Ti-V-Cr固溶体储氢合金的结构及电化学性能研究

本论文首先研究了Ni、Zr分别对Ti-V－Cr固溶体储氢合金中Cr和Ti部分取代的影响，得到了性能良好的Ti0．17Zr0．08V0．35Cr0．10Ni030基质合金。在此基础上进一步研究了入甄、B、Fe、Co、Al元素的添加或取代对基质合金的结构及电化学性能的影响。采用XRD、ICP、SEM一EDX、XPS、EIS、线性极化和阳极极化等表征手段对Ti一V－Cr固溶体储氢合金的结构及电化学性能进行分析和表征，主要结果如下：①Ti一V－Cr合金自身在碱性电解液中几乎无电化学活性。当用Ni部分取代Cr后，合金中出现具有电化学活性的第二相，其电化学性能得到有效地改善和提高。②Ti0.25-xZr_xV0.35Cr0.1Ni0.3（x＝0．05-0．15）合金主要是由bcc相和c14Laves相组成。随Zr含量从0．05增加到0．08，合金电极的放电容量和倍率放电能力增加；当x继续从0．08增加到0．15时，其变化较小。合金电极的电荷转移电阻随x增加而降低，当x在0．08到0．15之间变化时，电荷转移电阻变化也比较小。表明电荷转移电阻的大小与合金的电化学性能密切相关。③经过50次充、放电循环后，Tio．17zr"sV时scrol0Ni03。合金电极在303K和313K的放电容量能保持在90％以上；在70℃时的放电容量仍能达到275mA扮g。根据不同温度时的交换电流密度，计算了Ti。，17Zr008V时SCr川0Ni030合金电极表面电化学反应的表观活化能，其值约为50kJ／mol。④通过Nln、B、Fe、C。、AI对Tio．17zroosvo35Crol0Nio3。合金基质的添加与取代的研究，得到了具有高容量的储氢合金。其中Tio．17Zr008Vo35Cro．10Ni020Mnol。合金室温最高放电容量达到390n1A扮g；在253一343K的温度范围内，Tiol7Zr08V035Cr0JONioz5Mnoos合金具有高的放电容量，其容量在167一298mA树g之间变化，但是这些合金的稳定性有待进一步的提高。⑤合金充、放电过程中，晶格的扭曲和膨胀、Zr和V的溶解使得合金结构发生变化；合金的严重粉化及表面致密氧化膜的形成，是导致Ti一V－Cr合金电化学性能的衰减的主要原因。

LnMsbO_6和Ln_2M_2O_7 (M = Zr, Ti)复合氧化物的合成、组成、结构及发光等性质的研究

在综合文献报导的基础上，我们选择了LnMsbO_6和Ln_2M_2O_7 (M = Zr, Ti)做为研究体系，对其合成、组成、结构以及稀土离子在其中的发光性质进行了较为系统的研究。用氢氧化物共沉淀的方法，在等摩尔阳离子原料配比条件下，我们制备了LnMsbO_6和Ln_2M_2O_7(M = Zr, Ti, Ln = La - Yb, Y除Ce和Pm)。根据对组成的分析结果并与文献对比，我们认为得到的化合物组成与给出的分子式是一致的。由热分析并结合x-ray衍射分析对LnZrsbO_6的形成反应进行了研究，其结果表明化合物的形成过程是一个较慢的固相反应过程。通过x-ray粉沫衍射物相分析并结合掺杂Eu~(3+)的发光光谱，我们确定了在不同条件下合成的LnMsbO_6和Ln_2M_2O_7化合物的结构类型，并计算了所有化合物的晶胞参数。在对上述结构特性及其变化规律进行研究后，我们认为Ln_2M_2O_7结构变化规律与ΔZ/(d~2) (Z为阳离子电荷，d为阳离子与阴离距离)有关，随ΔZ/(d~2)值由小到大，Ln_2M_2O_7(M = Zr, Ti)先是形成具有荧石结构的阳离子无序固溶体，然后逐渐过渡到荧石结构的变型——有序的立方烧绿石结构，最后变型到单斜晶系结构。LnMsbO_6(M = Zr, Ti)低温相结构与Ln_2M_2O_7(M = Zr, Ti)是有联系的，即基本保持了其立方晶系结构。然后锑的加入使这种结构变得很不稳定，因此在高温灼烧下上述立方相将不可逆地变为更稳定的高温结构相。利用磁天平对LnMsbO_6和Ln_2M_2O_7进行了室温条件下的磁学性质测量，其玻尔磁子数的实验值与Van Vleck理论值符合较好。由此也可说以说明化合物的组成与给出的分子式是一致的。用荧光光谱仪对Eu~(3+)在不同基质中做发光光谱，其结果表明Eu~(3+)在烧绿石结构的Ln_2M_2O_7中，Ln~(3+)是处于具有反演中心的D_(3d)格位，这时~5D_0 → ~7F_2的电体极跃迁（～610nm）是被禁阻的，因此Eu~(3+)主要的发光为~5D_0 → ~7F_1磁体极跃迁（～590nm），并劈裂为两条谱线。在其它不具有反演中心的格位中Eu~(3+)的~5D_0 → ~7F_2跃迁则是较强的。在La~(3+)有着多个较低对称性格位的La_2Ti_2O_7:Eu中，无论是Eu~(3+)的激发光谱，还是发射光谱，其~5D_0与~7F_0之间的跃迁谱线都不只一条，这与La~(3+)多对称性格位特性是一致的。在立方荧石结构的LnZrsbO_6:Eu中，用Eu~(3+)电荷迁移带激发的发光光谱与用其它激发带激发的很不相同，其~5D_1能级的跃迁谱线非常强，我们认为这可能是由于电荷迁移激发态，将大部分能量传递给3~5D_1能级的结果。另外，我们比较了在Ln_2Zr_2O_7和LnZrsbO_6中Eu~(3+)的发光强度，发现前者要比后者强许多。在研究Bi~(3+)对Eu~(3+)的敏化作用时，我们发现在Y_2M_2O_7:Bi, Bu中Bi~(3+)对Eu~(3+)有较好的敏化作用，而在YMsbO_6:Bi, Eu中则没有。同时我们注意到对于Eu~(3+)取代六配位La~(3+)格位时，其电荷还移带位置和符合Hoefdraad认为是不变的规律，而是随着基质晶格的不同发生变化的。对Dy~(3+)在LnMsbO_6和Ln_2M_2O_7基质中发光性质研究中，我们看到Dy~(3+)的发光主要为兰色的~4F_(9/2) → ~6H_(15/2)跃迁(～480nm)和黄色的~4F_(9/2) → ~6H_(13/2)跃迁(～580nm)。其黄光与兰光的强度比值（R）随基质晶格的不同可以有很大的变化。一般情况下R值总是要大小1，且不随湿度和Dy~(3+)掺杂浓度变化。同时我们比较了在Ln_2Zr_2O_7和LnZrsbO_6 (Ln = Y, Gd, La)基质体系中Dy~(3+)的发光强度，发现同Eu~(3+)类似前者较后者强许多。在论文中我们给出了在Y_2M_2O_7和YMsbO_6 (M = Zr, Ti)中Sm~(3+)的激发光谱与发射光谱，从中可以看到当Sm~(3+)在Y_2Ti_2O_7中取代占据D_(3d)格位的Y~(3+)时，其~4G_(5/2) → ~6H_(9/2) (～650nm)电体极跃迁是被禁阻的。同时还给出了在YZrsbO_6中H_0~(3+)和Er~(3+)的激发光谱与发射光谱。此外，我们研究了Eu~(3+)和Dy~(3+)在一些基质体系中发光强度随温度的变化规律。发现Y_2Zr_2O_7:Eu的临界猝来温度要比La_2Zr_2O_7:Eu的高，Ln_2Zr_2O_7:Dy (Ln = La, Y)的温度猝来曲线则大致相同，且随温度和猝来要比Ln_2Zr_2O_7:Eu缓慢，对于上述现象我们利用位形坐标给出了一定的解释。然而所有的样品发光强度从室温开始，随温度的升高都是单调下降的。

甲烷氧化偶联Ti-La-Li系多元氧化物催化剂的研究

本论文较详细地总结了目前文献中有关甲烷氧化偶联催化剂、活性中心及活性氧种、反应机理及动力学和甲烷氧偶联反应（OCM）的影响因素等方面的重要结果；叙述了催化剂的制备和表征方法；系统地研究了Ti-La-Li系多元氧化物催化剂关于OCM反应有关主要活性相及作用机制、催化剂的表面碱性和活性氧种的作用，探讨了Li的含稀土、过渡金属多元氧化物催化剂中的作用，考察了制备方法、焙烧温度和反应条件对OCM反应的影响，同时对催化剂的高温失活机理进行了探讨。

CONTROLLING OF SCHOTTKY-BARRIER HEIGHTS FOR AU/N-GAAS AND TI/N-GAAS WITH HYDROGEN INTRODUCED AFTER METAL-DEPOSITION BY BIAS ANNEALING

Up to now, in most of the research work done on the effect of hydrogen on a Schottky barrier, the hydrogen was introduced into the semiconductor before metal deposition. This letter reports that hydrogen can be effectively introduced into the Schottky barriers (SBs) of Au/n-GaAs and Ti/n-GaAs by plasma hydrogen treatment (PHT) after metal deposition on [100] oriented n-GaAs substrates. The Schottky barrier height (SBH) of a SB containing hydrogen shows the zero/reverse bias annealing (ZBA/RBA) effect. ZBA makes the SBH decrease and RBA makes it increase. The variations in the SBHs are reversible. In order to obtain obvious ZBA/RBA effects, selection of the temperature for plasma hydrogen treatment is important, and it is indicated that 100-degrees-C for Au/n-GaAs and 150-degrees-C for Ti/n-GaAs are suitable temperatures. It is concluded from the analysis of experimental results that only the hydrogen located at or near the metal-semiconductor interface, rather than the hydrogen in the bulk of either the semiconductor or the metal, is responsible for the ZBA/RBA effect on SBH.

STUDY OF TI/LNP INTERFACE BY PES

The interface of Ti/InP(110) was studied by X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS). It is evident that deposition of Ti on the surface of InP(110) at room temperature introduced a break of the In-P bond and a diffusion of In atoms into the Ti film. The interaction of Ti and P occurred at a temperature of 350-degrees-C.

A STUDY OF THE COMPOSITION DISTRIBUTION AT THE TI/AL2O3 INTERFACE USING THE MCS(+)-SIMS TECHNIQUE

In this article, the MCs(+)-SIMS technique has been used to characterize Ti/Al2O3 metal/insulator interfaces. Our experiment shows that by detecting MCs(+) secondary ions, the matrix and interface effects are reduced, and good depth profiles have been obtained. The experimental result also shows that with the increase of the annealing temperature (RT, 300 degrees C, 600 degrees C, 850 degrees C), the interface gets broadened gradually, indicating diffusion and reaction take place at the interface, and the interface reaction is enhanced with the increase in annealing temperature. When the temperature increases, the AlCs+ signal forms two plateaus in the Ti layer, indicating Al from the decomposition of Al2O3 diffuses into the Ti layer and exists as two new forms (phases). Also, with the increase of the annealing temperature, oxygen diffuses into the Ti layer gradually, and makes the O signal in the Ti layer increase significantly in the 850 degrees C annealed sample.

Homoepitaxial Growth of 4H-SiC and Ti/4H-SiC SBDs

Homoepitaxial growth of4H-SiC on off-oriented Si-face （0001） 4H-SiC substrates was performed at 1500℃ by using the step controlled Epitaxy. Ti/4H-SiC Schottky barrier diodes （SBDs） with blocking voltage over lkV have been made on an undoped epilayer with 32μm in thick and 2-5 × 10^15 cm^-3 in carrier density. The diode rectification ratio of forward to reverse （defined at ± 1V） is over 107 at room temperature and over 10^2 at 538K. Their electrical characteristics were studied by the current-voltage measurements in the temperature range from 20 to 265 ℃. The ideality factor and Schottky barrier height obtained at room temperature are 1.33 and 0. 905eV, respectively. The SBDs have on-state current density of 150A/cm^2 at a forward voltage drop of about 2.0V. The specific on-resistance for the rectifier is found to be as 7.9mΩ · cm^2 and its variation with temperature is T^2.0.

800nm Semiconductor Absorber with Low Temperature Method and Surface State Method Combined Absorber for Kerr Lens Modelocking of Ti∶Al2O3 Laser

A novel 800nm Bragg mirror type of semiconductor saturable absorption mirror with low temperature method and surface state method combined absorber is presented.With which passive Kerr lens mode locking of Ti∶Al2O3 laser pumped by argon ion laser is realized,which produces pulses as short as 40fs.The spectrum bandwidth is 56nm,which means that it can support the modelocking of 20fs.The pulse frequency is 97.5MHz;average output power is 300mW at the pump power of 4.45W.

高压 Ti/ 6H- SiC肖特基势垒二极管（英文）

在N型6H-SiC外延片上，通过热蒸发，制作Ti/6H-SiC肖特基势垒二极管(SBD)。通过化学气相淀积，进行同质外延生长，详细测量并分析了肖特基二极管的电学特性，该肖特基二极管具有较好的整流特性。反向击穿电压约为400V，室温下，反向电压V_R=200V时，反向漏电流J_R低于1×10~(-4)A/cm~2。采用Ne离子注入形成非晶层，作为边缘终端，二极管的击穿电压增加到约为800V。

Ti-AlN快速退火的界面

国家自然科学基金

Ti/莫来石陶瓷界面反应的俄歇电子能谱研究

结果表明，在淀积过程中，最初淀积的Ti与衬底表面的氧形成Ti-O键，界面区很窄；450℃退火1h后，有少量元素态Al、Si原子析出，界面区有所展宽，但变化不大；650℃退火1h后，界面发生强烈反应，有TiO和Ti-Al、Ti-Si化合物生成。850℃退火1h后，除上述反应产物外又生成了Ti_2O。