuum-buried defect states in semiconductors are generally expected to be optically inactive because of their strong coupling to continuum bands. Here, we show that such defects can instead host radiative electronic bound states in the continuum (BICs) using the silicon G center as a prototypical example. Hybrid functional first-principles calculations with a Hubbard U correction reveal that a localized defect state, initially buried below the valence band maximum (VBM) in the ground state, undergoes exchange-driven energy-level reordering under optical excitation and shifts above the VBM. This exchange-induced transition suppresses nonradiative decay and enables a robust radiative emission. By computing temperature-dependent nonradiative lifetimes and comparing them to experimental photoluminescence (PL) lifetimes, we quantitatively reproduce the observed temperature dependence of the emission. These results uncover a stabilization mechanism for continuum-embedded defect states and establish electronic BICs as a general paradigm for designing defect-based optical systems, including quantum emitters and qubits.

Hong, SeongYun↗
DOE OSTI2019

Unconventional Defects in a Quasi-One-Dimensional KMn 6 Bi 5

Quasi-one-dimensional (Q1D) structures comprising a compact array of indefinitely long 1D nanowires (NWs) are scarce, especially in a bulk device-scale showing metallic and semiconducting behaviors along different axes. Unlike plentiful observations of nature of defects in three-/two -dimensional materials, there is a notable paucity of such reports in Q1D. Herein we present unconventional motific defects and their properties in a bulk Q1D KMn 6 Bi 5 crystal, in which an individual NW motif acts as one body. We discovered motific inter- and intra-NW defects, such that a linear set of 1D motifs are displaced. Stress generates two domains with altered inter-NW spacings and a Bi–Mn solid solution grain, leading to a local bulk plasmon shift due to NW array reconfiguration as well as atomic rearrangement. The observation of such exotic defects and associated phenomena in this Q1D may provide guidance on overall defect mechanism in other Q1D systems and their collective anisotropic properties.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Behavior of Hydrogarnet‐Type Defects in Hydrous Stishovite at Various Temperatures and Pressures

Abstract Dense polymorphs of silica have been demonstrated experimentally to incorporate from 1.5 wt% to as much as 11.6 wt% H 2 O as OH groups, with implications for the hydrogen budgets of Earth and other planets. This OH is thought to enter the SiO 2 structure via a charge‐balanced substitution in which silicon vacancies (V Si ) are compensated by protonating four of the surrounding six oxygen atoms, often referred to as a hydrogarnet‐type defect. There are many possible configurations for this defect structure in dense silica, but the nature of these configurations and whether they can be distinguished experimentally is unknown. We present here density functional theory calculations that systematically assess the possible configurations of a hydrogarnet‐type defect in stishovite (rutile‐type SiO 2 ), with direct comparisons to experimental vibrational spectroscopy data. We predict that stishovite synthesized at 450 K and 10 GPa quenched to room temperature is dominated by a single defect type with tetrahedral geometry. This leads to OH stretching modes (2,500–3,000 cm −1 ) and SiOH bending modes (∼1,400–1,450 cm −1 ) largely consistent with experimentally observed modes. One remaining issue is that our calculations produce results compatible with experimental data on H to D exchange, but do not explain why a considerable fraction of the 1,420 cm −1 mode shifts by only 40 cm −1 in deuterated samples. At elevated pressures and temperatures, we find that a second square planar defect configuration also becomes favorable, leading to modes that should allow differentiation from the tetrahedral configuration.

Geochemistry & Geophysics↗
DOE OSTI2015

Orientational order of motile defects in active nematics

The study of equilibrium liquid crystals has led to fundamental insights into the nature of ordered materials, as well as many practical applications such as display technologies. Active nematics are a fundamentally different class of liquid crystals, which are driven away from equilibrium by the autonomous motion of their constituent rodlike particles. This internally-generated activity powers the continuous creation and annihilation of topological defects, leading to complex streaming flows whose chaotic dynamics appear to destroy long-range order. Here, we study these dynamics in experimental and computational realizations of active nematics. By tracking thousands of defects over centimeter distances in microtubule-based active nematics, we identify a non-equilibrium phase characterized by system-spanning orientational order of defects. This emergent order persists over hours despite defect lifetimes of only seconds. Lastly, similar dynamical structures are observed in coarse-grained simulations, suggesting that defect-ordered phases are a generic feature of active nematics.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Overcoming diffusion-related limitations in semiconductor defect imaging with phonon-plasmon-coupled mode Raman scattering

Carrier diffusion is of paramount importance in many semiconductor devices, such as solar cells, photodetectors, and power electronics. Structural defects prevent such devices from reaching their full performance potential. Although a large carrier diffusion length indicates high material quality, it also implies increased carrier depletion by an individual extended defect (for instance, a dislocation) and obscures the spatial resolution of neighboring defects using optical techniques. For commonly utilized photoluminescence (PL) imaging, the spatial resolution is dictated by the diffusion length rather than by the laser spot size, no matter the spot is at or below the diffraction limit. We show how Raman imaging of the LO phonon-plasmon-coupled mode can be used to recover the intrinsic spatial resolution of the optical system, and we demonstrate the effectiveness of the technique by imaging defects in GaAs with diffraction-limited optics, achieving a 10-fold improvement in resolution. Furthermore, by combining Raman and PL imaging, we can independently and simultaneously determine the spatial dependence of the electron density, hole density, radiative recombination rate, and non-radiative recombination rate near a dislocation-like defect, which has not been possible using other techniques.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2019

Local electronic descriptors for solute-defect interactions in bcc refractory metals

The interactions between solute atoms and crystalline defects such as vacancies, dislocations, and grain boundaries are essential in determining alloy properties. Here we present a general linear correlation between two descriptors of local electronic structures and the solute-defect interaction energies in binary alloys of body-centered-cubic (bcc) refractory metals (such as W and Ta) with transition-metal substitutional solutes. One electronic descriptor is the bimodality of the d-orbital local density of states for a matrix atom at the substitutional site, and the other is related to the hybridization strength between the valance sp- and d-bands for the same matrix atom. For a particular pair of solute-matrix elements, this linear correlation is valid independent of types of defects and the locations of substitutional sites. These results provide the possibility to apply local electronic descriptors for quantitative and efficient predictions on the solute-defect interactions and defect properties in alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Defect and structural evolution under high-energy ion irradiation informs battery materials design for extreme environments

Understanding defect evolution and structural transformations constitutes a prominent research frontier for ultimately controlling the electrochemical properties of advanced battery materials. Herein, for the first time, we utilize in situ high-energy Kr ion irradiation with transmission electron microscopy to monitor how defects and microstructures evolve in Na- and Li-layered cathodes with 3d transition metals. Our experimental and theoretical analyses reveal that Li-layered cathodes are more resistant to radiation-induced structural transformations, such as amorphization than Na-layered cathodes. The underlying mechanism is the facile formation of Li-transition metal antisite defects in Li-layered cathodes. The quantitative mathematical analysis of the dynamic bright-field imaging shows that defect clusters preferentially align along the Na/Li ion diffusion channels ( a-b planes), which is likely governed by the formation of dislocation loops. Our study provides critical insights into designing battery materials for extreme irradiation environments and understanding fundamental defect dynamics in layered oxides.

25 ENERGY STORAGE↗
DOE OSTI2021

Defect-driven selective metal oxidation at atomic scale

Nanoscale materials modified by crystal defects exhibit significantly different behaviours upon chemical reactions such as oxidation, catalysis, lithiation and epitaxial growth. However, unveiling the exact defect-controlled reaction dynamics (e.g. oxidation) at atomic scale remains a challenge for applications. Here, using in situ high-resolution transmission electron microscopy and first-principles calculations, we reveal the dynamics of a general site-selective oxidation behaviour in nanotwinned silver and palladium driven by individual stacking-faults and twin boundaries. The coherent planar defects crossing the surface exhibit the highest oxygen binding energies, leading to preferential nucleation of oxides at these intersections. Planar-fault mediated diffusion of oxygen atoms is shown to catalyse subsequent layer-by-layer inward oxide growth via atomic steps migrating on the oxide-metal interface. These findings provide an atomistic visualization of the complex reaction dynamics controlled by planar defects in metallic nanostructures, which could enable the modification of physiochemical performances in nanomaterials through defect engineering.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Decoherence of $V^{–}_{B}$ spin defects in monoisotopic hexagonal boron nitride

Spin defects in hexagonal boron nitride (hBN) are promising quantum systems for the design of flexible two-dimensional quantum sensing platforms. Here we rely on hBN crystals isotopically enriched with either 10 B or 11 B to investigate the isotope-dependent properties of a spin defect featuring a broadband photoluminescence signal in the near infrared. By analyzing the hyperfine structure of the spin defect while changing the boron isotope, we first confirm that it corresponds to the negatively charged boron-vacancy center ($V^{–}_{B}$). We then show that its spin coherence properties are slightly improved in 10B-enriched samples. This is supported by numerical simulations employing cluster correlation expansion methods, which reveal the importance of the hyperfine Fermi contact term for calculating the coherence time of point defects in hBN. Using cross-relaxation spectroscopy, we finally identify dark electron spin impurities as an additional source of decoherence. This work provides new insights into the properties of $V^{–}_{B}$ spin defects, which are valuable for the future development of hBN-based quantum sensing foils.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

The dynamic adsorption affinity of ligands is a surrogate for the passivation of surface defects

Abstract Surface defects in semiconducting materials, though they have been widely studied, remain a prominent source of loss in optoelectronic devices; here we sought a new angle of approach, looking into the dynamic roles played by surface defects under atmospheric stressors and their chemical passivants in the lifetime of optoelectronic materials. We find that surface defects possess properties distinct from those of bulk defects. ab initio molecular dynamics simulations reveal a previously overlooked reversible degradation mechanism mediated by hydrogen vacancies. We find that dynamic surface adsorption affinity (DAA) relative to surface treatment ligands is a surrogate for passivation efficacy, a more strongly-correlated feature than is the static binding strength emphasized in prior reports. This guides us to design targeted passivator ligands with high molecular polarity: for example, 4-aminobutylphosphonic acid exhibits strong DAA and provides defect passivation applicable to a range of perovskite compositions, including suppressed hydrogen vacancy formation, enhanced photovoltaic performances and operational stability in perovskite solar cells.

Science & Technology - Other Topics↗
DOE OSTI2017

Computationally predicted energies and properties of defects in GaN

Recent developments in theoretical techniques have significantly improved the predictive power of density-functional-based calculations. In this article, we discuss how such advancements have enabled improved understanding of native point defects in GaN. We review the methodologies for the calculation of point defects, and discuss how techniques for overcoming the band-gap problem of density functional theory affect native defect calculations. In particular, we examine to what extent calculations performed with semilocal functionals (such as the generalized gradient approximation), combined with correction schemes, can produce accurate results. The properties of vacancy, interstitial, and antisite defects in GaN are described, as well as their interaction with common impurities. We also connect the first-principles results to experimental observations, and discuss how native defects and their complexes impact the performance of nitride devices. Overall, we find that lower-cost functionals, such as the generalized gradient approximation, combined with band-edge correction schemes can produce results that are qualitatively correct. However, important physics may be missed in some important cases, particularly for optical transitions and when carrier localization occurs.

36 MATERIALS SCIENCE↗
DOE OSTI2017

First-principles calculation of intrinsic defect chemistry and self-doping in PbTe

Semiconductor dopability is inherently limited by intrinsic defect chemistry. In many thermoelectric materials, narrow band gaps due to strong spin-orbit interactions make accurate atomic level predictions of intrinsic defect chemistry and self-doping computationally challenging. For this study, we use different levels of theory to model point defects in PbTe, and compare and contrast the results against each other and a large body of experimental data. We find that to accurately reproduce the intrinsic defect chemistry and known self-doping behavior of PbTe, it is essential to (a) go beyond the semi-local GGA approximation to density functional theory, (b) include spin-orbit coupling, and (c) utilize many-body GW theory to describe the positions of individual band edges. The hybrid HSE functional with spin-orbit coupling included, in combination with the band edge shifts from G0W0 is the only approach that accurately captures both the intrinsic conductivity type of PbTe as function of synthesis conditions as well as the measured charge carrier concentrations, without the need for experimental inputs. Our results reaffirm the critical role of the position of individual band edges in defect calculations, and demonstrate that dopability can be accurately predicted in such challenging narrow band gap materials.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Deep learning analysis of defect and phase evolution during electron beam-induced transformations in WS2

Abstract Recent advances in scanning transmission electron microscopy (STEM) allow the real-time visualization of solid-state transformations in materials, including those induced by an electron beam and temperature, with atomic resolution. However, despite the ever-expanding capabilities for high-resolution data acquisition, the inferred information about kinetics and thermodynamics of the process, and single defect dynamics and interactions is minimal. This is due to the inherent limitations of manual ex situ analysis of the collected volumes of data. To circumvent this problem, we developed a deep-learning framework for dynamic STEM imaging that is trained to find the lattice defects and apply it for mapping solid state reactions and transformations in layered WS 2 . The trained deep-learning model allows extracting thousands of lattice defects from raw STEM data in a matter of seconds, which are then classified into different categories using unsupervised clustering methods. We further expanded our framework to extract parameters of diffusion for sulfur vacancies and analyzed transition probabilities associated with switching between different configurations of defect complexes consisting of Mo dopant and sulfur vacancy, providing insight into point-defect dynamics and reactions. This approach is universal and its application to beam-induced reactions allows mapping chemical transformation pathways in solids at the atomic level.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Single-defect phonons imaged by electron microscopy

Crystal defects affect the thermal and heat-transport properties of materials by scattering phonons and modifying phonon spectra. To appreciate how imperfections in solids influence thermal conductivity and diffusivity, it is thus essential to understand phonon–defect interactions. Sophisticated theories are available to explore such interactions, but experimental validation is limited because most phonon-detecting spectroscopic methods do not reach the high spatial resolution needed to resolve local vibrational spectra near individual defects. In this paper, we demonstrate that space- and angle-resolved vibrational spectroscopy in a transmission electron microscope makes it possible to map the vibrational spectra of individual crystal defects. We detect a red shift of several millielectronvolts in the energy of acoustic vibration modes near a single stacking fault in cubic silicon carbide, together with substantial changes in their intensity, and find that these changes are confined to within a few nanometres of the stacking fault. These observations illustrate that the capabilities of a state-of-the-art transmission electron microscope open the door to the direct mapping of phonon propagation around defects, which is expected to provide useful guidance for engineering the thermal properties of materials.

42 ENGINEERING↗
DOE OSTI2017

Direct Observation of Sink-Dependent Defect Evolution in Nanocrystalline Iron under Irradiation

Crystal defects generated during irradiation can result in severe changes in morphology and an overall degradation of mechanical properties in a given material. Nanomaterials have been proposed as radiation damage tolerant materials, due to the hypothesis that defect density decreases with grain size refinement due to the increase in grain boundary surface area. The lower defect density should arise from grain boundary-point defect absorption and enhancement of interstitial-vacancy annihilation. In this study, low energy helium ion irradiation on free-standing iron thin films were performed at 573 K. Interstitial loops of a 0 /2 [111] Burgers vector were directly observed as a result of the displacement damage. Loop density trends with grain size demonstrated an increase in the nanocrystalline (<100 nm) regime, but scattered behavior in the transition from the nanocrystalline to the ultra-fine regime (100–500 nm). To examine the validity of such trends, loop density and area for different grains at various irradiation doses were compared and revealed efficient defect absorption in the nanocrystalline grain size regime, but loop coalescence in the ultra-fine grain size regime. Lastly, a relationship between the denuded zone formation, a measure of grain boundary absorption efficiency, grain size, grain boundary type and misorientation angle is determined.

42 ENGINEERING↗