Atomic Defects Research Articles

Atomic scale disorder and reconstruction in bulk infinite-layer nickelates lacking superconductivity

The recent discovery of superconductivity in infinite-layer nickelate films has sparked significant interest and expanded the realm of superconductors, in which the infinite-layer structure and proper chemical doping are both of the essence. Nonetheless, the reasons for the absence of superconductivity in bulk infinite-layer nickelates remain puzzling. Herein, we investigate atomic defects and electronic structures in bulk infinite-layer Nd0.8Sr0.2NiO2 using scanning transmission electron microscopy. Our observations reveal the presence of three-dimensional (3D) block-like structural domains resulting from intersecting defect structures, disrupting the continuity within crystal grains, which could be a crucial factor in giving rise to the insulating character and inhibiting the emergence of superconductivity. Moreover, the infinite-layer structure, without complete topotactic reduction, retains interstitial oxygen atoms on the Nd atomic plane in bulk nickelates, possibly further aggravating the local distortions of NiO2 planes and hindering the superconductivity. These findings shed light on the existence of structural and atomic defects in bulk nickelates and provide valuable insights into the influence of proper topotactic reduction and structural orders on superconductivity.

Full solar spectrum available hierarchical porous ZIF/Fe-DCA (70) co-assisted by isolated Fe and rich defects for boosted environmental remediation efficiency

The cationic defects engineering and molecular-scale cages effect work together to harvest rich defects and high-density isolated Fe on ZIF, endowing ZIF/Fe-DCA (70) with exposed active sites, facilitating photogenerated carrier separation and optimizing electronic structure. The LSPR effect, intermediated energy band and photothermal transition broaden the light absorption to NIR range with Eg = 2.15 eV. Removal rates for TC (60 mg/L), MB (10 mg/L), MO (10 mg/L) and GV (10 mg/L) are 93 %/86.3 %, 98.2 %/85.1 %, 83.7 %/70.2 % and 82 %/68 % after Vis/NIR irradiation, respectively. A satisfactory purifying efficiency was also detected on the mixed pollutants solution under real sunlight. Besides, the infrared thermography was employed to verify the photothermal conversion visually. The ‧O2−, 1O2, and triplet state are the most effective active species, and the ‧OH and h+ both apparently participate in the photodegradation. This study provides effective design ideas involving single atomic co-catalyst and defects into MOFs as full-spectrum photocatalysts to repair environment.

Discovery of atomic clock-like spin defects in simple oxides from first principles

Virtually noiseless due to the scarcity of spinful nuclei in the lattice, simple oxides hold promise as hosts of solid-state spin qubits. However, no suitable spin defect has yet been found in these systems. Using high-throughput first-principles calculations, we predict spin defects in calcium oxide with electronic properties remarkably similar to those of the NV center in diamond. These defects are charged complexes where a dopant atom — Sb, Bi, or I — occupies the volume vacated by adjacent cation and anion vacancies. The predicted zero phonon line shows that the Bi complex emits in the telecommunication range, and the computed many-body energy levels suggest a viable optical cycle required for qubit initialization. Notably, the high-spin nucleus of each dopant strongly couples to the electron spin, leading to many controllable quantum levels and the emergence of atomic clock-like transitions that are well protected from environmental noise. Specifically, the Hanh-echo coherence time increases beyond seconds at the clock-like transition in the defect with 209Bi. Our results pave the way to designing quantum states with long coherence times in simple oxides, making them attractive platforms for quantum technologies.

Characterization of Transparent Electrodes with Ag Metal-mesh using MATLAB

It is well-known that optical transparence and electric resistance have a trade-off relationship in transparent electrodes. For this reason, developing methods to predict this relation have been important in various fields of academic research as well as for industrial applications. Herein, we suggest a simple method which reveals the relationship between optical transparence and electric resistance using MATLAB, based on the geometric characteristics of a random metal network. Ag metal-mesh transparent electrodes were fabricated with various conditions using colloidal silica cracked-templates and a Radio Frequency (RF) sputtering system. MATLAB software was used to analyze structural images of the Ag mesh network, automatically quantifying the density and width of the Ag meshes. From these data, the transparency and sheet resistance values of the Ag mesh electrodes were predicted and compared with measured values. Regarding transparency, the introduction of fitting parameters revealed minimal differences between the experimental and predicted values obtained from the structure images. Although the predicted sheet resistance was slightly different than the real measured values due to atomic defects or imperfections in the crystals of the Ag-mesh network, it was possible to observe a similar trend between the measured and predicted sheet resistances with changes in the fractional coverage area of the Ag-mesh network.

Harnessing Quantum Capacitance in 2D Material/Molecular Layer Junctions for Novel Electronic Device Functionality.

Two-dimensional (2D) materials promise advances in electronic devices beyond Moore's scaling law through extended functionality, such as non-monotonic dependence of device parameters on input parameters. However, the robustness and performance of effects like negative differential resistance (NDR) and anti-ambipolar behavior have been limited in scale and robustness by relying on atomic defects and complex heterojunctions. In this paper, we introduce a novel device concept that utilizes the quantum capacitance of junctions between 2D materials and molecular layers. We realized a variable capacitance 2D molecular junction (vc2Dmj) diode through the scalable integration of graphene and single layers of stearic acid. The vc2Dmj exhibits NDR with a substantial peak-to-valley ratio even at room temperature and an active negative resistance region. The origin of this unique behavior was identified through thermoelectric measurements and ab initio calculations to be a hybridization effect between graphene and the molecular layer. The enhancement of device parameters through morphology optimization highlights the potential of our approach toward new functionalities that advance the landscape of future electronics.

Quantification of alloy atomic composition sites in 2D ternary MoS2(1-x)Se2x and their role in persistent photoconductivity, enhanced photoresponse and photo-electrocatalysis

Engineering transition metal dichalcogenides-based semiconducting two-dimensional (2D) layered materials for photo(electro)chemical (PEC) hydrogen evolution reaction (HER) by water splitting is an enduring challenge. Here, alloy-assisted photoconductivity and photoresponse from CVD-grown MoS2(1-x)Se2x (MSSE) 2D ternary atomic layered alloy-based photodetector device is presented for the realization of PEC HER. The explicit role of ‘S–Se’ and ‘Se2’ atomic alloy sites including chalcogen-induced vacancy defects on the photoconductivity/photoresponse and PEC HER performance of MSSE 2D alloy is investigated. Alloy formation, atomic site-by-site ‘Se’ composition and atomic structure are characterized using Raman/Photoluminescence (PL) spectroscopy, high-angle annular dark field (HAADF)- scanning transmission electron microscopy (STEM) extensively and supported with Auger Electron Spectroscopy (AES) mapping. Further, the local density and concentration of S–Se, Se2 atomic sites and defects were quantitatively estimated using HAADF-STEM image analysis in correlation with AES and it is found between the range of ∼15–20 % in MSSE alloy. A 10-fold high photoresponsivity in the case of MSSE concerning as-grown MS having fast photocurrent growth time and the prolonged decay time originates from the ‘Se’ and this alloy assisted states to enhance the PEC performance of MSSE alloy. The enhanced PEC HER activity of MSSE alloy was identified in terms of overpotential and current density. In addition, increased density of states as a function of ‘Se’ alloying, shifts in a p-band centre and lowers ΔGH* according to density functional theory calculations, which makes MSSE alloy an efficient HER activity. Further, the PEC stability and presence of the ‘S–Se’ and ‘Se2’ alloying and their role towards HER have been correlated by the spectral line shape analysis of PL and Raman spectra from post-PEC HER catalysts. These experimental and theoretical findings establish the role of chalcogen, and transition metal-based 2D alloy, leading to the design of new PECs of engineered 2D atomic layer interfaces.

Zero energy bound states on nano atomic line defect in iron-based high temperature superconductors

Motivated by recent scanning tunneling microscopy experiments on Fe atomic line defect in iron-based high temperature superconductors, we explore the origin of the zero energy bound states near the endpoints of the line defect by employing the two-orbit four-band tight binding model. With increasing the strength of the Rashba spin–orbit coupling along the line defect, the zero energy resonance peaks move simultaneously forward to negative energy for s+− pairing symmetry, but split for s++ pairing symmetry. The superconducting order parameter correction due to As(Te, Se) atoms missing does not shift the zero energy resonance peaks. Such the zero energy bound states are induced by the weak magnetic order rather than the strong Rashba spin–orbit coupling on Fe atomic line defect.

Phase division and recognition of crystal HRTEM images based on machine learning and deep learning

The High Resolution Transmission Electron Microscope (HRTEM) images provide valuable insights into the atomic microstructure, dislocation patterns, defects, and phase characteristics of materials. However, the current analysis and research of HRTEM images of crystal materials heavily rely on manual expertise, which is labor-intensive and susceptible to subjective errors. This study proposes a combined machine learning and deep learning approach to automatically partition the same phase regions in crystal HRTEM images. The entire image is traversed by a sliding window to compute the amplitude spectrum of the Fast Fourier Transform (FFT) in each window. The generated data is transformed into a 4-dimensional (4D) format. Principal component analysis (PCA) on this 4D data estimates the number of feature regions. Non-negative matrix factorization (NMF) then decomposes the data into a coefficient matrix representing feature region distribution, and a feature matrix corresponding to the FFT magnitude spectra. Phase recognition based on deep learning enables identifying the phase of each feature region, thereby achieving automatic segmentation and recognition of phase regions in HRTEM images of crystals. Experiments on zirconium and oxide nanoparticle HRTEM images demonstrate the proposed method achieve the consistency of manual analysis. Code and supplementary material are available at https://github.com/rememberBr/HRTEM2.

Antiprotozoal Pt(II) Complexes as Luminophores Bearing Monodentate P/As/Sb-Based Donors: An X-ray Diffractometric, Photoluminescence, and 121Sb-Mössbauer Spectroscopic Study with TD-DFT-Guided Interpretation and Predictive Extrapolation toward Bi.

In this study, it is demonstrated that the radiative rate constant of phosphorescent metal complexes can be substantially enhanced using monodentate ancillary ligands containing heavy donor atoms. Thus, the chlorido coligand from a Pt(II) complex bearing a monoanionic tridentate C^N*N luminophore ([PtLCl]) was replaced by triphenylphosphane (PPh3) and its heavier pnictogen congeners (i.e., PnPh3 to yield [PtL(PnPh3)]). Due to the high tridentate-ligand-centered character of the excited states, the P-related radiative rate is rather low while showing a significant boost upon replacement of the P donor by heavier As- and Sb-based units. The syntheses of the three complexes containing PPh3, AsPh3, and SbPh3 were completed by unambiguous characterization of the clean products using exact mass spectrometry, X-ray diffractometry, bidimensional NMR, and 121Sb-Mössbauer spectroscopy (for [PtL(SbPh3)]) as well as steady state and time-resolved photoluminescence spectroscopies. Hence, it was shown that the hybridization defects of the Vth main-group atoms can be overcome by complexation with the Pt center. Notably, the enhancement of the radiative rate constants mediated by heavier coligands was achieved without significantly influencing the character of the excited states. A rationalization of the results was achieved by TD-DFT. Even though the Bi-based homologue was not accessible due to phenylation side reactions, the experimental data allowed a reasonable extrapolation of the structural features whereas the hybridization defects and the excited state properties related to the Bi-species and its phosphorescence rate can be predicted by theory. The three complexes showed an interesting antiprotozoal activity, which was unexpectedly notorious for the P-containing complex. This work could pave the road toward new efficient materials for optoelectronics and novel antiparasitic drugs.

Pd(II)/Pd(IV) redox shuttle to suppress vacancy defects at grain boundaries for efficient kesterite solar cells

Charge loss at grain boundaries of kesterite Cu2ZnSn(S, Se)4 polycrystalline absorbers is an important cause limiting the performance of this emerging thin-film solar cell. Herein, we report a Pd element assisted reaction strategy to suppress atomic vacancy defects in GB regions. The Pd, on one hand in the form of PdSex compounds, can heterogeneously cover the GBs of the absorber film, suppressing Sn and Se volatilization loss and the formation of their vacancy defects (i.e. VSn and VSe), and on the other hand, in the form of Pd(II)/Pd(IV) redox shuttle, can assist the capture and exchange of Se atoms, thus contributing to eliminating the already-existing VSe defects within GBs. These collective effects have effectively reduced charge recombination loss and enhanced p-type characteristics of the kesterite absorber. As a result, high-performance kesterite solar cells with a total-area efficiency of 14.5% (certified at 14.3%) have been achieved.

Observation of parabolic electron bands on superconductor LaRu2As2

Abstract Ru-based superconductor LaRu2As2 has been discovered exhibiting the highest critical temperature of ∼ 7.8 K among iron-free transition metal pnictides with the ThCr2Si2-type crystal structure. However, microscopic research on this novel superconducting material is still lacking. Here, we utilize scanning tunneling microscopy/spectroscopy to uncover the superconductivity and surface structure of LaRu2As2. Two distinct terminating surfaces are identified on the cleaved crystals, namely, the As surface and the La surface. Atomic missing line defects are observed on the La surface. Both surfaces exhibit a superconducting gap of ∼ 1.0 meV. By employing quasiparticle interference techniques, we observe standing wave patterns near the line defects on the La atomic plane. These patterns are attributed to quasiparticle scattering from two electron type parabolic bands.

Impact of Atomic Vacancy Defects on Vibrational Characteristics of Chiral MWCNT for Viruses/Bacteria

In this study the authors investigated the vibrations performance of chiral multi-walled carbon nanotubes (MWCNTs). They examined chiral MWCNTs with attached bacteria positioned at both the tip and middle sections of the nanotubes. The main goal of this research was to create a sensor with the ability to detect and distinguish bacteria or viruses that could potentially adhere to the surfaces of chiral MWCNTs. The authors considered two boundary conditions, fixed-fixed and fixed -free for the chiral MWCNT. They utilized a molecular structural mechanics approach. In this approach the vibrational responses of chiral MWCNT-based nano-biosensors with different diameters of the chiral MWCNTs were examined. The study’s objective was to fill research gaps by introducing an innovative approach for detecting defects in chiral MWCNTs through vibrational analysis. They simulated 432 MWCNT samples to investigate the vibrational performance of defective chiral MWCNTs. The results suggested that the first mode of the vibrational frequency of the chiral MWCNT is particularly significant for sensing applications. It was observed that as the percentage of vacancy defects increased, the natural frequency decreased for both boundary conditions.

Defect dynamics in the presence of excess energetic carriers and high electric fields in wide-gap semiconductors

Irradiation of semiconductors by energetic beams generates excess electrons and holes and may cause device degradation or failure. Both gradual degradation by total ionizing radiation (TID) and sudden degradation/failure (soft/hard breakdown) by a combination of energetic heavy ions and high voltages (typically single-event effects or SEEs) are mediated by excess carriers. The role of defect dynamics in TID degradation has been adequately understood by a combination of experiments and density-functional-theory (DFT) quantum calculations, but little has been done so far to document a role for ion-induced defects in SEE. Here, we report proof-of-principle DFT calculations in a model cubic GaN system for two defect-related excess-carrier phenomena that can play a role in various forms of device degradation and failure. The first phenomenon is the existence, dynamics, and potential roles of defect-induced quasi-localized “resonant states” in the energy-band continua. These states can enhance TID-excess-carrier and hot-carrier degradation. Furthermore, they evolve and multiply during energetic-ion-induced atom recoils and defect creation (displacement damage) and can potentially serve as excess-carrier conduction paths in SEE. The second phenomenon is the conversion of isolated vacancies into nanovoids that can participate in the formation of conducting defect “nanowires” dressed by resonances or in explosive SEE hard breakdowns.

Study of Surface Chemistry, Temperature and Strain Rate on the Tensile Properties of Monolayer Graphene Oxide

The mechanical properties of graphene oxide (GO) during tensile fracture were studied using molecular dynamics methods, and the influence of hydroxyl and epoxy groups on the mechanical properties of GO was explored. In addition, the changes in mechanical properties of GO under different temperatures and strain rates were studied to gain a deeper understanding of its mechanical behavior. The results indicate that hydroxyl and epoxy groups have a significant influence on the elastic modulus, ultimate stress, and ultimate strain of GO. The presence of hydroxyl and epoxy groups can alter the molecular structure of GO, thereby affecting its ultimate stress and strain. When the number of hydroxyl groups is 16 and the number of epoxy groups is 20, the ultimate stress decreases by about 31% and the elastic modulus decreases by about 20%. The variation of elastic modulus, ultimate stress, and ultimate strain of GO with temperature was studied at three temperatures: 300[Formula: see text]K, 500[Formula: see text]K, and 800[Formula: see text]K. As the temperature increases, the amplitude of atomic vibration increases and internal defects and cracks in GO continue to form and expand. At the same time, its coefficient of thermal expansion also increases, causing deformation and loosening of the crystal structure, resulting in a decrease of about 10% in the ultimate stress of GO, and a slight decrease in the ultimate strain and elastic modulus. Finally, the influence of different strain rates on the mechanical properties of GO was studied. As the strain rate increases, the intermolecular interactions within GO are rapidly altered, and the previously loose structure gradually becomes tightly ordered, resulting in an increasing trend in the elastic modulus, ultimate stress, and ultimate strain of GO.

Impact of crystallinity on thermal conductivity of RF magnetron sputtered MoS2 thin films

This study investigates the effects of sulfur atomic defects and crystallinity on the thermal conductivity of MoS2 thin films. Utilizing scanning transmission electron microscopy (STEM), X-ray diffraction (XRD), and Raman spectroscopy, we examined MoS2 films, several nanometers thick, deposited on Si/SiO2 substrates. These films were prepared via a combination of RF magnetron sputtering and sulfur vapor annealing (SVA) treatment. Structural analyses, including cross-sectional STEM and in-plane and out-of-plane XRD measurements, revealed an increase in the S/Mo ratio and grain size of the MoS2 films following SVA treatment. Notably, the in-plane thermal conductivity of MoS2 films treated with SVA was found to be at least an order of magnitude higher than that of films without SVA treatment. This research suggests that the in-plane thermal conductivity of MoS2 thin films can be significantly enhanced through crystallinity improvement via SVA treatment.

Orbital hybridization and defective states of vacancy defects in AlN

Intrinsic atomic defects pose a great effect in wide-bandgap semiconductors owing to the high tendency of forming in-gap defective states. Utilizing density-functional theory, the atomic vacancy defects of Al and N vacancies in hexagonal wurtzite aluminum nitride (AlN) are investigated. We find that the most energetically favorable form of vacancies is predicted to be negatively trivalent charged Al vacancy (VAl−3) in n-type AlN and positively monovalent charged N vacancy (VN+1) in p-type AlN, respectively. N vacancy generally has a low formation energy and could be either an acceptor or a donor: Under p-type conduction, it is a deep donor with a positively monovalent charge of +1, acting as a compensating center for holes; Under n-type conduction, it is a deep acceptor carrying charge of −3, acting as a compensating center for electrons. For the Al vacancy, it tends to be a shallow acceptor in p-type AlN but a high formation energy or a deep acceptor in n-type AlN with low formation energy, most possibly at a negatively trivalent charged state. Our orbital hybridization analysis shows that these vacancies can be facilely generated which are rooted in the antibonding coupling Al3 s-N2p states in valence band. The above finding is independent of the chemical potential of nitrogen and aluminum and holds true under both nitrogen rich and poor conditions. Our work provides a guide to experimental works by providing the energetics and atomic-scale mechanism of doping nature of atomic vacancies in AlN.

Combining machine-learned and empirical force fields with the parareal algorithm: application to the diffusion of atomistic defects

Combining machine-learned and empirical force fields with the parareal algorithm: application to the diffusion of atomistic defects

Local charge rectification and electronic interactions in ZnIn2S4-x-Bi2MoO6-x heterojunction for enhancing synergistic piezo-photocatalytic hydrogen evolution and benzylamine oxidation

The synergistic utilization of vacancies and heterojunctions in piezo-photocatalysis holds great promise for mitigating the issue of charge recombination. However, the charge aggregation effect in vacancies and the disordered positive and negative charge centers in piezoelectric materials may potentially compromise the performance of synergistic piezo-photocatalysis. Here, the well-designed dual vacancies of ZnIn2S4-x and Bi2MoO6-x S-scheme heterojunction (BZ) was prepared for synergistic piezo-photocatalytic amines coupling to generate imines integrated with H2 production. Impressively, BZ-2 demonstrated an efficient N-benzylidenebenzylamine production rate of 4680 µmol g−1 h−1 and H2 formation rate of 4480 µmol g−1 h−1 without using any solvent or cocatalyst, where the formation rate of H2 is 10.25 times greater than that of ZnIn2S4-x. Experimental data and DFT calculations demonstrated that the presence of dual vacancies induces the formation of an interfacial Bi-S bond, which effectively regulates electronic interactions and rectifies charge disorder at the surface of the S-scheme heterojunction. Furthermore, this interfacial Bi-S bond acts as a strain center for providing a substantial electric field to drive charge transfer. Additionally, the electronic structural coupling contributes to lowering the activation energy and enhancing the reaction kinetics. This study offers profound insights into the relationship between atomic defects and S-scheme heterojunctions in piezo-photocatalysis, facilitating the design of high-efficiency materials.

Precision Engineering of Nanorobots: Toward Single Atom Decoration and Defect Control for Enhanced Microplastic Capture

AbstractNanorobots are being received with a great attention for their move‐sense‐and‐act capabilities that often originate from catalytic decomposition of fuels. In the past decade, single‐atom engineering has demonstrated exceptional efficiency in catalysis, energy‐related technologies, and medicine. Here, a novel approach involving point defect engineering and the incorporation of platinum (Pt) single atoms and atomic level species onto the surface of titanium dioxide nanotubes (TiO2‐NT)‐based nanorobots is presented and its impact on the propulsion capabilities of the resulting nanorobots is investigated. The achievement of point defect engineering is realized through the annealing of TiO2‐NT in a hydrogen atmosphere yielding to the point‐defect decorated nanotube (TiO2‐HNT) nanorobots. Subsequently, the atomic level Pt species decorated TiO2 nanotube (TiO2‐SA‐NT) nanorobots are achieved through a wet‐chemical deposition process. Whereas TiO2‐SA‐NT nanorobots showed the highest negative photogravitaxis when irradiated with ultraviolet (UV) light, TiO2‐HNT nanorobots reached the highest velocity calculated in 2D. Both TiO2‐HNT and TiO2‐SA‐NT nanorobots demonstrated a pronounced affinity for microplastics, exhibiting the capability to irreversibly capture them. This pioneering approach utilizing point‐defect and atomic level Pt species nanorobotics is anticipated to pave the way for highly efficient solutions in the remediation of nano‐ and microplastics and related environmental technologies.

Unveiling the nature of atomic defects in graphene on a metal surface.

Low-energy argon ion bombardment of graphene on Ir(111) induces atomic-scale defects at the surface. Using a scanning tunneling microscope, the two smallest defects appear as a depression without discernible interior structure suggesting the presence of vacancy sites in the graphene lattice. With an atomic force microscope, however, only one kind can be identified as a vacancy defect with four missing carbon atoms, while the other kind reveals an intact graphene sheet. Spatially resolved spectroscopy of the differential conductance and the measurement of total-force variations as a function of the lateral and vertical probe-defect distance corroborate the different character of the defects. The tendency of the vacancy defect to form a chemical bond with the microscope probe is reflected by the strongest attraction at the vacancy center as well as by hysteresis effects in force traces recorded for tip approach to and retraction from the Pauli repulsion range of vertical distances.