Atomic Defects Research Articles

A novel combining Raman-photoluminescence method to characterize the brittle and plastic states of fused silica based on nanoscale ring structures and atomic point defects

Fused silica has been widely used in many key technical domains. However, the inevitably induced micron-sized brittle fractures during manufacturing processes seriously affect its service performance. Scanning electron and atomic force microscopes are mainly employed to estimate the brittle and plastic states (BPS) of the precise fused silica components, which would put strict demands on the dimensions of detected components and damage the detected surfaces. Herein, the evolution rules of the D2 characteristic peak intensities in Raman spectra corresponding to three-fold rings with the BPS were explored. Interestingly, it is found that the D2 peak intensity first greatly increases in brittle-plastic mixing zones and then sharply decreases in brittle zones. The evolution mechanisms of the nanoscale rings with respect to the BPS were further revealed using the molecular dynamics modeling. The enveloping-space compression of rings and the ring conversion from large- to small rings are found to be the leading factors of the significant increase of the three-fold rings in brittle-plastic mixing zones. And the abrupt destruction of ring structures due to amounts of damaged Si-O bonds in brittle zones contributes to the sharp decrease of the three-fold rings. Based on the evolution rules of the nanoscale rings with the BPS, the brittle-plastic mixing zones could be distinguished from the brittle and plastic zones. It also implies that the rings, especially three-fold rings may dominate the BPS. Moreover, the change laws of the photoluminescence properties with BPS were also studied. It has been found that the photoluminescence envelope area sharply increases with the BPS. It indicates that the concentrations of the atomic point defects would sharply increase with the BPS. Based on the evolution rules of the atomic point defects with the BPS, the brittle and plastic zones could be distinguished. Therefore, a novel Raman-photoluminescence combined method was proposed to characterize the BPS. Finally, its wide applicability was also verified in various specific cases. To sum up, the investigation develops a novel spectral method to effectively characterize the BPS. It is significant for the early warning of the material brittle fractures and the nondestructive characterization of fused silica during the manufacturing processes, which could vigorously promote the further application of fused silica components in various fields.

Transmittance enhancement of amorphous SiO2 via ultraviolet irradiation to eliminate atomic defects

Optical absorption defects seriously degrade the performance of amorphous-SiO2. Laser/UV conditioning (LC/UC) emerge as promising methods for defects elimination, yet its mechanism is still debated due to insufficient defect characterization methods. In this study, the experiments and machine learning potential were used to characterize the defects in Raman, phonon/vibrational density of states, and XRD spectra, the UC mechanism was implied. The UC transforms the atomic defects into medium-range order structure (n-fold rings) to reduce the absorption, the mobile oxygen O0 reduces the energy barrier in the reaction and shorter wavelength of UC is suggested. Experimental results validated that the absorption coefficient below 300 nm after 254 nm UC decreases 62% higher than that after 365 nm UC.

Resonant structure for improved directionality and extraction of single photons

Abstract Fluorescent atomic defects, particularly in dielectric materials such as diamond, are promising for several emerging quantum applications. However, efficient light extraction, directional emission, and narrow spectral emission are key challenges. We have designed a dielectric metasurface exploiting Mie-resonance and Kerker conditions to address these issues. Our designed diamond metasurface, tailored for nitrogen-vacancy (NV) defect centers in diamond, predicts up to 500x improvement in the collection of 637 nm (zero phonon line) photons over that from the bare diamond. Our design achieves highly directional emission, predominantly emitting in a 20° lobe in the forward direction. This makes the light collection more efficient, including fiber-based collection. The predicted results are stable against the position of the emitter placed in the metaelement, thus alleviating the challenging fabrication requirement of precise positioning of the defect center. Equally importantly, our design approach can be applied to enhance single photon emission also from other defects such as SiV, other materials such as hBN, and other sources such as quantum dots.

Synergistic Inclusion of Reaction Activator and Reaction Accelerator to Ni-MOF Toward Extra-Ordinary Performance of Urea Oxidation Reaction.

Recently electrochemical urea oxidation reaction (UOR) has emerged as the technology of demand for commercialization of urea-based energy conversion. However, the nascent idea is limited by the energy burden of threshold voltage and the sluggish reaction kinetics involving a six-electron transfer mechanism. Herein, for the first time, the engineering of electrocatalysts are proposed with simultaneous inclusion of UOR activator and UOR accelerator. Nitrogen-doped carbon-decorated Ni-based Metal Organic Framework (MOF)has been synthesized as the base catalyst material. MoO2 and rGO with varied loading have been attached to the MOF to get the desired MoO2/Ni-MOF/rGO heterostructure incorporating defects and crystal strain within the materials. Investigations reveal that the invoked lattice strain and atomic defects promote plenteous Ni3+ active sites. The optimized sample demonstrates extraordinary performance of UOR having the potential value as low as 1.32V versus RHE to reach the current density of 10mAcm-2 and the tafel slope is only 31mVdec-1 reflecting very fast reaction kinetics. Here MoO2 plays the role of UOR activator whereas optimized loading of rGO proliferates the reaction speed. This work, experimentally and theoretically, presents a new insight to enhance electrocatalytic urea oxidation reaction opening an avenue of urea-based energy-harvesting technology.

Exploring electron-beam induced modifications of materials with machine-learning assisted high temporal resolution electron microscopy

Directed atomic fabrication using an aberration-corrected scanning transmission electron microscope (STEM) opens new pathways for atomic engineering of functional materials. In this approach, the electron beam is used to actively alter the atomic structure through electron beam induced irradiation processes. One of the impediments that has limited widespread use thus far has been the ability to understand the fundamental mechanisms of atomic transformation pathways at high spatiotemporal resolution. Here, we develop a workflow for obtaining and analyzing high-speed spiral scan STEM data, up to 100 fps, to track the atomic fabrication process during nanopore milling in monolayer MoS2. An automated feedback-controlled electron beam positioning system combined with deep convolution neural network (DCNN) was used to decipher fast but low signal-to-noise datasets and classify time-resolved atom positions and nature of their evolving atomic defect configurations. Through this automated decoding, the initial atomic disordering and reordering processes leading to nanopore formation was able to be studied across various timescales. Using these experimental workflows a greater degree of speed and information can be extracted from small datasets without compromising spatial resolution. This approach can be adapted to other 2D materials systems to gain further insights into the defect formation necessary to inform future automated fabrication techniques utilizing the STEM electron beam.

Point-defect-induced electronic polarization to enhance H* generation for removal of bisphenol A

Intrinsic point defects in metal core-shell materials can regulate electron redistribution, thereby reducing catalytic energy barriers and enhancing their ORR activity. However, their specific contributions to electron transfer and mass transport pathways remain unclear. In this study, defect-rich hollow OCo@Co3O4 nanoparticles were successfully synthesized using ZIF-67(Co) as a sacrificial template through controlled annealing and internal electric field substitution reactions. High-resolution electron microscopy analysis and density functional theory (DFT) calculations co-revealed the growth mechanism of Co and O vacancies, as well as antisite defects. The formation of oxygen vacancies significantly lowered the energy barrier for Co vacancy formation, playing a crucial bridging role in the development of antisite defects. The electric field polarization induced by Co-O atomic displacement resulted in asymmetric charge distribution, optimizing the adsorption of active hydrogen (H*) and oxygen atoms and facilitating the generation and release of reactive oxygen species (ROS). Electrocatalytic experiments demonstrated that under the combined action of singlet oxygen (1O2) and H*, bisphenol A (BPA) can be efficiently degraded. This study successfully bridges the knowledge gap between atomic defects and advanced electrocatalysis, providing a new perspective and insight for the in-depth analysis of the structure-performance relationship of electrocatalyst materials in the future.

Atom-Vacancy-Defect-Derived Electric Hysteresis Loops and Stochastic Low-Frequency Noises in Few-Atom Layer MoS2.

Atom-vacancy-defects present in various materials yield numerous interesting physical phenomena, even obstructing high performance in some cases. On the other hand, their valuable applications to novel devices, such as nitrogen vacancy centers in diamond for quantum bits, have gathered significant attention. In particular, these tendencies become more substantial in two-dimensional (2D) (atomically) thin van der Waals layers. However, correlations with various kinds of atom defects are still under exploration. Herein, we find the stochastic behaviors of large hysteresis loops with strong photoresponse in the static electrical properties in few-atom layer semiconductors, molybdenum disulfide (MoS2). The temperature dependence and transmission electron microscopy reveal that they arise from pairs of two neighboring in-plane S-vacancy defects, which predominantly present only around the interface at the MoS2 flake/substrate, with activation energies ∼0.35 eV. The low-frequency (f) (LF) noise measurements clarify a high f shift in the two 1/f2-dependent regimes, implying stochastic behaviors of electric charges through the S-vacancy pairs with high-speed charge(spin) transitions across low kinetic energy barriers between narrow discrete states. The shallow energy sates are formed from the highly uniform S-vacancy pairs interacting with Mo atoms, which act like quantum dots. The observed stochastic operation holds promise for various application, particularly for probabilistic neuromorphic computation in artificial intelligence.

Photon Upconversion of Defect-Bound Excitons in hBN-Encapsulated MoS2 Monolayer.

Atomic defects associated with vacancies in two-dimensional transition metal dichalcogenide monolayers efficiently trap charged carriers and strongly localize excitons. Defects in semiconducting monolayers are seldomly utilized for enhancing optical phenomena, although they may provide resonant intermediate states within the energy band gap for applications with multiphoton excitations, like highly efficient and thermally robust photon upconversion. In an MoS2 monolayer encapsulated by hBN with high defect and resident electron densities, we observe an upconversion of localized exciton (XL) emission with a huge energy gain of up to 290 meV. The upconverted XL emission is robust up to temperatures of about 120 K and exhibits a sublinear or a nearly linear laser power dependence for the energy gain of about 100 meV and above 200 meV, respectively. The upconversion mechanism is explained by a cooperative energy transfer process between the photocreated and resident electrons, in which hybridized pairs of single sulfur vacancies likely act as real intermediate states. Additionally, we find a weak upconversion of the neutral exciton photoluminescence with an energy gain of about 350 meV for quasi-resonant excitation of the XL exciton. It is attributed to a two-step, two-photon absorption.

High-Density Atomic Level Defect Engineering of 2D Fe-Based Metal-Organic Frameworks Boosts Oxygen and Hydrogen Evolution Reactions.

Electrocatalysts based on metal-organic frameworks (MOFs) attracted significant attention for water splitting, while the transition between MOFs and metal oxyhydroxide poses a great challenge in identifying authentic active sites and long-term stability. Herein, we employ on-purpose defect engineering to create high-density atomic level defects on two-dimensional Fe-MOFs. The coordination number of Fe changes from 6 to 4.46, and over 28% of unsaturated Fe sites are formed in the optimized Fe-MOF. In situ characterizations of the most optimized Fe-MOF0.3 electrocatalyst during the oxygen evolution reaction (OER) process using Fourier transform infrared and Raman spectroscopy have revealed that some Fe unsaturated sites become oxidized with a concomitant dissociation of water molecules, causing generation of the crucial *OH intermediates and Fe oxyhydroxide. Moreover, the presence of Fe oxyhydroxide is compatible with the Volmer and Heyrovsky steps during the hydrogen evolution reaction (HER) process, which lower its energy barrier and accelerate the kinetics. As a result, the optimized Fe-MOF electrodes delivered remarkable OER (259 mV at 10 mA cm-2) and HER (36 mV at 10 mA cm-2) performance. Our study offers comprehensive understanding of the effect of phase transformation on the electrocatalytic process of MOF-based materials.

Coherent Driving of a Single Nitrogen Vacancy Center by a Resonant Magnetic Tunnel Junction.

Nitrogen vacancy (NV) centers, atomic spin defects in diamond, represent an active contender for advancing transformative quantum information science (QIS) and innovations. One of the major challenges for designing NV-based hybrid systems for QIS applications results from the difficulty of realizing local control of individual NV spin qubits in a scalable and energy-efficient way. To address this bottleneck, we introduce magnetic tunnel junction (MTJ) devices to establish coherent driving of an NV center by a resonant MTJ with voltage controlled magnetic anisotropy. We show that the oscillating magnetic stray field produced by a resonant micromagnet can be utilized to effectively modify and drive NV spin rotations when the NV frequency matches the corresponding resonance conditions of the MTJ. Our results present a new pathway to achieve all-electric control of an NV spin qubit with reduced power consumption and improved solid-state scalability for implementing cutting-edge QIS technological applications.

Controlled Spalling of 4H Silicon Carbide with Investigated Spin Coherence for Quantum Engineering Integration.

We detail scientific and engineering advances which enable the controlled spalling and layer transfer of single crystal 4H silicon carbide (4H-SiC) from bulk substrates. 4H-SiC's properties, including high thermal conductivity and a wide bandgap, make it an ideal semiconductor for power electronics. Moreover, 4H-SiC is an excellent host of solid-state atomic defect qubits for quantum computing and quantum networking. Because 4H-SiC substrates are expensive (due to long growth times and limited yield), techniques for removal and transfer of bulk-quality films are desirable for substrate reuse and integration of the separated films. In this work, we utilize updated approaches for stressor layer thickness control and spalling crack initiation to demonstrate controlled spalling of 4H-SiC, the highest fracture toughness crystal spalled to date. We achieve coherent spin control of neutral divacancy (VV0) qubit ensembles and measure a quasi-bulk spin T2 of 79.7 μs in the spalled films.

Gapped and Rotated Grain Boundary Revealed in Ultra‐Small Au Nanoparticles for Enhancing Electrochemical CO2 Reduction

AbstractAlthough gapped grain boundaries have often been observed in bulk and nanosized materials, and their crucial roles in some physical and chemical processes have been confirmed, their acquisition at ultrasmall nanoscale presents a significant challenge. To date, they had not been reported in metal nanoparticles smaller than 2 nm owing to the difficulty in characterization and the high instability of grain boundary (GB) atoms. Herein, we have successfully developed a synthesis method for producing a novel chiral nanocluster Au78(TBBT)40 (TBBT=4‐tert‐butylphenylthiolate) with a 26‐atom gapped and rotated GB. This nanocluster was precisely characterized using single‐crystal X‐ray crystallography and mass spectrometry. Additionally, an offset atomic defect linked to the peripheral Au(TBBT)2 staple was found in the structure. Comparing it to similarly face‐centered cubic‐structured Au36(TBBT)24, Au44(TBBT)28, Au52(TBBT)32, Au92(TBBT)44, and ~5 nm nanocrystals, the bridging Au78(TBBT)40 nanocluster exhibited higher catalytic activity in the electroreduction of CO2 to CO. This enhanced activity was explained through density functional theory calculations and X‐ray photoelectron spectroscopy analysis, which highlight the impact of GBs and point defects on the surface properties of metal nanoclusters in balancing intermediate adsorption and product desorption.

Gapped and Rotated Grain Boundary Revealed in Ultra-Small Au Nanoparticles for Enhancing Electrochemical CO2 Reduction.

Although gapped grain boundaries have often been observed in bulk and nanosized materials, and their crucial roles in some physical and chemical processes have been confirmed, their acquisition at ultrasmall nanoscale presents a significant challenge. To date, they had not been reported in metal nanoparticles smaller than 2 nm owing to the difficulty in characterization and the high instability of grain boundary (GB) atoms. Herein, we have successfully developed a synthesis method for producing a novel chiral nanocluster Au78(TBBT)40 (TBBT=4-tert-butylphenylthiolate) with a 26-atom gapped and rotated GB. This nanocluster was precisely characterized using single-crystal X-ray crystallography and mass spectrometry. Additionally, an offset atomic defect linked to the peripheral Au(TBBT)2 staple was found in the structure. Comparing it to similarly face-centered cubic-structured Au36(TBBT)24, Au44(TBBT)28, Au52(TBBT)32, Au92(TBBT)44, and ~5 nm nanocrystals, the bridging Au78(TBBT)40 nanocluster exhibited higher catalytic activity in the electroreduction of CO2 to CO. This enhanced activity was explained through density functional theory calculations and X-ray photoelectron spectroscopy analysis, which highlight the impact of GBs and point defects on the surface properties of metal nanoclusters in balancing intermediate adsorption and product desorption.

Imaging Quantum Interference in a Monolayer Kitaev Quantum Spin Liquid Candidate

Single atomic defects are prominent windows to look into host quantum states because collective responses from the host states emerge as localized states around the defects. Friedel oscillations and Kondo clouds in Fermi liquids are quintessential examples. However, the situation is quite different for quantum spin liquid (QSL), an exotic state of matter with fractionalized quasiparticles and topological order arising from a profound impact of quantum entanglement. Elucidating the underlying local electronic property has been challenging due to the charge neutrality of fractionalized quasiparticles and the insulating nature of QSLs. Here, using spectroscopic-imaging scanning tunneling microscopy, we report atomically resolved images of monolayer α−RuCl3, the most promising Kitaev QSL candidate, on metallic substrates. We find quantum interference in the insulator manifesting as incommensurate and decaying spatial oscillations of the local density of states around defects with a characteristic bias dependence. The oscillation differs from any known spatial structures in its nature and does not exist in other Mott insulators, implying it is an exotic oscillation involved with excitations unique to α−RuCl3. Numerical simulations suggest that the observed oscillation can be reproduced by assuming that itinerant Majorana fermions of Kitaev QSL are scattered across the Majorana Fermi surface. The oscillation provides a new approach to exploring Kitaev QSLs through the local response against defects like Friedel oscillations in metals. Published by the American Physical Society 2024

Quantum Physical Unclonable Function Based on Multidimensional Fingerprint Features of Single Photon Emitters in Random AlN Nanocrystals

AbstractPhysical unclonable function (PUF) has emerged as a unique physical'fingerprint' that is inherently difficult to replicate. It shows tremendous application value in various hardware security areas such as identity authentication, chip anticounterfeiting, communication encryption, blockchain, etc. However, with the rapid development of 3D nanoprinting, classical PUFs constructed with disordered micro‐nanostructures face tremendous threats from physical cloning attacks. Herein, this study proposes and demonstrates the utilization of room‐temperature single‐photon emitters derived from atomic defects in randomly distributed pyramidal aluminum nitride (AlN) nanocrystals as a novel quantum PUF to resist physical cloning attacks. The fabrication of this quantum PUF on silicon (Si) wafers enables seamless integration with silicon photonic integrated circuits. The multidimensional fingerprint features of the single‐photon emitters are highly sensitive to the lattice parameters of the uneven AlN nanocrystals. Furthermore, each single photon emitter can work as a quantum random number generator to ensure the fundamental unpredictability of PUFs. The subatomic precision requirement coupled with unpredictable quantum emission behavior makes it practically impossible to attack the proposed quantum PUF, providing a promising solution for information security in the post‐quantum era.

Physicochemical Modulations in MXenes for Carbon Dioxide Mitigation and Hydrogen Generation: Tandem Dialogue between Theoretical Anticipations and Experimental Evidences

The dawn of MXenes has fascinated researchers under their intriguing physicochemical attributes that govern their energy and environmental applications. Modifications in the physicochemical properties of MXenes pave the way for efficient energy-driven operations such as carbon capture and hydrogen generation. The physicochemical modulations such as interface engineering through van der Waals coupling with homo/hetero-junctions render the tunability of optoelectronic variables driving the photochemical and electrochemical processes. Herein, we have reviewed the recent achievements in physicochemical properties of MXenes by highlighting the role of intercalants/terminal groups, atomic defects, surface chemistry and few/mono-layer formation. Recent findings of MXenes-based materials are systematically surveyed in a tandem manner with the future outlook for constructing next-generation multi-functional catalytic systems. Theoretical modelling of MXenes surface engineering proffers the mechanistic comprehension of surface phenomena such as termination, interface formation, doping and functionalization, thereby enabling the researchers to exploit them for targeted applications. Therefore, theoretical anticipations and experimental evidences of electrochemical/photochemical carbon dioxide reduction and hydrogen evolution reactions are synergistically discussed.

Abnormal Relaxation Behavior of Excited Electrons in the Flat Band of Kagome Compound Nb3Cl8.

Carrier dynamics is crucial in semiconductors, and it determines their conductivity, response time, and overall functionality. In flat bands (FBs), carriers with high effective masses are predicted to host unconventional transport properties. The FBs usually overlap with other trivial energy bands, however, making it difficult to accurately distinguish their carrier dynamics. In this paper, we have investigated the flat-band carrier dynamics of excited electrons in Nb3Cl8, which hosts ideal nonoverlapping FBs near the Fermi level. The optical transition between Hubbard bands is abnormally weakened, exhibiting weak interband absorption and its related slow photoresponse with a time constant of ∼120 s, which are associated with flat-band Mottness-induced large electron effective mass and parity-forbidden transitions. Besides, the localized states created by chlorine vacancies also act as trapping centers for carriers with a time constant of ∼600 s, which are similar to those of the compact localized states of the FB, making the relaxation behavior even more extraordinary. The presence and impacts of atomic defects are confirmed experimentally and theoretically. This work has revealed the abnormal flat-band carrier dynamics of Nb3Cl8, which is essential for understanding the optical, electrical, and thermal transport properties of flat-band materials.

Atomic defects (vacancy, substitutional, and Stone-Wales) in monolayer aluminum nitride: a density-functional-theory simulation

Abstract Aluminum nitride (AlN) is a mechanically strong material with a high melting point and excellent thermal conductivity. In this study, the AlN is modeled with defects in vacancies, substitutions, and Stone-Wales using a density functional theory (DFT). We model six configurations, two configurations of monovacancies: aluminum vacancy (VAl) and vacancy nitrogen (VN), two configurations of substitutions: aluminum substitution (SN→Al) and nitrogen substitution (SAl→N), the interchange (IAl↔N), and Stone-Wales (S–W). We find structural changes in each defect with outward relaxation and VN with inward relaxation. the band structure calculations show that the geometric structure introduces new states near the Fermi level except for the VAl system.

Effect of Atomic Vacancy Defect in h – BN Monolayer on Electronic Properties: A DFT Study

Abstract h-BN is a 2D material which also has considerable development potential in several fields. 2D materials such as h-BN are basically insulating materials but have unique properties and it would be good if they could be developed, especially to meet future energy needs or in the development of electronic devices. Therefore, the properties of h-BN are certainly needed to support this, one of which is the magnetic properties of h-BN. In this research, we modified the h-BN structure by providing defects in the form of vacancy defects by removing atoms in the h-BN layer. We modeled a monolayer h-BN with a supercell size of 4 x 4 x 1, and our calculations were carried out with Quantum ESPRESSO, which is based on density functional theory. The results we obtained showed the emergence of magnetic moment values in h-BN due to defects in the form of atomic vacancies. Furthermore, this research successfully illustrates how vacancy defects in h-BN can modify the band structure, leading to changes in electron behavior around the Fermi energy level.

First-principles computational methods for quantum defects in two-dimensional materials: A perspective

Quantum defects are atomic defects in materials that provide resources to construct quantum information devices such as single-photon emitters and spin qubits. Recently, two-dimensional (2D) materials gained prominence as a host of quantum defects with many attractive features derived from their atomically thin and layered material formfactor. In this Perspective, we discuss first-principles computational methods and challenges to predict the spin and electronic properties of quantum defects in 2D materials. We focus on the open quantum system nature of the defects and their interaction with external parameters such as electric field, magnetic field, and lattice strain. We also discuss how such prediction and understanding can be used to guide experimental studies, ranging from defect identification to tuning of their spin and optical properties. This Perspective provides significant insights into the interplay between the defect, the host material, and the environment, which will be essential in the pursuit of ideal two-dimensional quantum defect platforms.