Formation Of Vacancy Defects Research Articles

Study of the effect of CdCl2 introduction on the high temperature activation treatment of CdTe:As polycrystalline thin films

V-doped CdTe polycrystalline films can achieve both doping activation and defect passivation by high-temperature CdCl2 heat treatment, but this requires simultaneous modulation of the amount of CdCl2 introduced to obtain high-quality films. It is found that increasing the CdCl2 introduction does not change the physical phase structure and lattice constant of CdTe:As thin films, but promotes grain recrystallisation, and can promote the formation of A-center, and inhibit the formation of Cd vacancy (VCd) defects, as well as the formation of deep energy level defects. The results provide guidance for the improvement of high-temperature CdCl2 heat treatment of V-doped CdTe polycrystalline thin films.

Realizing Ultrahigh Conversion Efficiency of ≈9.0% in YbCd2Sb2/Mg3Sb2 Zintl Module for Thermoelectric Power Generation.

Recently, YbCd2Sb2-based Zintl compounds have been widely investigated owing to their extraordinary thermoelectric (TE) performance. However, its p orbitals of anions that determined the valence band structure are split due to crystal field splitting that provides a good platform for band manipulation by doping/alloying and, more importantly, the YbCd2Sb2-based device has yet to be reported. In this work, single-phase YbCd1.5Zn0.5Sb2 is successfully obtained through precise chemical composition control. Then, YbMg2Sb2-alloying increases the cationic vacancy defect formation energy and further optimizes carrier concentration. Moreover, the band structure of YbCd1.5Zn0.5Sb2 is subtly manipulated, and the underlying mechanism is experimentally explored. Combined with the reduced lattice thermal conductivity, a high peak ZT value of ∼1.43 at 700K is obtained for YbCd1.425Zn0.475Mg0.1Sb2. Subsequently, choosing Fe90Sb10 as the diffusion barrier layer and adopting the transient liquid phase bonding technique, for the first time, it is demonstrated that YbCd2Sb2/Mg3(Sb, Bi)2 TE module with an ultrahigh conversion efficiency of ≈9.0% at a heat difference of 430K. More importantly, this module displays good thermal stability. This work paves the way for YbCd2Sb2 materials and devices in mid-temperature heat recovery.

The breakthrough of oxide pathway mechanism in stability and scaling relationship for water oxidation.

An in-depth understanding of electrocatalytic mechanisms is essential for advancing electrocatalysts for the oxygen evolution reaction (OER). The emerging oxide pathway mechanism (OPM) streamlines direct O-O radical coupling, circumventing the formation of oxygen vacancy defects featured in the lattice oxygen mechanism (LOM) and bypassing additional reaction intermediates (*OOH) inherent to the adsorbate evolution mechanism (AEM). With only *O and *OH as intermediates, OPM-driven electrocatalysts stand out for their ability to disrupt traditional scaling relationships while ensuring stability. This review compiles the latest significant advances in OPM-based electrocatalysis, detailing design principles, synthetic methods, and sophisticated techniques to identify active sites and pathways. We conclude with prospective challenges and opportunities for OPM-driven electrocatalysts, aiming to advance the field into a new era by overcoming traditional constraints.

Boosting electrocatalytic urea oxidation performance of NiSx-VS4-C mediated via glycerol coking

Ni is regarded as active site for provoking urea oxidation reaction (UOR); nevertheless, monometallic Ni-based catalysts can not possess sufficiently high performance owing to poisoning susceptibility of Ni towards carbonaceous intermediates and the poor electrical conductivity. In response, NiSx-VS4-C is synthesized via a facile glycerol coking strategy in hydrothermal system. It is found that NiSx-VS4-C is composed of many nanoparticles with a relatively small size (approximately 70 nm). Besides acting as the precursor of carbon, glycerol can regulate the morphology and structure of catalysts, and promote the formation of vacancy defects. Using as catalyst for UOR, a specific current activity of 652 mA cm−2 mg−1 for NiSx-VS4-C can be achieved at 0.52 V (vs. Hg/HgO), which is much higher than that for NiSx or VS4 synthesized in glycerol solution. Glycerol coking is important for boosting catalytic activity. NiSx-VS4-C synthesized in glycerol solution exhibits much better catalytic activity than that synthesized in other alcohol solutions. Potential dependent impedance analyses reveal that urea indirect electro-oxidation mechanism should be mainly obeyed when NiSx-VS4-C is employed as catalyst. Both Ni and V with high chemical valence are active sites, where Ni species is mainly in charge of the oxidation of amine intermediate and V species is mainly in charge of the oxidation of CO intermediate. Carbon, especially graphitized phase, will significantly enhance the electrical conductivity and accelerate the charge transfer process. Therefore, constructing dual active sites and enhancing electrical conductivity via polyalcohol coking provide promising strategies for Ni-based catalysts towards UOR.

Study of radiation-induced structural changes in the near-surface layer of ZrO2 ceramics caused by He2+ irradiation

Abstract The aim of this study is to determine changes in the near-surface layer of ZrO2 ceramics caused by irradiation with low-energy He2+ ions, as well as the associated formation of defects and structural deformations. During the experimental work conducted, it was established that the accumulation of deformation-structural distortions is of two stage nature, having a direct dependence on irradiation fluence and, therefore, on atomic displacement value. It was determined that at small atomic displacement values (less than 10 dpa), the main mechanisms of structural distortions are caused by tensile residual stresses, the value of which is less than 0.1 GPa. At the same time, the deformation distortion of chemical bonds has a pronounced anisotropy associated with a more pronounced distortion of the Zr–OI chemical bonds, the distortion of which results in the formation of vacancy defects in the form of VO. During determination of alterations in optical characteristics depending on the atomic displacement value, it was found that the dominant role at small values of dpa (less than 10 dpa) is played by point defects, which influence the formation of obstacles in the form of absorbing centers. In this case, an increase in the irradiation fluence above 1017 ion/cm2 results in a growth in the linear refractive index, the change of which has a direct correlation with the value of residual stresses in the damaged layer. Certain dependencies of changes in structural features and their relationship with deformation distortions, as well as the accumulation of vacancy defects, can subsequently be used to predict the potential of using these ceramics as materials for new generation nuclear reactors.

Photocatalytic CO2 Reduction Using Zinc Indium Sulfide Aggregated Nanostructures Fabricated under Four Anionic Conditions.

Zinc indihuhium sulfide (ZIS), among various semiconductor materials, shows considerable potential due to its simplicity, low cost, and environmental compatibility. However, the influence of precursor anions on ZIS properties remains unclear. In this study, we synthesized ZIS via a hydrothermal method using four different anionic precursors (ZnCl2/InCl3, Zn(NO3)2/In(NO3)3, Zn(CH3CO2)2/In(CH3CO2)3, and Zn(CH3CO2)2/In2(SO4)3), resulting in distinct morphologies and crystal structures. Our findings reveal that ZIS produced from Zn(CH3CO2)2/In2(SO4)3 (ZIS-AceSO4) exhibited the highest photocatalytic CO2 reduction efficiency, achieving a CO production yield of 134 μmol g-1h-1. This enhanced performance is attributed to the formation of more zinc and indium vacancy defects, as confirmed by EDS analysis. Additionally, we determined the energy levels of the valence band maximum (VBM) and the conduction band minimum (CBM) via UPS and absorption spectra, providing insights into the band alignment essential for photocatalytic processes. These findings not only deepen our understanding of the anionic precursor's impact on ZIS properties but also offer new avenues for optimizing photocatalytic CO2 reduction, marking a significant advancement over previous studies.

Enhanced Thermal and Photostability of Perovskite Solar Cells by a Multifunctional Eu (III) Trifluoromethanesulfonate Additive

AbstractPerovskite solar cells (PSCs) have witnessed a meteoric rise in device performance. However, maintaining photostability, particularly under thermal stress, remains a challenge due to defect formation in the perovskite layer. This study introduces europium (III) trifluoromethanesulfonate [Eu(OTF)3] as a multifunctional additive in two‐step processed perovskite films, significantly improving the performance and high‐temperature photostability of n‐i‐p PSCs. Density function theory (DFT) calculations reveal that the OTF− anion strongly coordinates with Pb2+, effectively inhibiting iodine vacancy defect formation. The addition of Eu(OTF)3 promotes perovskite grain growth to ≈2 µm and enhances film crystallinity. PSCs with a structure of ITO/SnO2/perovskite/PDCBT/NiOx/Au achieve a champion power conversion efficiency (PCE) of 23.8%. Under 85 ± 5 °C and 1 sun illumination at an open circuit in ambient air, the PSCs with Eu(OTF)3 retain 82% of their initial PCE after aging for 1500 h.

Synergistic Effect of Zn2+ Cation Doping and Te2− Anion Passivation on CsPbBrxI3‐x Nanocrystals for Efficient Perovskite Light‐Emitting Diodes

AbstractThe challenges of instability and surface defects in CsPbBrxI3‐x nanocrystals (NCs) pose significant limitations on their potential application in high‐performance pure‐red perovskite light‐emitting diodes (PeLEDs). Herein, a synergistic strategy of divalent cation (Zn2+) doping and anion (Te2−) passivation is proposed to solve these issues. Density functional theory analysis reveals that the synergistic effect can not only reduce the formation energy of CsPbBrxI3‐x NCs but also increase theiodide vacancy defect formation energy of CsPbBrxI3‐x NCs. Consequently, the optimized Zn2+/Te2− co‐modified CsPbBrxI3‐x NCs exhibit significantly enhanced stability with a near‐unity photoluminescence efficiency. Pure‐red PeLEDs based on these CsPbBrxI3‐x NCs possess outstanding spectral stability with a maximum external quantum efficiency and luminance of 16.1% and 1397.2 cd m−2, respectively. This synergistic strategy provides a new approach for enhancing the performance of mixed halide perovskite NCs and the corresponding optoelectronic devices.

Study on fluorine vacancy defects in yttrium fluoride coating materials

Abstract Rare-earth fluoride coating materials have attracted wide attention as a substitute for ThF4 low-refractive index materials. However, the coating materials and coated films fail to achieve the desired results due to vacancy defects caused by their fluorine-loss decomposition characteristics. To explore the rare earth fluoride coating materials’ fluorine loss influence law, the melt crystallization method is used to simulate the yttrium fluoride (YF3) pre-melting process through the electronic paramagnetic resonance (EPR) obtained at different temperatures under the fluorine vacancy defects change rule. According to the number of unpaired spintrons, the number of spintrons in each vacancy is calculated. The results show that the fluorine vacancy defects increase with the increase of temperature, the formation of YF3 fluorine vacancy defects does not affect the change of crystal structure, and the addition of the additive ammonium hydrogen fluoride (NH4HF2) can reduce the oxygen content of YF3 and effectively inhibit the formation of fluorine vacancy. The effect is gradually obvious with the amount of additives added.

Enhancement of nitric oxide sensing performance via oxygen vacancy promotion on strontium-doped LaFeO3 perovskites

The potential of Sr-doped LaFeO3 as a nitrogen oxide–sensing material was studied by experimentation and theory calculation. The test results showed a much higher sensitivity and selectivity for a nitric oxide sensor based on Sr-doped LaFeO3 than on pure LaFeO3. The response, which was increased nearly 0.5-fold compared to pure LaFeO3, was attributed to an enhancement of oxygen vacancy and adsorbed oxygen. Further theoretical analysis indicated that Sr doping resulted in the formation of oxygen vacancy defects and altered the adsorption energy of the material, leading to an increase in chemisorbed oxygen species and intermolecular interactions. This work emphasizes the significance of oxygen vacancy defects in gas sensors and provides a feasible approach for enhancing the properties of gas sensors.

Improving Hybrid Tin Halide Films by Tin Trifluoromethanesulfonate for Lead-Free Perovskite Solar Cells.

Tin-based perovskite solar cells (Sn-PSCs) without toxic lead ions outperform other types of lead-free PSCs in terms of photovoltaic performance. To avoid the oxidation of Sn2+ cations and the formation of vacancy defects, most reports involve the addition of SnF2 to the perovskite precursor solution, but hybrid tin halide (Sn-PVK) films still suffer from poor crystallinity and stability. In this work, we used an alternative additive of tin trifluoromethanesulfonate (Sn(OTF)2). Compared to SnF2, the solubility of Sn(OTF)2 in the precursor solution is greatly improved, and the crystal nucleation process is delayed, resulting in the enhancement of crystal growth. The coordination ability of the OTF- anions suppresses the oxidation of Sn2+ cations, which promotes the stability of Sn-PVK films. By replacing the conventional additive of SnF2 with Sn(OTF)2, the device achieves an increase in power conversion efficiency from 7.96% to 10.3%, while the stability of the devices is improved simultaneously.

Synchronous effect of coordination and hydrogen bonds boosting the photovoltaic performance of perovskite solar cells

Superior quality of perovskite film with perfect crystalline and low defect density is crucial for achieving excellent photovoltaic performance and durability of perovskite solar cells (PSCs), and regulation of growth of perovskite crystal and defects passivation by additive is remain challenge. Herein, two acyl molecules (Succinimide: SCI, and Hydantoin: HDT) were incorporated into perovskite precursor solution as additive. It can be found that the HDT molecule can not only passivate undercoordinated Pb2+ defects in perovskite films by the -C=O groups with coordination bonds, but also formed hydrogen bonds with I− by -NH- group, which effectively inhibited the formation of iodine vacancy defects and regulated growth rate of perovskite crystals, and the quality of perovskite films was optimized with enlarging grain size and reduced trap-density. Consequently, power conversion efficiency of HDT-based device was enhanced from 19.47 % to 21.00 %, with an enhancement of JSC and VOC. Moreover, the HDT-based device without encapsulation retained 83.7 % of its initial PCE after being aged at 10–20 % RH for 60 days. Obviously, such a study could provide a new strategy to optimize quality of perovskite film for boosting performance of PSCs.

Kornblum Oxidation Reaction-Induced Collective Transformation of Lead Polyhalides for Stable Perovskite Photovoltaics.

The iodide vacancy defects generated during the perovskite crystallization process are a common issue that limits the efficiency and stability of perovskite solar cells (PSCs). Although excessive ionic iodides have been used to compensate for these vacancies, they are not effective in reducing defects through modulating the perovskite crystallization. Moreover, these iodide ions present in the perovskite films can act as interstitial defects, which are detrimental to the stability of the perovskite. Here, an effective approach to suppress the formation of vacancy defects by manipulating the coordination chemistry of lead polyhalides during perovskite crystallization is demonstrated. To achieve this suppression, an α-iodo ketone is introduced to undergo a process of Kornblum oxidation reaction that releases halide ions. This process induces a rapid collective transformation of lead polyhalides during the nucleation process and significantly reduces iodide vacancy defects. As a result, the ion mobility is decreased by one order of magnitude in perovskite film and the PSC achieves significantly improved thermal stability, maintaining 82% of its initial power conversion efficiency at 85°C for 2800h. These findings highlight the potential of halide ions released by the Kornblum oxidation reaction, which can be widely used for achieving high-performance perovskite optoelectronics.

Characteristics of 4-inch (100) oriented Mg-doped β-Ga2O3 bulk single crystals grown by a casting method

In this Letter, 4-inch diameter (100) magnesium-doped monoclinic gallium oxide (Mg:β-Ga2O3) bulk single crystals were grown by a casting method. The crystallographic structure, electrical, optical properties, and defects of Mg-doped β-Ga2O3 was thoroughly investigated by XRD rocking curves, AFM, non-contact resistivity measurements, XPS, optical transmission spectra, Raman spectroscopy, and defect-selective chemical etching processes. Comparing to the UID samples, the larger bandgap of 4.75 eV and high resistivity of 3.50×1012 Ω∙cm indicated Mg a proper dopant for fabricating semi-insulating β-Ga2O3 substrates which could be preferred for power devices. XPS spectra exhibited the ability of Mg2+ to inhibit the formation of oxygen vacancy defects in the crystals. Meanwhile, the high crystalline quality and low density of defects demonstrated the advantages of casting method in achieving large-size and high-quality β-Ga2O3 bulk single crystals with changeable resistivity. This result indicates a high potential to achieve high-quality and low-cost substrates which satisfy the requirement of high-performance power electronic devices.

Ab-initio study of point defects in Th and U alloy

Point defect formation energies are calculated along with several structural and elastic properties for the fcc (α) and bcc (β) Th crystal structures. Th-self defects and single uranium impurity defects are modeled in the fcc phase, whereas only Th self-defects are modeled in the high temperature bcc phase. Additionally, an analysis of several well known exchange-correlation functionals is given in regard to defect modeling performance. Overall, defect formation energies in the bcc phase were lower in energy compared to their defect equivalents in the fcc phase. In both phases, vacancies were found be the most stable, with the bcc vacancy being ∼0.8 eV lower in energy than the fcc vacancy, regardless of form of the exchange-functional. The most stable interstitial defects were in the octahedral and <110> dumbbell positions for the fcc and bcc phases, respectively. It was also found that the <110> and <111> dumbbell defects were unstable in the fcc phase, but not in the bcc phase. Overall, the choice of exchange-correlation functional was found to have almost a negligible effect on the calculated formation energies. The most notable difference between functionals was in the prediction of the vacancy defect formation energies, which may be attributed to differences in the way each functional handles exchange and correlation in regions of low electron density relative to the bulk of a material, such as in the internal surface of a vacancy or vacancy cluster.

Molecular dynamics simulation of effects of loading parameters on fatigue crack growth behavior in titanium single crystal

AbstractThe fatigue crack growth behavior in single‐crystal titanium with a prismatic crack was simulated using molecular dynamics (MD) considering the effects of applied temperature, strain ratio, and strain rate. The results indicate that the material exhibits transient cyclic hardening behavior and dominant cyclic softening behavior. The peak tensile stress decreases with increasing temperature or decreasing strain rate. The deformation mechanism for crack growth involves prismatic dislocation emission and the formation of vacancy defects at different loading conditions. Deformation twinning occurs at the highest temperature, and a secondary crack emerges at the highest strain rate. The Mises stress concentration at the twin boundary and the coalescence between the initial and secondary cracks may accelerate crack propagation. The ΔJ shows good linear relationships with fatigue crack growth rate (FCGR), indicating that ΔJ possesses the potential to assess fatigue crack growth behavior at the atomic scale for ductile metallic materials.

Molecular insights into vacancy defect formation in silicon anodes induced by femtosecond laser

Silicon anodes in lithium-ion batteries have garnered attention due to their high capacity. However, the volume changes during charging and discharging lead to fracturing and reduced lifespan. To address this, femtosecond laser processing technology has been introduced to improve silicon anodes. This involves structural adjustments and the introduction of vacancy defects to enhance the diffusion rate of lithium ions and mitigate volume expansion. This study employs molecular dynamics simulation methods and, based on the Lambert-Beer law, constructs a complex three-dimensional model of a femtosecond laser-ablated silicon anode. The model enables atomic-level observation and tracking of the formation and evolution of vacancy defects in silicon anodes during the heating process induced by femtosecond laser pulses. The results reveal the dynamics of femtosecond laser-induced silicon vacancies, which can be divided into ballistic, combination, and stabilization phases. It was found that the concentration of vacancy defects significantly depends on the laser energy density and pulse width. Statistical analysis of the microstructural evolution of femtosecond laser-processed silicon anodes indicates that the locally induced high temperature and pressure by the femtosecond laser are the primary drivers of changes in vacancy defect concentration. Additionally, a quantitative analysis of laser-induced high-coordination structures was conducted, and an appropriate balance between vacancy concentration and high-coordination structures was established. The study shows that increasing the laser energy density or reducing the pulse width, while inducing more vacancy defects, also results in a higher number of high-coordination structures, which may affect the diffusivity of lithium ions. These findings not only provide in-depth molecular-level insights into the variations of femtosecond laser-induced vacancy defects but also offer significant theoretical support for the application of femtosecond laser-ablated silicon anodes.

Constructing Charge Bridge Path for High‐Performance Tin Perovskite Photovoltaics

AbstractTin‐based perovskite solar cells (TPSCs) have attracted significant research interest due to their exceptional optoelectronic properties and environmentally friendly characteristics. However, TPSCs with ideal bandgap suffer from substantial current losses, necessitating the development of innovative interface engineering strategies to enhance device performance. In this study, an unprecedented approach constructing charge transfer path is presented by a simple post‐growth treatment of 3‐Aminomethylbenzo[b]thiophene (3‐AMBTh) on the perovskite film. The selective reaction of 3‐AMBTh with exposed FA+ on the perovskite surface suppresses the formation of iodine vacancy defects, leading to a reduction in trap density. Additionally, the residual aromatic rings on the surface form an effective π–π stacking interaction system with subsequently deposited ICBA, facilitating enhanced charge transfer at the interface. By harnessing the potential of the charge transfer path, the TPSCs exhibit remarkable device efficiency of up to 14.53%, positioning them among the top‐performing TPSCs reported to date.

Growth of two-dimensional covalent organic frameworks on substrates: insight from microsecond atomistic simulations.

While growing two-dimensional covalent organic frameworks (2D COFs) on substrates holds promise for producing functional monolayers, the presence of many defects in the resulting crystals often hinders their practical applications. Achieving structural order while suppressing defect formation necessitates a detailed atomic-level understanding. The key lies in understanding the polymerization process with high nano-scale accuracy, which presents significant challenges. Here, we perform microsecond atomistic molecular dynamics simulations to describe the deposition and polymerization of cyclohexa-m-phenylene on metal substrates, closely mimicking experimental conditions. Our improved approach highlights that 2D polymerization occurs through monomer addition and island coalescence, with a pre-bonding stage allowing monomers/oligomers to dynamically adjust their configurations to the expanding island structures. Our results elucidate the mechanisms underlying the formation of vacancy and dislocation defects during 2D polymerization as well as their healing processes. Overall, our findings underscore the significant roles that high surface mobility, effective monomer-substrate anchoring, high framework rigidity, moderate monomer coordination, and low bonding rate play in forming large, extended 2D crystals while suppressing vacancy and dislocation defects. We demonstrate how these factors can be tuned through substrate selection, deposition rate modulation, and temperature control, thereby offering valuable insight for strategically optimizing on-surface 2D polymerizations.

A negative photoconductivity photodetector based on two-dimensional Nb3Cl8.

Negative photoconductivity (NPC)-based photodetectors offer a new direction for energy-efficient photodetection technologies, featuring low energy consumption and high responsivity. Two-dimensional (2D) materials are particularly promising for implementing NPC due to their large surface area, abundant surface states, and tunable bandgap properties. In this context, 2D Nb3Cl8, with its unique kagome lattice structure and broad absorption spectrum, has attracted considerable interest. Notably, metal halides such as Nb3Cl8 demonstrate significant potential as NPC materials due to their low anionic and cationic bonding strength, which allows for the formation of vacancy defects with high probability. However, the NPC characteristics of Nb3Cl8 have not been thoroughly investigated. In this study, we fabricated field-effect transistors (FETs) using Nb3Cl8 single crystals synthesized via chemical vapor transport (CVT). These devices exhibited an electron mobility of 4.24 × 10-3 cm2 V-1 s-1 and a high Ion/Ioff ratio of 1.42 × 104. Notably, Nb3Cl8-based photodetectors demonstrated consistent NPC behavior across a wide wavelength range of 400-1050 nm, with a high responsivity of 156.82 mA W-1 at 400 nm. We propose that the trapping effect due to defect levels within the bandgap is the primary cause of this NPC phenomenon. The present findings reveal the unique photodetector properties of Nb3Cl8 and highlight its promise in energy-efficient photodetectors and various optoelectronic applications.