Defect Concentration Research Articles

Analysis method of point defects evolution in fused silica under multi-pulse nanosecond laser irradiation

Although no optically visible damage is produced in the fused silica under laser irradiation below its laser-induced damage threshold (LIDT), defect proliferation may occur due to the evolution of its internal atomic structure. The escalation in defect content leads to heightened absorption, and resulting in the degradation of the optical performance of the optics. In recent decades, there have been a lot of experimental studies on laser-induced damage and laser conditioning, but there is still a great lack of in-depth understanding and theoretical analysis of the evolution process of point defects in fused silica. In this study, the emphasis is on the evolution of point defects and fatigue damage in fused silica under multi-pulse nanosecond laser irradiation. To address this, a point-defect evolution model is developed, and the coupled evolution law of temperature and defect during laser irradiation is derived by integrating it with a numerical model. The results demonstrate that the model effectively predicts the defect evolution of fused silica under laser irradiation and facilitates the prediction of fatigue damage. It is revealed that the rate of defect evolution in fused silica is more influenced by temperature than stress, and a temperature threshold can be used to judge the condition of damage occurrence. Furthermore, through an analysis of the effect of laser fluence on defect relaxation rate, a defect relaxation method employing variable laser fluence was proposed. This study provides a reliable theoretical analysis method for understanding the fatigue damage induced by multi-pulse laser irradiation in fused silica and offers a new perspective for the annealing treatment of point defects in fused silica.

First-principles prediction of point defect energies and concentrations in the tantalum and hafnium carbides

First-principles calculations are combined with a statistical–mechanical model to predict the equilibrium point-defect concentrations in the refractory carbides TaC and HfC as a function of temperature and chemical composition. Several different types of point defects (vacancies, interstitials, antisite atoms) and their clusters are treated in a unified manner. The defect concentrations either strictly follow or can be closely approximated by Arrhenius functions with parameters predicted by the model. The model is general and applicable to other carbides, nitrides, borides, or similar chemical compounds. Implications of this work for understanding the diffusion mechanisms in TaC and HfC are discussed.

Defect-engineering-based titanium dioxide nanowires for artificial optoelectronic synapses

Artificial optoelectronic synapses, as a typical neuromorphic device, have garnered significant attention due to their concurrent capabilities in processing visual perception and memory. In this study, we propose an artificial optoelectronic synapse with a dual-terminal metal-semiconductor-metal (Au/TiO2/Cr/Au) structure. By modulating the concentration of oxygen vacancy defects in TiO2, the device exhibits a significant persistent photoconductivity (PPC) effect. The devices successfully simulated the synaptic behaviors, including paired-pulse facilitation (PPF), short-term plasticity (STP), long-term plasticity (LTP), and the learning-forgetting process. In addition, the device array has the capability to recognize optical signals and exhibits an obvious response gradient under different optical powers. This demonstrates its ability to adaptively detect optical signals and simulate human visual memory.

Surface quality and microstructure evolution in fused silica under SF6/Ar reactive ion beam etching

The SF6/Ar reactive ion beam etching (RIBE) was proposed to explore the evolution of surface quality, subsurface defects, surface molecular structure, and chemical composition of fused silica. Also, the mechanism of reactive ion beam etching of fused silica surfaces was discussed. The results show that RIBE can maintain the original surface roughness by choosing suitable process parameters. this etching process can suppress the replication and expansion of subsurface defects and the deposition of reactants without bringing obvious contamination. The concentration of structural defects reaches a minimum at an etching depth of about 2 μm. However, further etching may lead to an increase in the chemical structure defects on the surface. The evolution of the intrinsic ring structure demonstrates that most intrinsic defects tend to reorganize into short (Si-O) ring structures. The etching mechanisms of Ar ions were discussed by simulating the stopping power and energy deposition. Phonon dissipation through atomic displacements and atomic vibrations is an important way of energy loss. Phonon vibrations and atomic dislocations induced by nuclear collisions are not only important factors causing the enhancement of electron-phonon coupling but also important causes of surface structural defects. The researches provide a theoretical basis for in-depth understanding of fused silica surface defect repair.

Influence of catalyst shape on plasma-assisted dry reforming of methane: A comparative study of Ni-CeO2 nano-cubes and nano-octahedra

This study investigated the performance of 10 wt% Ni-CeO2 nano-cubes (NC) and nano-octahedra (NO) shaped catalysts in plasma-assisted dry reforming of methane (DRM) environment to understand the influence of catalyst morphology on catalytic activity and global reaction pathway. The presence of different exposed crystal planes (i.e., (111), (110), and (100)) in the CeO2 shapes led to varied NiOx-CeO2 interactions, with the NO-shaped catalyst exhibiting a higher oxygen vacancy concentration, lattice defects, and moderate basic sites compared to the NC catalyst. This interaction in the plasma DRM environment significantly enhances conversions for both shaped catalysts, with the effect more pronounced in the case of the NO-shaped catalyst. The performance data suggest that running plasma DRM at moderate temperature and higher plasma power is relatively efficient. Increasing temperatures or plasma power diverts the DRM reaction towards more H2 production, reducing CO production for both shaped catalysts. This confirms the crucial role of the catalyst in controlling the global reaction pathway considering plasma power or temperature enhancement. Plasma interactions create additional surface defects during the DRM reaction, and defect concentration is closely linked to catalyst morphology. Carbon deposits on the catalyst surface can be readily removed via CO2 plasma regeneration treatment without affecting catalyst performance. Additionally, prolonged plasma exposure leads to NiO phase separation into concentrated Ni, suggesting a cyclical DRM and regeneration approach rather than a continuous reaction.

Defect Engineering in Ce-Based Metal-Organic Frameworks toward Enhanced Catalytic Performance for Hydrogenation of Dicyclopentadiene.

Defective metal-organic frameworks (MOFs) have shown great potential for catalysis due to abundant active sites and adjustable physical and chemical properties. A series of Ce-based MOFs with different defect contents were synthesized via a modulator-induced defect engineering strategy with the aid of the cell pulverization technique. The effects of modulators on the pore structure, morphology, valence distribution of Ce, and Lewis acidity of Ce-MOF-801 were systematically investigated. Among the different samples studied, the optimal Ce-MOF-801-50eq sample exhibited remarkable catalytic activity for DCPD hydrogenation, achieving a conversion rate of 100%, which is significantly higher compared to other Ce-MOF-801-neq samples as well as the Zr-MOF-801-50eq and Hf-MOF-801-50eq samples. The enhanced catalytic performance of Ce-MOF-801-50eq can be attributed to advantages provided by defect engineering, such as the high specific surface area, proper pore size distribution, abundant unsaturated metal sites, and Ce3+/Ce4+ atom ratio, which have been supported by various characterizations. This study provides important insights into the rational design of Ce-MOFs in the field of catalytic DCPD hydrogenation.

Effect of Ar-ion irradiation on electrical transport of WS2 monolayer

Two-dimensional transition metal dichalcogenides (2D-TMDs), such as WS2 and MoS2, have attracted exceptional attention as promising materials for future optoelectronic systems due to their unique properties, including a direct band gap, high quantum efficiency, and flexibility. However, exploiting these materials’ potential in their pristine state remains a key challenge because of limited tunability and control over their properties. The introduction of crystal defects, such as vacancies and dopants, induces localized mid-gap states in 2D materials, enhances electrical transport, and creates a platform for tuning and exploiting these materials for practical applications. Our study explores the effect of Ar-ion beam irradiation on monolayer WS2, resulting in enhanced electrical transport compared to the pristine sample. We regulated the Ar-ion bombardment energy to vary the defect concentration from 0.1 to 0.5 keV. Photoluminescence (PL) and Raman investigations, revealed the extent of damage to the material. At the same time, x-ray photoelectron spectroscopy showed changes in the oxidation state with increasing irradiation energy. Our results demonstrated that Ar-ion treatment at low-energy irradiation enhanced electrical transport by ∼12 fold compared to pristine till 0.2 keV of irradiation by incorporating defects. However, higher irradiation energies reduced electrical transport due to increased disorder in the WS2 monolayer. This investigation highlights the potential for controlled defect engineering to optimize the properties of 2D-TMDs for practical applications.

Tuning Stark effect by defect engineering on black titanium dioxide mesoporous spheres for enhanced hydrogen evolution

Defects can strongly affect the lattice, strain, and electronic structures of nanomaterials photocatalysts, like a double-edged sword of both positive significance and negative influence on photocatalytic performances. To date, most studies into defects only partially elucidated their beneficial or detrimental roles in photocatalysis. However, a quantitative understanding of the photocatalytic performances modulated by defect concentration still needs to be discovered. Here, a series of TiO2−X mesoporous spheres (MS) with different oxygen vacancy concentrations for photocatalytic applications were prepared by high-temperature chemical reduction. The link between oxygen vacancy concentration and photocatalytic performance was successfully established. The localization of carriers dominated by the Stark effect is first enhanced and then weakened with increasing oxygen vacancy concentration, which is a crucial factor in explaining the double-edged sword role of defect concentration in photocatalysis. As the reduction temperature rises to 300 °C, carrier localization dominated by the quantum-confined Stark effect maximizes the separation ability of photo generated electron hole pairs, thus exhibiting the best catalytic performance for photocatalytic hydrogen production and the degradation of organic pollutants, as demonstrated by a hydrogen evolution rate of 523.7 µmol g-1 h-1 and a ninefold higher RhB photodegradation rate compared to TiO2 MS. The work offers excellent flexibility for precisely constructing high-performance photocatalysts by understanding vacancy engineering.

Optimizing methane plasma pyrolysis for instant hydrogen and high-quality carbon production

The European Green Deal has set a target for Europe to achieve net-zero greenhouse gas emissions by 2050, necessitating a transition to more sustainable energy sources. Hydrogen gas (H2) has emerged as a promising solution, with methane pyrolysis presenting a viable method for its production. This study explores the optimization of methane plasma pyrolysis for hydrogen and high-quality carbon production. Employing a statistical approach by a design of experiment software, critical process parameters are systematically analyzed to predict their impact within a defined range. Additionally, the paper conducts comprehensive characterization of the solid carbon produced during pyrolysis using imaging, spectroscopic and elemental analysis, and gas sorption analysis methods. The experimental investigation was conducted using a thermal plasma reactor with several settings of influential parameters including methane gas (CH4) content in the plasma gas, electric current, and arc length. The DC-transferred plasma arc is formed using a variable gas mixture of argon gas (Ar) and CH4, with a constant flow rate of 5 Nl/min. Thirteen tests were designed, evaluating responses such as power input, process stability, and H2 yield. The H2 yield indicates the hydrogen produced from CH4, with 100% representing total conversion. While the process exhibited inconstancy, attributed to reactor design constraints, a high H2 yield of 67%–100% was achieved. The results indicate that a higher CH4 content in the plasma gas and extended arc lengths disturb the plasma arc, hence reducing the H2 yield. Increased power input, achieved through higher amperage levels, and a wider reaction zone eased by extending the arc length both led to an improved H2 yield. Scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS) revealed microstructural differences, with carbon samples from the filter exhibiting finer textures and carbon samples from the reactor larger sizes and dendritic particles. Raman spectroscopy confirmed crystalline graphitic-like structures with low defect concentrations, a finding supported by X-ray diffraction (XRD) analysis. Inductively coupled plasma mass spectroscopy (ICP-MS) analysis confirmed high-purity carbon with slight impurities from initial filter contamination. Brunauer-Emmett-Teller (BET) specific surface area calculations based on gas sorption analysis showed significant variations, with filter-collected samples exhibiting 40–170 m2/g and reactor-collected ones showing 7–30 m2/g.

Unveiling the Effect of Cooling Rate on Grown-in Defects Concentration in Polycrystalline Perovskite Films for Solar Cells with Improved Stability.

Numerous efforts are devoted to reducing the defects at perovskite surface and/or grain boundary; however, the grown-in defects inside grain is rarely studied. Here, the influence of cooling rate on the point defects concentration in polycrystalline perovskite film during heat treatment processing is investigated. With the combination of theoretical and experimental studies, this work reveals that the supersaturated point defects in perovskite films generate during the cooling process and its concentration improves as the cooling rate increases. The supersaturated point defects can be minimized through slowing the cooling rate. As a result, the optimized FAPbI3 polycrystalline films achieve a superior carrier lifetime of up to 12.6 µs and improved stability. The champion device delivers a 25.47% PCE (certified 24.7%) and retain 90% of their initial value after >1100 h of operation at the maximum power point. These results provide a fundamental understanding of the mechanisms of grown-in defects formation in polycrystalline perovskite film.

Enhanced Quantum Metric due to Vacancies in Graphene.

Random vacancies in a graphene monolayer induce defect states that are known to form a narrow impurity band centered around zero energy at half filling. We use a space-resolved formulation of the quantum metric and establish a strong enhancement of the electronic correlations in this impurity band. The enhancement is primarily due to strong correlations between pairs of vacancies situated on different sublattices at anomalously large spatial distances. We trace the strong enhancement to both the multifractal vacancy wave functions, which ties the system exactly at the Anderson insulator transition for all defect concentrations, and preserving the chiral symmetry.

Insight into the configuration of hard-soft carbon composites for high performance sodium-ion batteries

Hard carbon materials are considered suitable anode materials for sodium-ion batteries due to their abundant defect sites and large interlayer distance, which are respectively beneficial to the adsorption/desorption and insertion/extraction behaviors of Na+ during the electrochemical process. However, the poor electrical conductivity resulting from the intrinsic short-range ordered structure in the carbon skeleton and limited active sites significantly hinders their electrochemical performance. Herein, hard and soft carbon composites with various configurations are developed using a layer-by-layer coating method with SiO2 nanospheres as templates. These composites, including the hard carbon coated soft carbon composite structure (SC@HC), soft carbon coated hard carbon composite structure (HC@SC), and uniformly mixed soft and hard carbon composites (HSC), are prepared through confined-carbonization under the outermost SiO2 layer. The resulting hollow nanospheres possess ultra-small diameters (approximately 50 nm), ultra-thin wall thicknesses (5-6 nm), and different hard/soft carbon layer arrangements. Evaluation of sodium storage properties showed that the combination of soft and hard carbon outperformed pure soft or hard carbon, with HC@SC configuration offering materials with larger interlayer spacing, higher defect concentration, and a more complete conductive network. This enhances sodium storage capacity (293 mAh g-1@1 A g-1) and rate performance (242 mAh g-1@5 A g-1). The findings of this study present a novel approach to designing soft and hard carbon composites for high-performance sodium-ion batteries.

Unraveling the Deep‐Level Defects Induced Optical Losses in LilnSe2 Crystal toward Enhancement of Mid‐Infrared Laser Radiation

AbstractMid‐infrared (MIR) lasers generated by nonlinear optical (NLO) crystals have aroused extensive attention in various military and civilian applications. Among the MIR NLO crystal family, LiInSe2 (LISe) is a promising candidate in the generation of MIR lasers due to its wide transmission range, large bandgap, and high laser‐induced damage threshold. However, the intrinsic defects in LISe induce optical losses, which will induce laser damage and hinder the performance of MIR laser generation. In this work, the mechanism of optical absorption induced by defects is revealed in LISe through transient absorption (TA) spectroscopy. It is verified that the deep‐level defects in LISe give rise to the extra optical absorption, which is owing to the excited state absorption (ESA) and photo‐induced absorption (PIA). Accordingly, for improving the optical properties of LISe crystals, Li2Se vapor‐mediated annealing to reduce defects concentration is rationally designed. The results confirmed that the optical properties of annealed LISe are improved due to the decrease of defects concentration. Ultimately, the performance of MIR laser generation is successfully enhanced by using the annealed LISe crystal. This work provides deep insights into the defect‐induced absorption losses in LISe crystals and promotes the application of LISe crystals in MIR laser generation.

Impact of Defects and Disorder on the Stability of Ta3N5 Photoanodes

AbstractThe photoelectrochemical performance of Ta3N5 photoanodes is strongly impacted by the presence of shallow and deep defects within the bandgap. However, the role of such states in defining stability under operational conditions is not well understood. Here, a highly controllable synthesis approach is used to create homogenous Ta3N5 thin films with tailored defect concentrations to establish the relationship between atomic‐scale point defects and macroscale stability. Reduced oxygen contents increase long‐range structural order but lead to high concentrations of deep‐level states, while higher oxygen contents result in reduced structural order but beneficially passivate deep‐level defects. Despite the different defect properties, the synthesized photoelectrodes degrade similarly under water oxidation conditions due to the formation of a surface oxide layer that blocks interfacial hole injection and accelerates charge recombination. In contrast, under ferrocyanide oxidation conditions, it is found that Ta3N5 films with high oxygen concentrations exhibit long‐term stability, whereas those possessing lower oxygen contents and higher deep‐level defect concentrations rapidly degrade. These results indicate that deep‐level defects result in rapid trapping of photocarriers and surface oxidation but that shallow oxygen donors can be introduced into Ta3N5 to enable kinetic stabilization of the interface.

DFT study of the role and possible contribution of defects to lithium metasilicate [formula omitted] luminescence

Lithium metasilicate (Li2SiO3) has recently been shown to display outstanding stimulated luminescence properties, which are governed by defects and/or impurities. Here, the possible contribution and character of native point and complex defects to stimulated luminescence of lithium metasilicate have been investigated employing calculations based on the density functional theory (DFT). Under high concentrations of acceptor defects, isolated lithium interstitials were found to be the defects with the lowest formation energy (0.41 eV) but it is shown that they cannot contribute to luminescence. On the other hand, Oi−2 are the most favorable and stable defects under high concentrations of donor defects. F-centers and oxygen peroxides were identified as first- and second-order processes of point defects, which would explain experimental observations in the literature. Bridging oxygen vacancies were shown to introduce shallow electron traps able to trap up to four electrons. On the contrary, non-bridging oxygen vacancies lead to the formation of deep color centers with the capability of trapping up to two carriers/center, which could be the final state for the radiative process of luminescence. These results provide guidance for the interpretation of experimental measurements of luminescence.

Unraveling interfacial thermal transport in β-Ga2O3/h-BN van der Waals heterostructures

As global power consumption rapidly increases with generation of significant amount of heat, efficient thermal management in electronic equipments becomes an urgent task, which requires a comprehensive understanding on thermal transport in heterostructures within devices. Here, we present detailed examination on the interfacial thermal transport of van der Waals (vdW) heterostructures, composed of β-Ga2O3 and hexagonal boron nitride (h-BN) multilayers. Through extensive molecular dynamics simulations, we show that the interfacial thermal conductance (ITC) of β-Ga2O3/h-BN system becomes as high as 136.8MWm−2K−1, and the high ITC value results from substantial phonon interaction across the interface. In addition to the pristine interface, the effect of structural modulation including strain, vacancies and substitutional defects in h-BN multilayers on the ITC is also analyzed, and it is demonstrated that there exists ranges of strain values and defect concentrations which increase the ITC, and that the enhanced ITC is the result of the interplay among the interfacial distance, the overlap in the phonon density of states and elastic mismatch between β-Ga2O3 and h-BN multilayers. These results not only provide insights into understanding interfacial phonon transport in vdW systems but also offer guiding principles for designing efficient heat dissipators in device applications.

Microstructure, optical, dielectric, and nonlinear properties of Cd1-xBi2x/3Cu3Ti4O12 ceramics

Microstructure features along with optical, dielectric and nonlinear properties of Cd1-xBi2x/3Cu3Ti4O12 (x = 0, 0.3, 0.6, 0.9, and 1.0) ceramics were investigated systematically. With increase in Bi3+ doping content, Cd1-xBi2x/3Cu3Ti4O12 structure sightly distorted and eventually formed more stable configuration. Bi3+ doping also caused grain refinement and increased compactness of ceramics, whereas Bi-rich phase appeared at grain boundaries. Optical band gap (Eg) decreased due to increase in defect concentration. Dielectric loss (tanδ) dropped with increase in Bi3+ doping content while dielectric constant (ɛ′) remained high. The most optimal dielectric characteristics (the lowest tanδ of ∼0.033, giant ɛ′ of ∼10028 at 10 kHz and room temperature, the highest nonlinear coefficient (α of 4.62) and breakdown field strength (Eb of up to ∼9.23 kV/cm) were achieved at x = 0.9. Impedance spectra revealed semiconducting grains and insulating grain boundaries. Dielectric response evolution in Cd1-xBi2x/3Cu3Ti4O12 ceramics was described using internal barrier layer capacitor model. Electric modulus values indicated that low-frequency relaxation originated from grain boundaries. High energy barrier of grain boundaries was beneficial for enhancement of nonlinear properties of ceramics. Thus, Bi3+ doping improved both dielectric and nonlinear characteristics of Cd1-xBi2x/3Cu3Ti4O12 ceramics.

Effect of Carbon on Void Nucleation in Iron.

The study reports the significance of carbon presence in affecting void nucleation in Fe. Without carbon, void nucleation rates decrease gradually at high temperatures but remain significantly high and almost saturated at low temperatures. With carbon present, even at 1 atomic parts per million, void nucleation rates show a low-temperature cutoff. With higher carbon levels, the nucleation temperature window becomes narrower, the maximum nucleation rate becomes lower, and the temperature of maximum void nucleation shifts to a higher temperature. Fundamentally, this is caused by the change in effective vacancy diffusivity due to the formation of carbon-vacancy complexes. The high sensitivity of void nucleation to carbon comes from the high sensitivity of void nucleation to the vacancy arrival rate in a void. The void nucleation is calculated by first obtaining the effective vacancy diffusivity considering the carbon effect, then calculating the defect concentration and defect flux change considering both carbon effects and pre-existing dislocations, and finally calculating the void nucleation rate based on the recently corrected homogeneous void nucleation theory. The study is important not only in the fundamental understanding of impurity effects in ion/neutron irradiation but also in alloy engineering for judiciously introducing impurities to increase swelling resistance, as well as in the development of simulation and modeling methodologies applicable to other metals.

Surface oxygen vacancies induced by cu-doping in hexagonal ZnMn2O4 nanoplates for high efficiency photothermocatalytic oxidation of toluene

The exploitation of efficient and stable photothermal catalyst for the deep mineralization of volatile organic compounds (VOCs) is crucial and challenging. Herein, a photothermal catalyst with abundant oxygen defects was prepared for the first time via Cu-doped ZnMn2O4 hexagonal nanoplate. Experimental characterization results reveal that Cu doping enhances not only the ZnMn2O4 defect contents but also the light absorption and thermal conversion ability of ZnMn2O4. Compared to the undoped ZnMn2O4 (ZMO), the ZnMn2O4 with optimal Cu doping amount (ZMO-4Cu) exhibits excellent photothermal catalytic performance (94% toluene conversion and 87% toluene mineralization) and good resistance to low concentration SO2 under full-spectrum light irradiation. Experimental characterizations and theoretical calculations jointly demonstrated that the oxygen vacancies of ZMO-4Cu surface are more conducive to the adsorption of O2, effectively reduce the oxygen dissociation energy of ZMO-4Cu, thus generating abundant active oxygen species and improving the photothermal catalytic activity for toluene oxidation. In situ IR experiments disclosed that photothermal catalysis is more conducive to the toluene deep oxidation than thermal catalysis. This work provides new insights for the design of high efficiency photothermal catalysis for the deep oxidation of VOCs.

Probing of CoO-induced nano-sized defects in Li2SO4–MgO–P2O5 glasses: Insights from positron annihilation lifetime spectroscopy

This study investigates the influence of CoO doping on concentration and characteristics of nano-sized cavities in Li₂SO₄-MgO-P₂O₅ glasses using positron annihilation lifetime spectroscopy (PALS). These defects are known to significantly impact the physical properties of glasses. Glasses with compositions of 20 Li₂SO₄-20MgO-(60-x) P₂O₅: x CoO (0 ≤ x ≤ 1.0 mol%), were prepared using melt-quench technique. PALS analysis revealed a strong dependence of positronium (e⁺- e⁻ pair) lifetime on CoO concentration. The analysis of the results further indicated that the fraction of free volume Δf/f0) and cavity radius (R) reached minimum values between 0.6 and 0.8 mol% CoO, but increased with further CoO doping. This suggests that cobalt ions prefer Oh sites, act as network modifiers, and create a larger concentration of free volume defects when CoO is increased beyond 0.8 mol%. Notably, the PALS-derived free volume defect concentration with CoO concentration is found to follow nearly same trend exhibited by the results of optical absorption and AC conductivity studies.