脉冲激光沉积LiMn2O4薄膜的研究

在氧气氛下采用355nm脉冲激光烧蚀制备了LiMn₂O₄薄膜,并用四极质谱和发光光谱技术考察了脉冲激光烧蚀过程及环境氧气对薄膜沉积过程的影响.质谱测定结果表明,355nm激光烧蚀LiMn₂O₄的产物主要有Li⁺、Mn⁺等离子和O₂、O、LiO₂、LiMnO、MnO及锂原子的多聚体等中性产物.不同氧气压下测定的发光光谱表明烧蚀原子在环境氧气氛中存在氧化过程.用循环伏安法和X射线衍射法对薄膜进行了表征.     

脉冲激光沉积纳米TiO2薄膜电极的现场光电化学

在O3 /O2 气氛中采用 35 5nm激光烧蚀金属钛靶的反应性沉积薄膜方法 ,成功地在镀ITO膜的玻璃基片上制备了纳米锐钛矿相TiO2 薄膜电极 .用循环伏安法研究了在Li/TiO2 电池中TiO2 薄膜电极的电化学嵌入Li离子的行为 .由现场快速紫外可见吸收光谱实时监测TiO2 薄膜电极的显色特性 ,在波长 42 0和 6 5 0nm附近出现 2个明显的吸收峰 ,并发现TiO2 薄膜电极的吸收谱的涨落过程与Li离子的嵌入和脱嵌过程具有相关性与可逆性 ,表明该纳米TiO2 薄膜电极具有高质量的光电化学性能 .     

Ga2O3薄膜的光致发光及激光烧蚀产物的分布

采用脉冲激光沉积技术在氧气氛中制备了Ga2O3薄膜。X射线衍射表明薄膜属于β单斜晶系,薄膜的颗粒在纳米量级;原子力显微镜显示随着氧气压强的增加,薄膜颗粒增大。测定了薄膜的光致发光,发现沉积时氧气压强的增加可以提高 纯Ga2O3薄膜的发光强度,且峰位红移。Ga2O3靶物质中掺杂少量的CeO2后所得到的薄膜,其发光强度可以明显地增加。此外,还利用发光光谱技术研究了由激光 烧蚀所产生的羽状物中Ga原子或离子的氧化反应。     

激光烧蚀La~2O~3产生的等离子体的发光光谱研究

用发光光谱法研究了355nm脉冲激光在真空和O~2气氛中烧蚀La~2O~3产生的等离子体的组成和形成过程。对等离子体中La^+离子和LaO的空间和时间分辨发光光谱分析表明,在O~2气氛中LaO有两个生成通道:一是在靶附近的等离子体内直接生成的,另一是由La,La^+与O^2发生氧化反应而生成的。测定了激光能量密度,离靶表面的距离和O~2压力对产物发光的延迟时间和发光强度的影响。此外,还讨论了激光烧蚀La~2O~3诱导产生等离子体的形成和演化机理。     

角分辨飞行时间法研究紫外激光烧蚀Ta2O5的反应

利用角分辨飞行时间法研究了３５５ｎｍ脉冲激光烧蚀Ｔａ２Ｏ５的反应，由四极质谱测得的煤蚀产物除了Ｏ，Ｔａ，ＴａＯ和ＴａＯ２中性碎片外，在较高激光能量密度时还有Ｏ，Ｔａ，ＴａＯ，ＴａＯ２离子碎片，它们的飞行时间（ＴＯＦ）谱可以用于级分带质心速度的Ｍａｘｗｅｌｌ－Ｂｏｌｚｔｍａｎｎ分布函数较好地拟合，原生离子碎片的平均动能与激光能量密度无关，烧蚀产物原生离子和中性粒子的角分布可以分别用ａｃｏｓ＾ｎθ（ｎ     

脉冲激光沉积纳米NiO薄膜

Na Cl型 Ni O是一种 p型半导体 ,广泛用于传感器、催化剂、涂料、磁性材料及电极材料等领域[1～ 5] .最近 ,Poizot等 [6] 又报道了 Ni O可作为锂离子电池的阳极材料 ,使 Ni O成为又一新的研究热点 .纳米 Ni O粉末的制备方法有多种 ,主要包括化学沉淀法和沉淀转换法 ,Ni O薄膜的制备主要采用磁控溅射、化学气相沉积和电沉积等方法 [7～ 12 ] .脉冲激光沉积法具有操作简单和成膜纯净等优点 ,因此是制备薄膜的重要方法之一 .本文采用脉冲激光沉积 (PLD)法在氧气氛中使用金属镍作为靶材料 ,不锈钢作为基片 ,对 Ni O薄膜的制备进行了研究…     

Ta2O5/Si薄膜界面结构及光催化活性

利用溶胶-凝胶法和旋转镀膜法在单晶Si(110)基底上制备了Ta2O5光催化剂薄膜. 薄膜颗粒的晶粒度和大小随着热处理温度的升高而增加. 利用扫描俄歇电子能谱(AES)的表面成分分析、深度剖析和线形分析技术研究了热处理温度对Ta2O5/Si 样品膜层和基底的界面化学状态和相互作用的影响规律. 研究表明, 在700 ℃以下热处理时, Ta2O5/Si薄膜界面处以扩散作用为主;在800 ℃高温热处理时,在界面扩散的同时也引发界面反应, 生成了SiO2物种, 界面扩散和界面反应会对薄膜和基底元素的化学价态发生影响. 在紫外光下降解水杨酸的光催化活性的研究表明, 在600 ℃下焙烧制备的Ta2O5/Si薄膜具有与TiO2/Si薄膜相当的光催化活性.     

355 nm激光烧蚀LiMn2O4反应产物的飞行时间质谱

采用角分辨飞行时间质谱法研究了355 nm脉冲激光烧蚀LiMn2O4的反应. 在较低激光能量密度(0.8 J·cm^-2)测得的离子和中性烧蚀产物主要有Li, O, LiO, LiO₂ , Mn, Li₂, Li₄, Li₆, LiMn, MnO, MnO₂等. 激光能量密度较大时, 烧蚀产物中的氧化物不仅相对量增加, 而且物种更加丰富. 它们的飞行时间谱可用带质心速度的Maxwell-Boltzmann分布函数拟合. 烧蚀产物Li, LiO, LiO₂ 和 Mn存在能量密度表观阈值, 并且离子产物的阈值比相应的中性产物高. 烧蚀产物中原生离子和中性产物的空间角分布可用cosⁿ θ 或θ cosθ+(1-δ)cosⁿθ拟合. 此外, 对355 nm脉冲激光对LiMn₂O₄的烧蚀机理进行了讨论.     

Ta2O5在Si(100)表面原子层沉积反应机理的密度泛函研究

采用密度泛函方法研究了以TaCl5和H2O作为前驱体在硅表面原子层沉积(ALD) Ta2O5的初始反应机理. Ta2O5的原子层沉积过程包括两个连续的“半反应”, 即TaCl5和H2O“半反应”. 两个“半反应”都经历了一个相似的吸附中间体反应路径. 通过H钝化和羟基预处理硅表面反应能量的比较发现, TaCl5在羟基预处理硅的表面反应是热力学和动力学都更加有利的反应. 另外, 从能量上看, H2O的“半反应”不容易向生成产物的方向进行.     

H2O2-Na2S2O3反应对pH和反应物起始浓度比的依赖性

在H2O2-Na2S2O3反应体系中，pH值和[H2O2]0/[Na2S2O3]0对反应产物的浓度大小起着关键作用.本文通过考察这两种因素对反应产物的影响，以及对反应机理的模拟，得出了pH值和氧化剂与还原剂浓度比影响反应产物浓度的一般规律.结果表明：pH< 3时，反应主要生成单质硫， 3< pH< 6时， 较为稳定，提高pH和[H2O2]0/[Na2S2O3]0有利于SO42-生成，在中性或弱碱性溶液中S(Ⅳ)(HSO42-或SO32-)物质浓度出现峰值.     

Gas-phase oxidation reactions of Ta2+: synthesis and properties of TaO(2+) and TaO2(2+)

Gas-phase reactions of Ta(2+) and TaO(2+) with oxidants, including thermodynamically facile O-atom donor N(2)O and ineffective donor CO, as well as intermediate donors C(2)H(4)O (ethylene oxide), H(2)O, O(2), CO(2), NO, and CH(2)O, were studied by Fourier transform ion cyclotron resonance mass spectrometry. All oxidants reacted with Ta(2+) by electron transfer yielding Ta(+), in accord with the high second ionization energy of Ta (ca. 16 eV). TaO(2+) was also produced with N(2)O, H(2)O, O(2), and CO(2), oxidants with ionization energies above 12 eV; CO reacted only by electron transfer. The following charge separation products were also observed: TaN(+) and TaO(+) with N(2)O; and TaO(+) with O(2), CO(2), and CH(2)O. TaOH(2+), formed with H(2)O, reacted with a second H(2)O by proton transfer. TaO(2+) abstracted an electron from N(2)O, H(2)O, O(2), CO(2), and CO. Oxidation of TaO(2+) by N(2)O was also observed to produce TaO(2)(2+); on the basis of density functional theory (DFT) results, this species is a dioxide, {O-Ta-O}(2+). TaO(2)(2+) reacted by electron transfer with N(2)O, CO(2), and CO to give TaO(2)(+). Additionally, it was found that TaO(2)(2+) oxidizes CO to CO(2) and that it acts as a catalyst in the oxidation of CO by N(2)O. TaO(2)(2+) also activates H(2) to form TaO(2)H(2+). On the basis of the rates of electron transfer from N(2)O, CO(2), and CO to Ta(2+), TaO(2+), and TaO(2)(2+), the following estimates were made for the second ionization energies of Ta, TaO, and TaO(2): IE[Ta(+)] = 15.8 ± 0.3 eV, IE[TaO(+)] = 16.0 ± 0.5 eV, and IE[TaO(2)(+)] = 16.9 ± 0.4 eV. These IEs, together with recently reported bond dissociation energies, D[Ta(+)-O] and D[OTa(+)-O], result in the following bond energies: D[Ta(2+)-O] = 657 ± 58 kJ mol(-1) and D[OTa(2+)-O] = 500 ± 63 kJ mol(-1), the first of which is in good agreement with the value obtained by DFT.     

Phase relationships in the BaO-Ga2O3-Ta2O5 system and the structure of Ba6Ga21TaO40

Phase relationships in the BaO-Ga(2)O(3)-Ta(2)O(5) ternary system at 1200 °C were determined. The A(6)B(10)O(30) tetragonal tungsten bronze (TTB) related solution in the BaO-Ta(2)O(5) subsystem dissolved up to ~11 mol % Ga(2)O(3), forming a ternary trapezoid-shaped TTB-related solid solution region defined by the BaTa(2)O(6), Ba(1.1)Ta(5)O(13.6), Ba(1.58)Ga(0.92)Ta(4.08)O(13.16), and Ba(6)GaTa(9)O(30) compositions in the BaO-Ga(2)O(3)-Ta(2)O(5) system. Two ternary phases Ba(6)Ga(21)TaO(40) and eight-layer twinned hexagonal perovskite solid solution Ba(8)Ga(4-x)Ta(4+0.6x)O(24) were confirmed in the BaO-Ga(2)O(3)-Ta(2)O(5) system. Ba(6)Ga(21)TaO(40) crystallized in a monoclinic cell of a = 15.9130(2) ?, b = 11.7309(1) ?, c = 5.13593(6) ?, β = 107.7893(9)°, and Z = 1 in space group C2/m. The structure of Ba(6)Ga(21)TaO(40) was solved by the charge flipping method, and it represents a three-dimensional (3D) mixed GaO(4) tetrahedral and GaO(6)/TaO(6) octahedral framework, forming mixed 1D 5/6-fold tunnels that accommodate the Ba cations along the c axis. The electrical property of Ba(6)Ga(21)TaO(40) was characterized by using ac impedance spectroscopy.     

First-principles density functional calculation of electrochemical stability of fast Li ion conducting garnet-type oxides

The research and development of rechargeable all-ceramic lithium batteries are vital to realize their considerable advantages over existing commercial lithium ion batteries in terms of size, energy density, and safety. A key part of such effort is the development of solid-state electrolyte materials with high Li(+) conductivity and good electrochemical stability; lithium-containing oxides with a garnet-type structure are known to satisfy the requirements to achieve both features. Using first-principles density functional theory (DFT), we investigated the electrochemical stability of garnet-type Li(x)La(3)M(2)O(12) (M = Ti, Zr, Nb, Ta, Sb, Bi; x = 5 or 7) materials against Li metal. We found that the electrochemical stability of such materials depends on their composition and structure. The electrochemical stability against Li metal was improved when a cation M was chosen with a low effective nuclear charge, that is, with a high screening constant for an unoccupied orbital. In fact, both our computational and experimental results show that Li(7)La(3)Zr(2)O(12) and Li(5)La(3)Ta(2)O(12) are inert to Li metal. In addition, the linkage of MO(6) octahedra in the crystal structure affects the electrochemical stability. For example, perovskite-type La(1/3)TaO(3) was found, both experimentally and computationally, to react with Li metal owing to the corner-sharing MO(6) octahedral network of La(1/3)TaO(3), even though it has the same constituent elements as garnet-type Li(5)La(3)Ta(2)O(12) (which is inert to Li metal and features isolated TaO(6) octahedra).     

Nitric oxide as an electron donor, an atom donor, an atom acceptor, and a ligand in reactions with atomic transition-metal and main-group cations in the gas phase

The room-temperature reactions of nitric oxide with 46 atomic cations have been surveyed systematically across and down the periodic table using an inductively-coupled plasma/selected-ion flow tube (ICP/SIFT) tandem mass spectrometer. Rate coefficients and product distributions were measured for the reactions of first-row cations from K+ to Se+, of second-row cations from Rb+ to Te+ (excluding Tc+), and of third-row cations from Cs+ to Bi+. Reactions both first and second order in NO were identified. The observed bimolecular reactions were thermodynamically controlled. Efficient exothermic electron transfer was observed with Zn+, As+, Se+, Au+, and Hg+. Bimolecular O-atom transfer was observed with Sc+, Ti+, Y+, Zr+, Nb+, La+, Hf+, Ta+, and W+. Of the remaining 32 atomic ions, all but 8 react in novel termolecular reactions second order in NO to produce NO+ and the metal-nitrosyl molecule, the metal-monoxide cation and nitrous oxide, and/or the metal-nitrosyl cation. K+, Rb+, Cs+, Ga+, In+, Tl+, Pb+, and Bi+ are totally unreactive. Further reactions with NO produce the dioxide cations CaO2+, TiO2+, VO2+, CrO2+, SrO2+, ZrO2+, NbO2+, RuO2+, BaO2+, HfO2+, TaO2+, WO2+, ReO2+, and OsO2+ and the still higher order oxides WO3+, ReO3+, and ReO4+. NO ligation was observed in the formation of CaO+(NO), ScO+(NO), TiO+(NO), VO+(NO)(1-3), VO2+(NO)(1-3), SrO+(NO), SrO2+(NO)1,2, RuO+(NO)(1-3), RuO2+(NO)1,2, OsO+(NO)(1-3), and IrO+(NO). The reported reactivities for bare atomic ions provide a benchmark for reactivities of ligated atomic ions and point to possible second-order NO chemistry in biometallic and metal-surface environments leading to the conversion of NO to N2O and the production of metal-nitrosyl molecules.     

Reactions of group V metal atoms with water molecules. Matrix isolation FTIR and quantum chemical studies

Laser-ablated group V metal atoms (V, Nb, Ta) were co-deposited with water molecules in excess argon. The V atoms reacted with water to form the inserted HVOH molecule spontaneously. The Nb atoms reacted with water to form the NbOH2 complex and the inserted HNbOH molecule. Broad-band photolysis produced the H2VO and H2NbO molecules as well as the VO and NbO monoxides. For Ta + H2O reactions, neither TaOH2 nor HTaOH was observed, while the H2TaO molecule was produced on annealing, and the H2 elimination process was not observed on photolysis. The aforementioned species were identified via isotopic substitutions as well as density functional calculations. Qualitative analysis of the possible reaction paths leading to the observed products is proposed. The results have been compared with our earlier works concerning the Sc and group IV metal atoms with water reactions in order to observe existent trends for the early transition metal atoms.     

Photocatalytic activity of R3MO7 and R2Ti2O7 (R=Y, Gd, La; M=Nb, Ta) for water splitting into H2 and O2

The photocatalytic activities of R3MO7 and R2Ti2O7 (R=Y, Gd, La; M=Nb, Ta) strongly depended on the crystal structure. Overall, photocatalytic water splitting into H2 and O2 proceeded over La3TaO7 and La3NbO7, which have an orthorhombic weberite structure, Y2Ti2O7 and Gd2Ti2O7, which have a cubic pyrochlore structure, and La2Ti2O7, which has a monoclinic perovskite structure. All of these materials are composed of a network of corner-shared octahedral units of metal cations (TaO6, NbO6, or TiO6); materials without such a network were inactive. The octahedral network certainly increased the mobility of electrons and holes, thereby enhancing photocatalytic activity.     

自组装超薄膜修饰Ta2O5介质膜及其特性研究

采用静电自组装方法在五氧化二钽(Ta2O5)介质氧化膜上制备了聚二烯丙基二甲基氯化铵(PDDA)/聚苯乙烯磺酸钠(PSS)和聚二烯丙基二甲基氯化铵/聚-3,4-乙烯二氧噻吩-聚苯乙烯磺酸钠(PEDOT-PSS)超薄膜.研究了两种自组装超薄膜在Ta2O5介质氧化薄膜上的组装特性.结果表明两种自组装膜能够稳定地组装于Ta2O5介质膜表面,并有效降低薄膜的表面粗糙度.进一步研究了两种自组装超薄膜修饰的Ta2O5电容结构的电性能.结果表明静电自组装膜对Ta2O5介质膜表面进行修饰后,有效地隔离了介质氧化膜中的缺陷,降低了电容的漏电流并提高耐电压能力;研究还发现不同厚度的超薄膜对Ta2O5电容结构的耐压特性有不同程度的影响,较厚的薄膜可以更好地提高电容的耐压能力并降低漏电流,但会增加电容的等效串联电阻(ESR).另外,在相同薄膜层数的情况下,聚合物电解质PEDOT-PSS良好的导电性能降低了复合超薄膜的电阻,使得PDDA/PEDOT-PSS修饰的电容结构ESR值较低.     

In situ infrared spectroscopic analysis of the adsorption of aromatic carboxylic acids to TiO2, ZrO2, Al2O3, and Ta2O5 from aqueous solutions

In situ infrared spectroscopy has been used to investigate the adsorption of a range of simple aromatic carboxylic acids from aqueous solution to metal oxides. Thin films of TiO2, ZrO2, Al2O3 and Ta2O5 were prepared by evaporation of aqueous sols on single reflection ZnSe prisms. Benzoic acid adsorbed very strongly to ZrO2, in a bridging bidentate fashion, but showed only weak adsorption to TiO2 and Ta2O5. Substituted aromatic carboxylic acids; salicylic, phthalic and thiosalicylic, were found to adsorb to each metal oxide. Salicylic and phthalic acids adsorbed to the metal oxides via bidentate interactions, involving coordination through both carboxylate and substituent groups. Thiosalicylic acid adsorbed to the metal oxides as a bridging bidentate carboxylate with no coordination through the thiol substituent group.