Minimizing the diffusivity difference between vacancies and interstitials in multi-principal element alloys.

Interstitial atoms usually diffuse much faster than vacancies, which is often the root cause for the ineffective recombination of point defects in metals under irradiation. Here, via ab initio modeling of single-defect diffusion behavior in the equiatomic NiCoCrFe(Pd) alloy, we demonstrate an alloy design strategy that can reduce the diffusivity difference between the two types of point defects. The two diffusivities become almost equal after substituting the NiCoCrFe base alloy with Pd. The underlying mechanism is that Pd, with a much larger atomic size (hence larger compressibility) than the rest of the constituents, not only heightens the activation energy barrier (Ea) for interstitial motion by narrowing the diffusion channels but simultaneously also reduces Ea for vacancies due to less energy penalty required for bond length change between the initial and the saddle states. Our findings have a broad implication that the dynamics of point defects can be manipulated by taking advantage of the atomic size disparity, to facilitate point-defect annihilation that suppresses void formation and swelling, thereby improving radiation tolerance.

Effect of local chemical order on the irradiation-induced defect evolution in CrCoNi medium-entropy alloy.

High- (and medium-) entropy alloys have emerged as potentially suitable structural materials for nuclear applications, particularly as they appear to show promising irradiation resistance. Recent studies have provided evidence of the presence of local chemical order (LCO) as a salient feature of these complex concentrated solid-solution alloys. However, the influence of such LCO on their irradiation response has remained uncertain thus far. In this work, we combine ion irradiation experiments with large-scale atomistic simulations to reveal that the presence of chemical short-range order, developed as an early stage of LCO, slows down the formation and evolution of point defects in the equiatomic medium-entropy alloy CrCoNi during irradiation. In particular, the irradiation-induced vacancies and interstitials exhibit a smaller difference in their mobility, arising from a stronger effect of LCO in localizing interstitial diffusion. This effect promotes their recombination as the LCO serves to tune the migration energy barriers of these point defects, thereby delaying the initiation of damage. These findings imply that local chemical ordering may provide a variable in the design space to enhance the resistance of multi-principal element alloys to irradiation damage.

Room Temperature Dynamics of an Optically Addressable Single Spin in Hexagonal Boron Nitride.

Hexagonal boron nitride (h-BN) hosts pure single-photon emitters that have shown evidence of optically detected electronic spin dynamics. However, the electrical and chemical structures of these optically addressable spins are unknown, and the nature of their spin-optical interactions remains mysterious. Here, we use time-domain optical and microwave experiments to characterize a single emitter in h-BN exhibiting room temperature optically detected magnetic resonance. Using dynamical simulations, we constrain and quantify transition rates in the model, and we design optical control protocols that optimize the signal-to-noise ratio for spin readout. This constitutes a necessary step toward quantum control of spin states in h-BN.

Mechanisms of Defect-Mediated Memristive Behavior in MoS2 Monolayer.

The switching dynamics of a Au∥VS2@MoS2 atomristor is explored by first-principles computations of the atomic-configuration energy and electron transport. It is found that external bias can reduce the energy barrier between the two (high- and low-) conduction states, to achieve nonvolatile resistive switching. We find that the force acting on the switching atom is a combination of electrostatic force (while its charge is induced both electrostatically and chemically) and also by electron-wind, whose effect may hinder the writing process at larger bias. The analysis uncovers how the writing and reading processes of the atomristor depend on several factors: (i) atomic structure details of the Au tip; (ii) the space-gap distance between the tip and MoS2 layer; and (iii) tip metal choice. The fundamental understanding of switching events provides useful guidance for memristor design and possible limitations.

Optoelectronic Synapse Based on 2D Electron Gas in Stoichiometry-Controlled Oxide Heterostructures.

Emulating synaptic functionalities in optoelectronic devices is significant in developing artificial visual-perception systems and neuromorphic photonic computing. Persistent photoconductivity (PPC) in metal oxides provides a facile way to realize the optoelectronic synaptic devices, but the PPC performance is often limited due to the oxygen vacancy defects that release excess conduction electrons without external stimuli. Herein, a high-performance optoelectronic synapse based on the stoichiometry-controlled LaAlO3/SrTiO3 (LAO/STO) heterostructure is developed. By increasing La/Al ratio up to 1.057:1, the PPC is effectively enhanced but suppressed the background conductivity at the LAO/STO interface, achieving strong synaptic behaviors. The spectral noise analyses reveal that the synaptic behaviors are attributed to the cation-related point defects and their charge compensation mechanism near the LAO/STO interface. The short-term and long-term plasticity is demonstrated, including the paired-pulse facilitation, in the La-rich LAO/STO device upon exposure to UV light pulses. As proof of concepts, two essential synaptic functionalities, the pulse-number-dependent plasticity and the self-noise cancellation, are emulated using the 5 × 5 array of La-rich LAO/STO synapses. Beyond the typical oxygen deficiency control, the results show how harnessing the cation stoichiometry can be used to design oxide heterostructures for advanced optoelectronic synapses and neuromorphic applications.

Non-radiative recombination centres in InGaN/GaN nanowires revealed by statistical analysis of cathodoluminescence intensity maps and electron microscopy.

The methodology of statistical analysis of cathodoluminescence (CL) intensity mappings on ensembles of several hundreds of InGaN/GaN nanowires (NWs) used to quantify non-radiative recombination centres (NRCs) was validated on InGaN/GaN NWs exhibiting spatially homogeneous cathodoluminescence at the scale of single NWs. Cathodoluminescence intensity variations obeying Poisson's statistics were assigned to the presence of randomly incorporated point defects acting as NRCs. Additionally, another type of NRCs, namely extended defects leading to spatially inhomogeneous cathodoluminescence intensity at the scale of single InGaN/GaN NWs are revealed by high resolution scanning transmission electron microscopy, geometrical phase analysis and two-beam diffraction conditions techniques. Such defects are responsible for deviations from Poisson's statistics, allowing one to achieve a rapid evaluation of the crystallographic and optical properties of several hundreds of NWs in a single cathodoluminescence intensity mapping experiment.

First-Principles Investigation of Near-Surface Divacancies in Silicon Carbide.

The realization of quantum sensors using spin defects in semiconductors requires a thorough understanding of the physical properties of the defects in the proximity of surfaces. We report a study of the divacancy (VSiVC) in 3C-SiC, a promising material for quantum applications, as a function of surface reconstruction and termination with -H, -OH, -F and oxygen groups. We show that a VSiVC close to hydrogen-terminated (2 × 1) surfaces is a robust spin-defect with a triplet ground state and no surface states in the band gap and with small variations of many of its physical properties relative to the bulk, including the zero-phonon line and zero-field splitting. However, the Debye-Waller factor decreases in the vicinity of the surface and our calculations indicate it may be improved by strain-engineering. Overall our results show that the VSiVC close to SiC surfaces is a promising spin defect for quantum applications, similar to its bulk counterpart.

Chemical Kinetics of Metal Single Atom and Nanocluster Formation on Surfaces: An Example of Pt on Hexagonal Boron Nitride.

The production of atomically dispersed metal catalysts remains a significant challenge in the field of heterogeneous catalysis due to coexistence with continuously packed sites such as nanoclusters and nanoparticles. This work presents a comprehensive guidance on how to increase the degree of atomization through a selection of appropriate experimental conditions and supports. It is based on a rigorous macro-kinetic theory that captures relevant competing processes of nucleation and formation of single atoms stabilized by point defects. The effects of metal-support interactions and deposition parameters on the resulting single atom to nanocluster ratio as well as the role of metal centers formed on point defects in the kinetics of nucleation have been established, thus paving the way to guided synthesis of single atom catalysts. The predictions are supported by experimental results on sputter deposition of Pt on exfoliated hexagonal boron nitride, as imaged by aberration-corrected scanning transmission electron microscopy.

Inhomogeneous spatial distribution of non radiative recombination centers in GaN/InGaN nanowire heterostructures studied by cathodoluminescence.

In order to elucidate the mechanisms responsible for cathodoluminescence intensity variations at the scale of single InGaN/GaN nanowire heterostructures, a methodology is proposed based on a statistical analysis on ensembles of several hundreds of nanowires exhibiting a diameter of 180, 240 and 280 nm. For 180 nm diameter, we find that intensitiy variations are consistent with incorporation of point defects obeying Poisson's statistics. For wider diameters, intensity variations at the scale of single NWs are observed and assigned to local growth conditions fluctuations. Finally, for the less luminescent nanowires, a departure from Poisson's statistics is observed suggesting the possible clustering of non independent point defects.

Growth kinetics and substrate stability during high-temperature molecular beam epitaxy of AlN nanowires.

We study the molecular beam epitaxy of AlN nanowires between 950 °C and 1215 °C, well above the usual growth temperatures, to identify optimal growth conditions. The nanowires are grown by self-assembly on TiN(111) films sputtered onto Al2O3. Above 1100 °C, the TiN film is seen to undergo grain growth and its surface exhibits {111} facets where AlN nucleation preferentially occurs. Modeling of the nanowire elongation rate measured at different temperatures shows that the Al adatom diffusion length maximizes at 1150 °C, which appears to be the optimum growth temperature. However, analysis of the nanowire luminescence shows a steep increase in the deep-level signal already above 1050 °C, associated with O incorporation from the Al2O3substrate. Comparison with AlN nanowires grown on Si, MgO and SiC substrates suggests that heavy doping of Si and O by interdiffusion from the TiN/substrate interface increases the nanowire internal quantum efficiency, presumably due to the formation of a SiNxor AlOxpassivation shell. The outdiffusion of Si and O would also cause the formation of the inversion domains observed in the nanowires. It follows that for optoelectronic and piezoelectric applications, optimal AlN nanowire ensembles should be prepared at 1150 °C on TiN/SiC substrates and will require anex situsurface passivation.

The Photonic Atom Probe as a Tool for the Analysis of the Effect of Defects on the Luminescence of Nitride Quantum Structures.

By collecting simultaneously optical and chemical/morphological data from nanoscale volumes, the Photonic Atom Probe (PAP) can be applied not only to the study of the relationship between optical and structural properties of quantum emitter but also to evaluate the influence of other factors, such as the presence of point defects, on the photoluminescence. Through the analysis of multiple layers of InGaN/GaN quantum dots (QDs), grown so that the density of structural defects is higher with increasing distance from the substrate, we establish that the light emission is higher in the regions exhibiting a higher presence of structural defects. While the presence of intrinsic point defects with non-radiative recombination properties remains elusive, our result is consistent with the fact that QD layers closer to the substrate behave as traps for non-radiative point defects. This result demonstrates the potential of the PAP as a technique for the study of the optical properties of defects in semiconductors.

Hydrogen Atoms on Zigzag Graphene Nanoribbons: Chemistry and Magnetism Meet at the Edge.

Although the unconventional π-magnetism at the zigzag edges of graphene holds promise for a wide array of applications, whether and to what degree it plays a role in their chemistry remains poorly understood. Here, we investigate the addition of a hydrogen atom─the simplest yet the most experimentally relevant adsorbate─to zigzag graphene nanoribbons (ZGNRs). We show that the π-magnetism governs the chemistry of ZGNRs, giving rise to a site-dependent reactivity of the carbon atoms and driving the hydrogenation process to the nanoribbon edges. Conversely, the chemisorbed hydrogen atom governs the π-magnetism of ZGNRs, acting as a spin-1/2 paramagnetic center in the otherwise antiferromagnetic ground state and spin-polarizing the charge carriers at the band extrema. Our findings establish a comprehensive picture of the peculiar interplay between chemistry and magnetism that emerges at the zigzag edges of graphene.

The role of point defects related with carbon impurity on the kink of logJ-Vin GaN-on-Si epitaxial layers.

Carbon impurity as point defects makes key impact on the leakage in GaN-on-Si structures. GaN-based epitaxial layers with different point defects by changing carbon-doped concentration were used to investigate the point defects behavior. It was found that leakage mechanisms correspond with space-charge-limited current models at low voltages, and after 1st kink, electron injection from silicon to GaN and PF conduction play a key role in the leakage of both point defects case with low carbon and high carbon doped. In addition, high carbon in GaN-on-Si epitaxial layers obtained lower leakage and larger breakdown voltage. The slope of logJ-Vhas two kinks and effective energy barrierEahas two peaks, 0.4247 eV at about 300 V and 0.3485 eV at about 900 V, respectively, which is related to accepted states and donor states related with carbon impurity. While the slope of logJ-Vhas one kink and effective energy barrierEahas one peak, 0.4794 eV at about 400 V of low carbon in GaN-on-Si epitaxial layers, indicating only field-induced accepted ionized makes impact on leakage. The comparative results of more donor trap density in high carbon indicate point defects related with carbon impurity play a key role in the kinks of logJ-Vslope.

Sub-bandgap photoluminescence properties of multilayer h-BN-on-sapphire.

Two-dimensional hexagonal boron nitride (h-BN) materials have garnered increasing attention due to its ability of hosting intrinsic quantum point defects. This paper presents a photoluminescence (PL) mapping study related to sub-bandgap-level emission in bulk-like multilayer h-BN films. Spatial PL intensity distributions were carefully analyzed with 500 nm spatial resolution in terms of zero phonon line (ZPL) and phonon sideband (PSB) emission-peaks and their linewidths, thereby identifying the potential quantum point defects within the films. Two types of ZPL and PSB emissions were confirmed from the point defects located at the non-edge and edge of the films. Our statistical PL data from the non-edge- and edge-areas of the sample consistently reveal broad and narrow emissions, respectively. The measured optical properties of these defects and the associated ZPL peak shift and line broadening as a function of temperature between 77° and 300° K are qualitatively and quantitatively explained. Moreover, an enhancement of the photostable PL emission by at least a factor of ×3 is observed when our pristine h-BN was irradiated with a 532 nm laser.

Imaging Nonradiative Point Defects Buried in Quantum Wells Using Cathodoluminescence.

Crystallographic point defects (PDs) can dramatically decrease the efficiency of optoelectronic semiconductor devices, many of which are based on quantum well (QW) heterostructures. However, spatially resolving individual nonradiative PDs buried in such QWs has so far not been demonstrated. Here, using high-resolution cathodoluminescence (CL) and a specific sample design, we spatially resolve, image, and analyze nonradiative PDs in InGaN/GaN QWs at the nanoscale. We identify two different types of PDs by their contrasting behavior with temperature and measure their densities from 1014 cm-3 to as high as 1016 cm-3. Our CL images clearly illustrate the interplay between PDs and carrier dynamics in the well: increasing PD concentration severely limits carrier diffusion lengths, while a higher carrier density suppresses the nonradiative behavior of PDs. The results in this study are readily interpreted directly from CL images and represent a significant advancement in nanoscale PD analysis.

Atomic Electrostatic Maps of Point Defects in MoS2.

In this study, we use differential phase contrast images obtained by scanning transmission electron microscopy combined with computer simulations to map the atomic electrostatic fields of MoS2 monolayers and investigate the effect of sulfur monovacancies and divancancies on the atomic electric field and total charge distribution. A significant redistribution of the electric field in the regions containing defects is observed, with a progressive decrease in the strength of the projected electric field for each sulfur atom removed from its position. The electric field strength at the sulfur monovacancy sites is reduced by approximately 50% and nearly vanishes at the divacancy sites, where it drops to around 15% of the original value, demonstrating the tendency of these defects to attract positively charged ions or particles. In addition, the absence of the sulfur atoms leads to an inversion in the polarity of the total charge distribution in these regions.

Identification of Point Defects in Atomically Thin Transition-Metal Dichalcogenide Semiconductors as Active Dopants.

Selective doping in semiconductors is essential not only for monolithic integrated circuity fabrications but also for tailoring their properties including electronic, optical, and catalytic activities. Such active dopants are essentially point defects in the host lattice. In atomically thin two-dimensional (2D) transition-metal dichalcogenides (TMDCs), the roles of such point defects are particularly critical in addition to their large surface-to-volume ratio, because their bond dissociation energy is relatively weaker, compared to elemental semiconductors. In this Mini Review, we review recent advances in the identifications of diverse point defects in 2D TMDC semiconductors, as active dopants, toward the tunable doping processes, along with the doping methods and mechanisms in literature. In particular, we discuss key issues in identifying such dopants both at the atomic scales and the device scales with selective examples. Fundamental understanding of these point defects can hold promise for tunability doping of atomically thin 2D semiconductor platforms.

Direct TEM Observation of Vacancy-Mediated Heteroatom Incorporation into a Zeolite Framework: Towards Microscopic Design of Zeolite Catalysts.

Incorporating hetero-metal-atom, e.g., titanium, into zeolite frameworks can enhance the catalytic activity and selectivity in oxidation reactions. However, the rational design of zeolites containing titanium at specific sites is difficult because the precise atomic structure during synthesis process remained unclear. Here, a titanosilicate with predictable titanium distribution was synthesized by mediating vacancies in a defective MSE-type zeolite precursor, based on a pre-designed synthetic route including modification of vacancies followed by titanium insertion, where electron microscopy (EM) plays a key role at each step resolving the atomic structure. Point defects including vacancies in the precursor and titanium incorporated into the vacancy-related positions have been directly observed. The results provide insights into the role of point defects in zeolites towards the rational synthesis of zeolites with desired microscopic arrangement of catalytically active sites.

Local perturbations of periodic systems. Chemisorption and point defects by GoGreenGo.

We present a software package GoGreenGo-an overlay aimed to model local perturbations of periodic systems due to either chemisorption or point defects. The electronic structure of an ideal crystal is obtained by worldwide-distributed standard quantum physics/chemistry codes, and then processed by various tools performing projection to atomic orbital basis sets. Starting from this, the perturbation is addressed by GoGreenGo with use of the Green's functions formalism, which allows evaluating its effect on the electronic structure, density matrix, and energy of the system. In the present contribution, the main accent is made on processes of chemical nature, such as chemisorption or doping. We address a general theory and its computational implementation supported by a series of test calculations of the electronic structure perturbations for benchmark model solids: simple, face-centered, and body-centered cubium systems. In addition, more realistic problems of local perturbations in graphene lattice, such as lattice substitution, vacancy, and "on-top" chemisorption, are considered.

Bottom-Up Synthesis of Hexagonal Boron Nitride Nanoparticles with Intensity-Stabilized Quantum Emitters.

Fluorescent nanoparticles are widely utilized in a large range of nanoscale imaging and sensing applications. While ultra-small nanoparticles (size ≤10 nm) are highly desirable, at this size range, their photostability can be compromised due to effects such as intensity fluctuation and spectral diffusion caused by interaction with surface states. In this article, a facile, bottom-up technique for the fabrication of sub-10-nm hexagonal boron nitride (hBN) nanoparticles hosting photostable bright emitters via a catalyst-free hydrothermal reaction between boric acid and melamine is demonstrated. A simple stabilization protocol that significantly reduces intensity fluctuation by ≈85% and narrows the emission linewidth by ≈14% by employing a common sol-gel silica coating process is also implemented. This study advances a promising strategy for the scalable, bottom-up synthesis of high-quality quantum emitters in hBN nanoparticles.