纳米管钛酸的ESR特性及其可见光照的影响

本报道了纳米管钛酸在真空-0．1MPa、温度100℃的条件下，经过不同时间处理后的ESR特性及其可见光照的影响．发现纳米管钛酸经一定处理后，不经光照即出现g=2．003 ESR信号，该信号是由捕获一个电子的氧空位(Vo)产生的，此信号随着处理时间的延长而增强；在532nm的可见光照射下，随着光照时间的延长信号强度随之增加，达到一定强度值后，不再随光照时间的延长而增加；光源关闭后，信号强度又逐渐减小，但不能恢复到原来信号强度的水平．     

Quenched-in vacancies in B2-structured intermetallic compound FeAl

The concentrations of quenched-in vacancies retained in B2 intermetallic compound Fe_1-cAl_c were obtained as functions of composition (0.39 < c < 0.51) and quenching temperature (773–1273 K) from lattice constant and density measurements. Obtained vacancy concentration indicates rather gradual increase with composition in lower Al content region, while it increased rapidly as the composition approaches to stoichiometric composition. Further, the data for slow-cooled (1 K min⁻¹) samples showed that retained vacancy concentration is higher than that for samples annealed at and quenched from 773 K. Observed lattice constant for each composition decreases linearly with vacancy concentration, which is interpreted in terms of atomic size effect. From changes in vacancy concentration with quenching temperature, apparent vacancy formation energies were estimated. The relation between vacancy concentration and microhardness was also examined. Present results of dependency of lattice constant on heat treatment condition confirm the hardening effect due to retained vacancy. Further, the proposed linear relation of hardness to the square root of vacancy concentration is supported by the present study.     

电压敏电容双功能元件制备

为提高元件半导化原理并提高元件的氧气灵敏度,对以SrTiO3为基材的样品分别在强还原气体条件和大气条件下的N型电压敏、电容双功能元件和P型氧气敏感元件,分别测试了N型元件的压敏电压U1mA等电参数和P型元件在不同的温度下的阻温特性、氧敏特性,并进行了TPD测量。研究表明氧空位是在SrTiO3晶体中杂质扩散、实现半导化的重要条件,因此控制氧空位的浓度成为制备钙钛矿型半导体功能陶瓷元件的重要因素;还原气氛烧结产生的氧空位是材料实现N型半导化的重要手段;受主杂质所产生的氧空位促进了环境氧与晶格氧的交换,是材料实现P型半导化的重要手段,也提高了元件的氧气灵敏度。     

硅在铝晶界上的析出与非平衡偏聚

经高温固溶处理后匀速冷却的Al-0.35%Si合金样品,晶界上可观察到富硅的析出相,析出量随着固溶处理温度的增加而增加。对于高温固溶处理,再在较低温度二次固溶处理不同时间后匀速冷却的样品,25min的晶界析出量最大;对于25min二次处理后直接水淬样品,晶界上可观察到1μm以上的析出相。实验结果表明,硅在铝界上存在着硅-空位复合体导致的非平衡偏聚。     

一个新的金属高温蠕变空洞形核理论模型

本文在以往的蠕变变形空洞形核模型的基础文上提出了一个新的空洞形核模型。该模型不但考虑了位错塞和所产生的应力集中的作用,同时也考虑了空位聚集的作用。从本文推导出的临界空洞半径表达式即可得出Raj等人提出的临界半径关系式,又可得出Smith等人提出的空洞形核临界应力关系式,从而说明本文提出的空洞形核模型比以往的模型具有更广泛的适用范围。     

Effects of excess tellurium on the properties of CdZnTe radiation detectors

Room-temperature radiation detectors have been fabricated on high-resistivity, indium-doped Cd_0.90Zn_0.10Te crystals grown under different amounts of excess Te. The effects of the excess Te on the properties of the detectors are explained by a simple model using only three parameters: the density of Cd vacancies, the density of Te antisites (Te at Cd sites), and the deep level of doubly ionized Te antisites. The best detectors, which can resolve the low-energy Np-L and Te-K peaks as well as Cd and Te escape peaks of ²⁴¹Am, are produced from crystals grown with 1.5% excess Te. The detectors fabricated from crystals grown without excess Te are unable to resolve any characteristic-radiation peaks of ²⁴¹Am and ⁵⁷Co. This result is explained by a model of networked p-type domains in an n-type matrix or vice versa, which is caused by the lack of sufficient deep-level Te antisites. Such conduction-type inhomogeneity causes massive electron and hole trapping. As for the detectors fabricated from Cd_0.90Zn_0.10Te crystals grown with 2% and 3% excess Te, they are able to resolve the ²⁴¹Am 59.5-keV, ⁵⁷Co 122-keV, and ⁵⁷Co 136-keV radiation peaks. However, the full-width at half-maximum (FWHM) values of these peaks are broadened, especially the high-energy ⁵⁷Co peaks. These phenomena are attributed to the hole and, possibly, electron trapping by Cd vacancies and Te antisites, respectively. The result of the analysis indicates that sufficient Te antisites and a low density of carrier traps in Cd_0.90Zn_0.10Te are essential for producing high-quality radiation detectors. In the analysis, it was discovered that most of the excess Te, on the order of 1–2 × 10²⁰ cm⁻³, remain electrically inactive. A possible explanation for this phenomenon is that the excess Te atoms form neutral Te-antisite and Cd-vacancy complexes, such as Te_Cd·(V_Cd)², during the post-growth cooling process.     

Roles of oxygen defects in copper oxide superconductors

Oxygen vacancy and interstitial defects can have a profound effect on the superconducting properties of copper oxide compounds. Recent work on compounds such as La₂CuO_4+x and HgBa₂CuO_4+x has provided new insight into the role of interstitial oxygen defects as a doping mechanism. The number of carriers created by each interstitial defect depends on the local defect structure. Studies of (La, Sr, Ca)₃Cu₂O_6+x with various metal compositions and metalsite ordering show that interstitial oxygen defects that form between the CuO₂ layers in this structure systematically lowerT _c and eventually destroy superconductivity. Conversely, oxygen vacancies in the CuO₂ planes have surprisingly little effect at concentrations below 3%. The infinite-layer compounds, ACuO₂, where A=La, Sr, Ca, Nd, etc., in solid-solution combinations, could offer a similar environment for the formation of interstitial oxygen defects between the CuO₂ planes, allowing interstitial oxygen defects to contribute to the doping of these compounds. However, neutron diffraction experiments on Sr_0.9La_0.1CuO₂ (T _c = 42 K) have not found any interstitial oxygen.     

Tuning oxygen vacancy of the Ba0·95La0·05FeO3−δ perovskite toward enhanced cathode activity for protonic ceramic fuel cells

Innovation of highly active cathode is of great significance to the development of protonic ceramic fuel cells (PCFCs). Herein, tailoring oxygen vacancies in Zn-doped Ba_0·95La_0·05FeO_3?δ (BLFZ) perovskite is proved to be beneficial for promoting the formation of proton defects. Hydration ability of the triple conducting BLFZ perovskites is confirmed by electrical conductivity relaxation (ECR). The results demonstrate that BLFZ exhibits a proton surface exchange coefficient of 1.34 × 10^?3 cm s^?1 at 600 °C, which greatly extends active sites from the electrolyte/cathode interface to the entire electrode. Mechanism and process elementary steps of the oxygen reduction reaction (ORR) of BLFZ-BaCe_0.7Zr_0·1Y_0.1Yb_0.1O_3?δ (BCZYYb) are detailedly studied. It is found that the rate-determining step of ORR is surface dissociative adsorption of oxygen on BLFZ-BCZYYb cathode. A maximum power density of 673 mW cm^?2 at 700 °C is achieved and BLFZ-BCZYYb based single-cell shows no obvious degradation at 600 °C for 200 h. The good performance is ascribed to the rapid proton diffusion of BLFZ-BCZYYb composite electrode by regulating the oxygen vacancies.     

Sulfur vacancy and CdS phase transition synergistically boosting one-dimensional CdS/Cu2S/SiO2 hollow tube for photocatalytic hydrogen evolution

Constructing an efficient photoelectron transfer route to improve carrier separation efficiency is crucial for photocatalytic hydrogen evolution. In this work, CdS/Cu₂S/SiO₂ heterostructure with one-dimensional hollow tube morphology was designed by the solvothermal method using CuO/SiO₂ hollow tube as carrier. The hexagonal phase CdS and sulfur vacancies were adjusted simultaneously by the reduction strategy of NaBH₄ aqueous solution. CdS/CuS/SiO₂ with cubic phase CdS was synthesized in the absence of NaBH₄ aqueous solution. CdS/Cu₂S/SiO₂ was characterized by SEM, TEM, XRD, XPS, SPV and so on. The results showed that hexagonal CdS and sulfur vacancies benefited the separation of photo-generated carriers. As a consequence, the CdS/Cu₂S/SiO₂-10 composite exhibited a high photocatalytic hydrogen production rate (1196.98 μmol/g/h), and its performance almost 7.18 times than that of CdS/CuS/SiO₂. Moreover, CdS/Cu₂S/SiO₂-10 showed an excellent cyclic stability. This was attributed to the strong electron interaction of CdS/Cu₂S/SiO₂ heterostructure and the sulfur vacancy acted as an electron trap, enhancing the separation of photo-induced electrons and holes.     

Effects of the cation and anion co-doping in perovskite as bifunctional electrocatalyst for water splitting

Element doping is a very important way to modify perovskite oxide (ABO₃) electrocatalyst. Herein, the O, B and A-site of BaCoO_3-δ are doped with F, Fe and Sr elements, respectively, which are used to investigate the effect of different doping sites on water splitting performance. The results show that doping F can generate more oxygen vacancies and increase the Co valence state. On the basis of anionic doping, when Co is partially substitute by Fe, the Fe⁴⁺ formed makes the O 2P orbital close to E_F, and the bandwidth is narrower, enhancing the conductivity. Subsequently, doping Sr in A-site can change the crystal structure from P63/mmc to pm-3m, and exhibit metallic properties. This work can contribute to an effective approach for the design of perovskite oxide materials for efficient electrocatalytic water splitting.