Photophysical investigation of the formation of defect levels in P doped ZnO thin films

Zinc oxide (ZnO) offers a major disadvantage of asymmetry doping in terms of reliability, stability, and reproducibility of p-type doping, which is the main hindrance in realization of optoelectronic devices. The problem is even more complicated due to formation of various native defects in unintentionally doped n-type ZnO. The realization of p-type conductivity in doped ZnO requires an in-depth understanding of the formation of an effective shallow acceptor, as well as donor-acceptor compensation. Photophysical properties such as photoconductivity along with photoluminescence (PL) studies have unprecedentedly and effectively been utilized in this work to monitor the evolution of various in-gap defects. Phosphorus (P) doped ZnO thin films have been grown by RF magnetron sputtering under various Ar to O₂ gas ratios to investigate the effect of O₂ on the donor-acceptor compensation by comprehensive photoconductivity measurements supported by the PL studies. Initial elemental analyses indicate presence of abundant zinc vacancies (V_Zn) in O-rich ambience. The results predict that P sits in the zinc (Zn) site rather than the oxygen (O) site causing the formation of P_Zn–2V_Zn acceptor-like defects, which compensates the donor defects in P doped ZnO films. Photocurrent spectra uniquely reveal presence of more oxygen vacancies (V_O) defects states in lower O₂ flow, which gets compensated with an increase in the O₂ flow. Successive photocurrent transients indicate probable presence of more V_O in the films grown with lower O₂ flow and more V_Zn in higher O₂ flow. Overall the photosensitivity measurements clearly present that O-rich ambience expedites the formation of acceptor defects which are compensated, thereby lowering the dark current and enhancing the ultraviolet photosensitivity.     

Theoretical investigation of intrinsic point defects and the oxygen migration behavior in rare earth hafnates

In this work, the composition-dependent point defect types and formation energies of RE₂Hf₂O₇ (RE = La, Ce, Pr, Nd, Pm, Sm, Eu and Gd) as well as the oxygen diffusion behavior are systematically investigated by first-principles calculations. The possible defect reactions and dominant defect complexes under stoichiometric and non-stoichiometric conditions are revealed. It is found that O Frenkel pairs are the predominant defect in stoichiometric pyrochlore hafnates. Hf-RE cation anti-site defects, accompanied by RE vacancies and/or oxygen interstitials, are stable in the non-stoichiometric case of HfO₂ excess. On the other hand, RE-Hf anti-site defects together with oxygen vacancies and/or RE interstitials are preferable in the case of RE₂O₃ excess. The energy barriers for the migration along the V_O48f - V_O48f pathway of pyrochlore hafnates were calculated to be between 0.81 eV and 0.89 eV. Based on these results, a defect engineering strategy is proposed and the pyrochlore hafnates investigated here are predicted to exhibit potential oxygen ionic conductivity.     

A strategy for defects healing in 3D printed ceramic compact via cold isostatic pressing: Sintering kinetic window and microstructure evolution

In this study, we developed a unique defect healing method for 3D printed ceramic compact via cold isostatic pressing (CIP) after debinding, and typical features of interlayer interface defects of 3D-printed zirconia compact were characterized and found to be reduced significantly. The characteristic sintering kinetics window and microstructure evolution of the healed sintered bodies were systematically investigated, which was found to be quite different from conventional shaping methods. The three sintering stages are probed by their feature microstructure details such as the mechanically flattening surface at the early sintering stage, the heterogeneous microstructure and high porosity in the interlayer interface region at the middle stage, and the slightly ripple-like structural features combined with the healed interlayer defects at the final stage. The evolution of the pore structure of the healed 3D printed bodies were traced and the mechanical properties such as the Young's modulus, hardness, and fracture toughness were measured to understand the significance of the heal effect.     

Intrinsic Defect Limit to the Growth of Orthorhombic HfO2 and (Hf,Zr)O2 with Strong Ferroelectricity: First-Principles Insights

It is believed that promoting the fraction of ferroelectric orthorhombic phase (o-phase) through O-poor growth conditions can increase the spontaneous polarization of HfO₂ and (Hf,Zr)O₂ thin films. However, the first-principles calculations show that the growth may be limited by the easy formation of point defects in the orthorhombic and tetragonal phases of HfO₂, ZrO₂, and (Hf,Zr)O₂. Their dominant defects, O interstitial (O_i) under O-rich conditions and O vacancy (V_O) under O-poor condition, have low formation energies and quite high density (10¹⁶–10¹⁹ cm⁻³ for 800–1400 K growth temperature). Especially, O_i has negative formation energy in tetragonal HfO₂ under O-rich condition, causing non-stoichiometry and limiting the crystalline-seed formation during o-phase growth. High-density defects can cause disordering of dipole moments and increase leakage current, both diminishing the polarization. These results explain the experimental puzzle that the measured polarization is much lower than the ideal value even in O-poor thin films and highlight that controlling defects is as important as promoting the o-phase fraction for enhancing ferroelectricity. The O-intermediate condition (average of O-rich and O-poor conditions) and low growth temperature are proposed for fabricating HfO₂ and (Hf,Zr)O₂ with fewer defects, lower leakage current, and stronger ferroelectricity, which challenges the belief that O-poor condition is optimal.     

Anisotropic effects of oxygen vacancy defects on the electrical properties of highly oriented bismuth titanate ferroelectric ceramics

Bismuth titanate (Bi₄Ti₃O₁₂, BIT) exhibits a high Curie temperature and anisotropic electrical performance owing to its layered perovskite structure, and hence, it is an important ferroelectric material for high-temperature piezoelectric applications. It is crucial to understand the effects of the anisotropy in BIT-based ferroelectrics for developing novel high-temperature piezoelectric materials. In this study, a highly textured BIT ceramic was fabricated using the tape-casting technique from highly grain-oriented BIT platelets prepared by the molten salt method. The textured BIT ceramic showed a dense microstructure and high grain orientation along the (00l) plane with a texturing degree F_00l = 0.86. It exhibited significant anisotropy in the electrical properties along the directions parallel and perpendicular to the axis of the tape-casting plane. Double ferroelectric hysteresis P–E loops and normal ferroelectric P–E loops were observed in the parallel and perpendicular samples, respectively. In addition to the layered crystal structure and domains, the anisotropy in the arrangement of the oxygen vacancy defects and their transport in the structure led to a significant anisotropy in the ferroelectric properties of the textured BIT ceramics. This work demonstrates the anisotropic arrangement of the oxygen vacancy defects and its effect on the electrical properties of high-temperature bismuth layer-structured ferroelectrics.     

A Smart Deep Convolutional Neural Network for Real-Time Surface Inspection

A proper detection and classification of defects in steel sheets in real time have become a requirement for manufacturing these products, largely used in many industrial sectors. However, computers used in the production line of small to medium size companies, in general, lack performance to attend real-time inspection with high processing demands. In this paper, a smart deep convolutional neural network for using in real-time surface inspection of steel rolling sheets is proposed. The architecture is based on the state-of-the-art SqueezeNet approach, which was originally developed for usage with autonomous vehicles. The main features of the proposed model are: small size and low computational burden. The model is 10 to 20 times smaller when compared to other networks designed for the same task, and more than 700 times smaller than general networks. Also, the number of floating-point operations for a prediction is about 50 times lower than the ones used for similar tasks. Despite its small size, the proposed model achieved near-perfect accuracy on a public dataset of 1800 images of six types of steel rolling defects.     

Enhancement of the radiation resistance of cerium-containing fluorophosphate glasses through codoping with Sb2O3 and Bi2O3

The growing demand for radiation-resistant optical glasses for space and nuclear radiation applications has attracted significant research interest. However, radiation-resistant fluorophosphate glasses have been poorly studied. In this work, we report on the tailoring and performance of radiation-resistant fluorophosphate glasses that contained cerium through codoping with Sb₂O₃ and Bi₂O₃. The physical properties, optical properties, microstructure, and defects of fluorophosphate glasses were investigated using transmittance measurements, absorption measurements, as well as Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and electron paramagnetic resonance (EPR) spectroscopy. The results showed that the radiation resistance of all codoped fluorophosphate glasses was better than the undoped cerium-containing fluorophosphate glasses after 10–250 krad(Si) irradiation. Especially in glasses doped with Bi₂O₃, the optical density increment at 385 nm was only 0.1482 after 250 krad(Si) irradiation. The CeO₂ prevented the development of phosphate-related oxygen hole center (POHC) defects, whereas further codoping with Bi₂O₃ suppressed the formation of oxygen hole center (OHC) and POEC defects, reducing the breaking of phosphate chains caused by CeO₂. Bi³⁺ is more likely than Sb³⁺ to change the valence, affecting the transition equilibrium of intrinsic defects and reducing the concentration of defects produced by irradiation. When codoping with Sb₂O₃ and Bi₂O₃, Bi₂O₃ does not enhance radiation resistance owing to the scission effect of Sb₂O₃ on the phosphate chain, which is not conducive to the radiation resistance of glasses. This indicates that the cerium-containing fluorophosphate glasses doped with Bi₂O₃ can effectively suppress the defects caused by irradiation and improve the radiation resistance of the glasses.     

缓倾斜极薄矿体全面法开采残留点柱回采方案及稳定性分析研究

某石英脉型钨矿床,矿体倾角平均20°,矿脉厚度0.3~0.8m,采用全面法开采。经过20多年的开采遗留下大量点柱和空区,而且相邻的采空区、以及相邻中段的采空区基本已相互贯通形成空区联合体。随着暴露时间的延长,采场应力集中,采空区安全隐患大,同时造成大量矿柱资源浪费。为了确保矿山生产安全和可持续发展,同时对遗留的矿柱进行回收,通过研究采场顶板允许暴露面积、结合开采技术条件、充填工艺研究等,确定的矿柱回收工艺和采场充填工艺,并针对试验采场的回收方案进行采场矿柱回收稳定性数值分析,综合验证了点柱充填回采的方案是安全可行的,从而为矿山空区治理与点柱安全回收提供指导。     

油气管道缺陷漏磁检测有限元模拟

为了研究油气管道缺陷的漏磁信号特征，基于漏磁检测技术基本原理，采用有限元方法，应用ANSYS软件对含裂纹和气孔缺陷管道磁化后产生的漏磁场进行模拟仿真，得到了描述漏磁场特征的磁通密度径向和轴向分布曲线。通过改变裂纹和气孔的尺寸，得出这两种缺陷形式不同尺寸下的漏磁场分布规律。结果表明，随着裂纹深度增加，磁通密度径向、轴向分量的峰值强度均明显增大；在距管壁表面相同深度下，气孔缺陷磁通密度的峰值随孔径增加而显著增大；相同孔径时，气孔距表面越近，漏磁信号越强。为管道漏磁检测过程中的裂纹和气孔缺陷的特征识别提供了理论基础和实践依据。     

Characterizing pathological imperfections in macromolecular crystals: lattice disorders and modulations

Macromolecular crystal structure determination can be complicated or brought to a halt by crystal imperfections. These issues motivated us to write up what we affectionately call ‘The Definitive Hitchhiker’s Guide to Pathological Macromolecular Crystals: Lattice Disorders and Modulations’. Perhaps the most challenging imperfections are lattice order–disorder phenomena and positional modulations. Many of these types of crystals have been solved, and progress has been made on the more challenging forms. Diagnostic tools and how to solve many of these problem crystal structures are reviewed. New avenues are provided for approaching the solution of incommensurately modulated crystals. There are a good number of case studies in the literature of lattice order–disorder phenomena and crystallographic modulations that make it timely to write a review. This review concludes with a projected pathway for solving incommensurately modulated crystals, personal views of future directions and needs of the crystallographic community.