VO2/GaAs异质结的制备及其光电特性研究

采用直流磁控溅射和后退火氧化工艺在p型GaAs单晶衬底上成功制备了n-VO_2/pGaAs异质结,研究了不同退火温度和退火时间对VO_2/GaAs异质结性能的影响,并分析其结晶取向、化学组分、膜层质量以及光电特性。结果表明,在退火时间2 h和退火温度693 K下能得到相变性能最佳的VO_2薄膜,相变前后电阻变化约2个数量级。VO_2/GaAs异质结在308 K、318 K和328 K温度下具有较好的整流特性,对应温度下的阈值跳变电压分别为6.9 V、6.6 V和6.2 V,该结果为基于VO_2相变特性的异质结光电器件的设计与应用提供了可行性。     

涪陵地区茅三段热液白云岩展布影响因素分析

针对热液白云岩展布非均质性强的问题,开展基底断裂与茅三段沉积演化关系研究,分析断裂样式与白云岩分布关系,建立沉积演化模式,预测白云岩的分布。研究结果表明:茅三段可划分为5个小层,1~3小层为白云岩发育主要时期,4~5小层为台地均一化时期,不发育白云岩;15-1、15-2和16号基底断裂控制了早期“台-洼”相间的沉积地貌,断裂附近的地貌高部位为生屑滩发育有利部位,为白云岩的发育提供物质基础;15-1、15-2号基底断裂样式为花状,周边生屑滩白云石化程度高,为白云岩发育最有利区;16号基底断裂为直立状,附近白云石化发育程度较低,为白云岩发育较有利区。研究成果可为热液白云岩领域的进一步勘探提供指导依据。     

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.     

Mechanical properties and wear behavior of Tin+1(Al,A)Cn (A = Ga,In, Sn,n = 1, 2) via quasi-high-entropy of single atomic thick A layer

The strengthening method of multi-element M-site solid solution is a common approach to improve mechanical properties of MAX phase ceramic. However, the research on capability of multi-element A-site solid solution to improve mechanical properties has rarely been reported. Thereupon, quasi-high-entropy MAX phase ceramic bulks of Ti₂(Al_1?xA_x)C and Ti₃(Al_1?xA_x)C₂ (A = Ga, In, Sn, x = 0.2, 0.3, 0.4) were successfully synthesized by in situ vacuum hot pressing via multi-elements solid solution. The multi-elements solid solution in single-atom thick A layer was confirmed by X-ray diffraction and X-ray photoelectron spectroscopy as well as by energy dispersive X-ray spectroscopy mappings. Effects of doped multi-elements contents on the phase, microstructure, mechanical properties, and high temperature tribological behaviors were studied. Results demonstrated that the Vickers hardness, anisotropic flexural strength, fracture toughness, and tribological properties of Ti–Al–C based MAX ceramics could be remarkably improved by constitution of quasi-high-entropy MAX phase in A layers. Moreover, the strengthening and wear mechanisms were also discussed in detail. This method of multi-element solid solution at A-site provides new way to enhance mechanical properties of other MAX phase ceramics.     

Process parameters influence on zone refining and thermodynamics analysis of 1,2-diphenylethane

Effective distribution coefficients of 9 impurities in 1,2-diphenylethane have been calculated by directional crystallization under different ambient frozen temperature. The effect of varied zone size, temperature difference between the melt and ambient frozen environment, number of zone on purity of 1,2-diphenylethane have been also investigated during the process of zone refining. The results indicate that the product purity in the intermediate purified region with varied zone size is higher 0.04%-0.2% than that with constant zone size. The product purity increases with temperature difference between the melt and ambient frozen environment. The appropriate temperature difference is adopted 50℃. The product purity in the intermediate region of sample bar with 2 molten zones is higher 0.05%-0.43% than that with 1 molten zone. In addition, the change of enthalpy and entropy between impurities and 1,2-diphenylethane have been determined.     

Liquid-phase epoxidation of propylene with molecular oxygen by chloride manganese meso-tetraphenylporphyrins

Propylene molecule owns two active sites, the direct epoxidation of propylene by dioxygen is still a challenge due to the limitation of selectivity. In this work, the direct liquid-phase propylene aerobic epoxidation protocol by chloride manganese meso-tetraphenylporphyrin (MnTPPCl) was developed. The conversion of propylene was 12.7%, and the selectivity towards PO (propylene oxide) reached up to 80.5%. The formation of PO was attributed to the mechanism via high-valent Mn species, which was confirmed by means of in situ UV–vis spectrum.     

Effect of nanostructured grains in co-sputtered Ni-GDC thin-film anode on methane conversion kinetics for low temperature solid oxide fuel cells operating on nearly dry methane

Direct-methane solid oxide fuel cells (DMSOFCs) have recently attracted substantial attention due to their simplified system, reduced cost, and the direct availability of methane fuel obtained from natural gas. Among oxygen-ion conductive materials, doped-ceria such as gadolinium-doped ceria (GDC) or samarium-doped ceria can be incorporated into Ni-based anodes to reinforce their coking resistance, enlarge their electrochemical reaction area, and improve the kinetics of the internal reforming/electrochemical oxidation of methane. To reduce the range of operating temperatures of DMSOFCs while maintaining their performance, the thin film deposition technique of magnetron sputtering was adopted in this work. An Ni-GDC thin-film anode and a Pt thin-film cathode were deposited on scandia-stabilized zirconia (ScSZ) electrolyte supports. This fuel cell was tested with directly supplied methane fuel (3% H₂O) at 500 °C. The results demonstrated the effects of the GDC volume fraction in the anode—which was controlled by co-sputtering power—on open circuit voltage and electrochemical performance. The co-sputtered Ni-GDC anode was able to survive through 36-h operation, although there was some performance degradation. Field-emission scanning electron microscopy results revealed no formation of filamentous carbon on the Ni catalysts, despite the fact that both X-ray photoelectron spectroscopy and Raman spectroscopy analyses detected carbon coking. The relatively high performance and resistance to carbon coking of co-sputtered thin-film anode were attributed to its intrinsic small grain size.     

Gd2Zr2O7 ceramics synthesized by solid-state reactive sintering: Effects of starting powders with different-scale particle sizes

In this work, the effects of starting oxide powders with different-scale particle sizes on the synthesis of gadolinium zirconate pyrochlore (Gd₂Zr₂O₇, GZO) and its physical properties were studied. Micron Gd₂O₃ (μG), micron ZrO₂ (μZ), nano Gd₂O₃ (nG), and nano ZrO₂ (nZ) powders were used. GZO ceramics were prepared by employing solid-state reactive sintering at 1300 °C, 1400 °C, 1500 °C and 1600 °C with mixed powders of different sizes (μGμZ, μGnZ, nGμZ and nGnZ). X-ray diffraction and Raman analyses of the ceramics revealed that nG has a more significant impact on the crystallization process than nZ. All ceramics synthesized with different sized oxide powders crystallized into pyrochlore phases except for those synthesized with μGnZ mixed powders, which resulted in a fluorite phase. The results indicated that decreasing the particle size of only ZrO₂ to synthesize pyrochlore-phase Gd₂Zr₂O₇ with high crystallinity may not be effective. Samples obtained at 1500 °C were further analyzed. Scanning electron microscopy results revealed that all four ceramics have a non-homogeneous grain size and that the average grain size ranges from 5.40 to 8.30 μm. In addition, the density and Vickers hardness measurements showed that the use of nanopowders significantly improves the mechanical properties.     

Effect of impact angle on wear behavior of Mo2NiB2–Ni cermets with different Ni content

Herein, the influence of the impact angle and Ni content on the wear behavior of Mo₂NiB₂–Ni cermets was studied using an erodent-carrying slurry comprising artificial seawater and SiO₂ sands. The results reveal that the material loss may be attributed to the wear damage caused by SiO₂ sands because cermets are expected to exhibit good corrosion resistance in artificial seawater. The relative density of cermets markedly influences their resistance to wear damage, and the material loss experienced by cermets with poor relative density is 2–4 times higher than that of cermets with good relative density; this occurs because a higher relative density can markedly enhance the mechanical properties and reduce the defects in the cermets. Moreover, the results indicate that as the impact angle increases from 0° to 60°, the manifestation of the wear mechanism changes from damaging the Ni binder phase (caused by single cutting wear) to damaging both the Mo₂NiB₂ ceramic and Ni binder phases due to the combination of cutting wear and impact wear. The wear damage is dominated by the cutting wear and impact wear from SiO₂ sand at the low and high impact angles, respectively. Furthermore, the severe deterioration of the single ceramic skeleton at high impact angles indicates that the synergistic influence of the Mo₂NiB₂ ceramic and Ni binder phases on enhancing the wear resistance of the cermets intensifies at high impact angles.     

Improvement of a commercial calcium phosphate bone cement by means of drug delivery and increased injectability

Calcium phosphate cements (CPCs) have been increasingly used as synthetic bone substitutes for repair and regeneration of bone defects given their biocompatibility, resemblance to bone and malleability. Moreover, their use as local antibiotic delivery systems is of main interest against bone infections, avoiding the adverse effects of high dosages of conventional therapy. The main goals of this work were to improve the properties of a commercial CPC (Neocement®), turning it injectable, and to provide it with a new functionality as a drug delivery system able to ensure a sustained release of an antibiotic commonly used in orthopaedics (gentamicin sulphate, GS). For this, the influence of the liquid phase amount (%LP) and type of polymer contained in the formulation (chitosan, Chi, or hydroxypropyl methylcellulose, HPMC) on the basic properties of the material was evaluated. It was found that the formulation containing 42%LP + HPMC+1.87% wt GS was the best one. It showed suitable setting and mechanical properties, and injectability around 87% (much superior to the original Neocement®, with 31%). It ensured a sustained release of GS for at least 14 days, at antibacterial levels. The antibiotic released is highly effective against S. epidermidis, but also presents some antibacterial activity against S. aureus. The CPC revealed to be non-cytotoxic. Moreover, it demonstrated good flowability and connectivity with human cadaveric trabecular bone.