纳米金属多层膜与多层纳米线的电化学制备及其表征

分别采用单槽法和双槽法电沉积Cu/Co多层膜.研究了两种电沉积方法制备多层膜的工艺条件,利用电化学方法、XRD和SEM对多层膜进行表征,并对Cu/Co多层膜的巨磁阻性能进行了测试. 采用电沉积多层膜的方法，以多孔铝阳极氧化膜（AAO）为模板,在纳米孔内沉积Cu/Co多层线,采用TEM对多层纳米线进行了表征.     

电沉积Co-Cu颗粒膜的巨磁电阻效应

从１９８８年Ｂａｉｂｉｃｈ首先在磁性Ｆｅ／Ｃｒ多层膜中发现巨磁电阻效应（ＧＭＲ）以来 ［１］,由于ＧＭＲ本身的科研价值和在磁记录、磁性传感器等方面的广泛应用前景 ,引起了人们的极大关注．继多层膜之后 ,人们在金属颗粒膜如Ｃｏ Ａｇ［２］,Ｃｏ Ｃｕ［３,４］等中也相继发现了巨磁电阻效应．颗粒膜是微颗粒镶嵌于薄膜中所构成的复合材料体系．原则上 ,颗粒的组成与薄膜的组成在制备条件上应互不固溶 ,因此颗粒膜区别于合金、化合物 ,属于非均匀相组成的材料．磁性颗粒膜是磁性粒子分布在非磁性金属材料薄膜中．在磁性颗粒与非…     

电结晶铜/钴纳米多层膜结构与磁性能研究

以n型Si(111)为基底, 在硼酸镀液体系中采用双槽法电结晶制备Cu/Co纳米多层膜, 确定了工艺条件. 用扫描电镜(SEM)和X射线衍射(XRD)对纳米多层膜的结构和形貌进行了表征, 显示多层膜具有良好周期性和超晶格结构. 并用物性测量系统PPMS测试了不同结构 Cu/Co纳米多层膜的磁性能. 磁滞回线表明: 不同周期数的纳米多层膜其矫顽力均较小. 巨磁阻(GMR)性能与纳米多层膜结构有关. GMR值随Co磁性层厚度增长先增大后减小, 有一极值; 随着Cu非磁性层厚度的增加GMR值发生周期性的振荡; 随周期数N的增大, GMR值先增大, 在N为60时达到了90%, 随着N的继续增加而减小, 当达到80周期时, GMR值趋于稳定.     

表面印迹制备牛血红蛋白分子印迹聚苯乙烯磁性纳米球

本工作将磁性纳米材料与分子印迹技术结合,以牛血红蛋白为模板分子,3-氨基苯硼酸为功能单体和交联剂,Fe3O4磁性纳米粒子为核,采用表面分子印迹技术,制备具有多层核。壳结构的蛋白质分子印迹聚苯乙烯磁性纳米球．用扫描透射电镜、X射线衍射仪、热重分析仪、磁强振动计研究了制备的蛋白质分子印迹磁性纳米球的表面形貌、粒径大小、多层结构和磁性能．吸附结合实验表明,表面为聚3-氨基苯硼酸分子印迹膜的磁性纳米球对模板蛋白牛血红蛋白具有动力学吸附速度快,特异性吸附选择性高的优点,同时具有在外加磁场下快速分离的特性,可应用于蛋白质分子的选择性分离和富集目标蛋白．     

小周期金属多层膜厚度评价

超晶格多层膜是随着现代科技的进步而发展起来的新一代电子薄膜材料,半导体超晶格和量子阱多层膜材料在光电子领域已经占据了不可取代的地位。1988年,法国科学家在由Fe、Cr交替沉积而形成的[Fe/Cr]金属多层膜中发现了超过50%的磁电阻变化率,这种现象被称为巨磁阻效应(GMR)[1]。     

Fe/RE多层膜磁性及其变化机制

研究了Ｆｅ／ＲＥ多层膜（Ｆｅ单层厚度〈２．０ｎｍ）沉积态退火过程中（温度≥４７３Ｋ）的结构与磁性，分析了磁性变化的原因。沉积态的Ｆｅ单层由分离的Ｆｅ岛组成，小尺寸的Ｆｅ岛呈超顺磁性导致了整个膜显示顺磁性，退火时Ｆｅ岛合并长大，膜由超顺磁转变为铁磁，同时磁化强度和妖顽力增加。     

半导体Si上电沉积Cu-Co颗粒膜及其巨磁电阻效应

采用电化学沉积方法在半导体Si上制备Cu-Co金属颗粒膜. XRD测试结果表明制备态的薄膜形成了单相亚稳态面心合金结构, 薄膜经退火后, XRD谱图中出现了析出的纯金属Co的衍射峰, 这表明薄膜在退火过程中发生了相分离. TEM测试结果也进一步证实了磁性的Co颗粒从非磁性的铜基体中析出. 随着退火温度的增加, 颗粒膜巨磁电阻(GMR)效应不断增大, 当退火温度为450 ℃时, Co0.20Cu0.80薄膜的巨磁电阻效应达到最大, 磁阻率为8.21％. 之后, 磁阻率又随退火温度的升高而降低. 退火前后样品磁滞回线的变化表明薄膜中发生了从超顺磁性到铁磁性的转变, 矫顽力、剩余磁化强度和饱和磁化强度均随退火温度的增高而逐渐增大. 超顺磁性颗粒的作用导致了GMR－H与M－H曲线的不同.     

分子沉积膜的纳米摩擦特性

利用原子力显微镜研究了金衬底、沉积单层和多层分子沉积膜的金表面以及非活性端基修饰的沉积单层和多层分子沉积膜金的表面的纳米摩擦特性．结果表明,金表面沉积分子沉积膜以及对分子沉积膜的非活性端基修饰对金衬底均有一定的减摩作用;当针尖与试样表面趋于原子级摩擦时,摩擦的作用主要取决于试样表面分子的端基结构,而与分子的链长、骨架及分子沉积膜的层数等无关;分子沉积膜的活性端基使其纳米摩擦特性不稳定,而非活性端基修饰可以使其纳米摩擦特性稳定,并且可以降低摩擦力;空气的相对湿度对摩擦力有显著的影响,相对湿度越大,摩擦力越小．     

TiO2/十六烷基三甲基溴化铵有序交替层状纳米复合薄膜的制备与结构表征

近年来有序交替的层状纳米结构薄膜的制备吸引了研究者们的极大关注. 目前, 这类薄膜的制备方法研究得最多的是LB技术[1～3]、基于化学吸附的自组装成膜技术[4,5]和交替沉积组装技术[6～8]. 但这几种方法都有明显的缺陷[9,10], 其中,通过LB技术制备有序交替层状纳米复合薄膜需要昂贵的仪器, 而且由于层间是分子相互作用, 膜的稳定性较差; 基于化学吸附的自组装成膜技术由于需要高反应活性的分子和特殊的基底表面, 并且由于化学反应的产率很难达到100%, 因此通过这种方法制备结构有序的多层膜并不容易; 利用交替沉积的方法制备出具有实用厚度的纳米多层膜需要耗费大量的时间. 最近, 出现了一种称为蒸发诱导的超分子自组装方法, 由这种方法制备的纳米多层膜具有成膜速度快和膜有序度高等优点, 此外还可以通过改变成膜物质浓度和拉膜速度来控制薄膜的厚度, 但与LB膜相比其厚度无法在分子水平上控制. 利用这种方法制备多层膜目前的文献报道仅限于线形SiO2与有机物的组装[10～13]. 本文利用这种方法制备了TiO2/十六烷基三甲基溴化铵纳米复合薄膜并对其结构进行了表征, 结果表明所制备的薄膜具有TiO2/十六烷基三甲基溴化铵有序交替的层状结构.     

重氮树脂基磁性超薄膜及其图形化

构建磁性薄膜,在磁性理论和应用技术上都有重要意义．通过磁性膜的研究,能揭示磁性机制,对界面磁性、维度磁性、磁性的藕合特征、磁性量子效应等建立新的认识．磁性膜还提供一种新的人造磁性材料,在信息储存、磁性图像、医学等方面有潜在应用．目前,形成磁性薄膜的技术主要有溅射(Sputtering)、分子外延性生长(Molecular beam epitaxy)、真空喷镀、电泳、脉冲激光沉积、Langmuir-Blodgett(LB)沉积、层层组装(LBL)等方法．     

Tuning the electrocrystallization parameters of semiconducting Co[TCNQ]2-based materials to yield either single nanowires or crystalline thin films

Electrocrystallization of single nanowires and/or crystalline thin films of the semiconducting and magnetic Co[TCNQ]2(H2O)2 (TCNQ=tetracyanoquinodimethane) charge-transfer complex onto glassy carbon, indium tin oxide, or metallic electrodes occurs when TCNQ is reduced in acetonitrile (0.1 M [NBu4][ClO4]) in the presence of hydrated cobalt(II) salts. The morphology of the deposited solid is potential dependent. Other factors influencing the electrocrystallization process include deposition time, concentration, and identity of the Co2+(MeCN) counteranion. Mechanistic details have been elucidated by use of cyclic voltammetry, chronoamperometry, electrochemical quartz crystal microbalance, and galvanostatic methods together with spectroscopic and microscopic techniques. The results provide direct evidence that electrocrystallization takes place through two distinctly different, potential-dependent mechanisms, with progressive nucleation and 3-D growth being controlled by the generation of [TCNQ]*- at the electrode and the diffusion of Co2+(MeCN) from the bulk solution. Images obtained by scanning electron microscopy reveal that electrocrystallization of Co[TCNQ]2(H2O)2 at potentials in the range of 0.1-0 V vs Ag/AgCl, corresponding to the [TCNQ]0/*- diffusion-controlled regime, gives rise to arrays of well-separated, needle-shaped nanowires via the overall reaction 2[TCNQ]*-(MeCN)+Co2+(MeCN)+2H2O right harpoon over left harpoon {Co[TCNQ]2(H2O)2}(s). In this potential region, nucleation and growth occur at randomly separated defect sites on the electrode surface. In contrast, at more negative potentials, a compact film of densely packed, uniformly oriented, hexagonal-shaped nanorods is formed. This is achieved at a substantially increased number of nucleation sites created by direct reduction of a thin film of what is proposed to be cobalt-stabilized {(Co2+)([TCNQ2]*-)2} dimeric anion. Despite the potential-dependent morphology of the electrocrystallized Co[TCNQ]2(H2O)2 and the markedly different nucleation-growth mechanisms, IR, Raman, elemental, and thermogravimetric analyses, together with X-ray diffraction, all confirmed the formation of a highly pure and crystalline phase of Co[TCNQ]2(H2O)2 on the electrode surface. Thus, differences in the electrodeposited material are confined to morphology and not to phase or composition differences. This study highlights the importance of the electrocrystallization approach in constructing and precisely controlling the morphology and stoichiometry of Co[TCNQ]2-based materials.     

Factors affecting the selectivity of the oxidation of methyl p-toluate by cobalt(III)

The anaerobic oxidation of methyl p-toluate by cobalt(III) in acetic acid was investigated. Observed products were 4-carbomethoxybenzaldehyde (2), 4-carbomethoxybenzoic acid (3), 4-carbomethoxybenzyl acetate (1), 4,4'-dicarbomethoxybibenzyl (6), methyl 2,4-dimethylbenzoate (8), and methyl 3,4-dimethylbenzoate (9). Deuterium isotope labeling showed that 2 was not formed from 1, but appeared to be formed directly from methyl p-toluate via 4-carbomethoxybenzyl alcohol (5). The ratio of (2 + 3) to 1 was 0.5 with [py3Co3O(OAc)5OH[PF6] and 1.0 with cobaltic acetate. Cobaltic acetate was generated in situ by the reaction of cobaltous acetate and peracetic acid. When the oxidation was carried out in the presence of chromium (0.05 equiv based on cobalt), the ratio increased dramatically and no 6 was observed. Other transition metals such as vanadium, molybdenum, and manganese had a similar effect, but were not as effective as chromium. Chromium was observed to form a mixed-metal cluster complex with cobalt. Treatment of an acetic acid solution of cobaltous acetate and methyl isonicotinate with K2CrO4 produced a solid tentatively identified as [(MIN)3Co2CrO(OAc)6][CrO4H] (MIN = methyl isonicotinate). The selectivity for the oxidation of methyl p-toluate exhibited by the mixed-metal cluster complex was similar to that observed by the addition of chromium to oxidations using [py3Co3O(OAc)5OH[PF6].     

Tetranuclear clusters containing a CrIII-doped MnIII4O2 core: syntheses, structures, and magnetic properties

The oxidation of MnII carboxylates by (NBu4)Cr2O7 in the presence of different phosphonic acids and chelating ligands results in six CrIII-doped tetranuclear manganese clusters formulated [Mn3CrO2(O2CCH3)4(O3PC5H4N)2(bpy)2] (1), [Mn3CrO2(O2CCH3)4(O3PC5H4N)2(phen)2] (2), [Mn3CrO2(O2CPh)4(O3PC5H4NO)2(phen)2] (3), [Mn3CrO2(O2CPh)4(O3PC6H11)2(bpy)2] (4), [Mn 3CrO2(O2CPh)4(O3PC6H11)2(phen) 2] (5), and [Mn3CrO2(O2CCH3)4(O3PC6H11)2(bpy)2] (6). Single-crystal X-ray analyses reveal that all the compounds contain similar [M4O2]8+ cores with the four metal sites arranged in planar topologies. The metal ions within the core are bridged by both carboxylate and phosphonate ligands. Temperature-dependent magnetic measurements show that in all cases dominant antiferromagnetic interactions are propagated between the metal centers. The ac magnetic measurements on compounds 5 and 6 reveal that both the in-phase and the out-of-phase signals are frequency dependent, characteristic of single-molecule magnet behaviors.     

A new approach to synthesis of layered fluorites containing molecular anions: synthesis of Ln2O2CO3, K(LnO)CO3, and Ln2O2CrO4 via metathesis reactions

A new synthetic approach is suggested for preparation of layered rare-earth oxide compounds containing [Ln2O2] slices and molecular anion sheets (CO32-, SO42-, and CrO42-). It is based on exchange reactions of rare-earth oxychlorides, [Ln2O2]Cl2, and alkali carbonates, sulfates, or chromates. Five new rare-earth oxychromates [Ln2O2]CrO4 (Ln=Pr-Gd) have been prepared which adopt a new, probably layered, structure type. In addition, significantly easier and more efficient synthetic pathways were found to the known compounds [Ln2O2]K2(CO3)2 and [La2O2]CrO4. The structure of the latter compound has been determined from neutron powder diffraction data. Factors affecting reaction pathways and products are discussed, as well as prospects for applying the approach to more complex layered compounds.     

Electrodeposition of Ni/ceria composites: an in situ visible reflectance investigation

Ni/cerium oxide coatings were electrodeposited from particle-free aqueous baths containing NiCl₂.6H₂O and CeCl₃.7H₂O. The mechanism of deposition was studied systematically by a combination of voltammetric, in situ spectroelectrochemical (visible reflectivity spectroscopy (VRS) and surface Raman spectroscopy), ex situ spectroscopic (spectroscopic ellipsometry) methods, as well as by scanning electron microscope imaging; yielding details on the steps of the composite formation process. Time- and potential-dependent electro VRS data were interpreted on the basis of an optical model, accounting for the formation of metal and ceramic phases and corresponding relative distribution and morphology. In the VRS curves measured with the pure Ni and Ce-containing solutions, the value of reflectivity drops sharply when the potential is lower than ca. ?0.9?V. The VRS curves measured in the Ce-containing solutions exhibit a second drop when the potential is lower than ca. ?1.1?V while, instead, for pure Ni solution an increase in reflectivity is observed. According to the proposed optical model, the drop found in the reflectivity transient can be explained with the nucleation of Ni on the Cu substrate, while the second one measured with Ce-containing solutions is due to secondary nucleation of Ni. The results showed that the deposition processes of Ni and Ni/cerium oxide can be divided into two and four stages, respectively. (1) In the case on Ni: nucleation and 3D growth, accompanied by roughening; (2) as far as Ni/cerium oxide is concerned: nucleation, formation of cerium oxide, secondary nucleation, and 3D growth and roughening.     

Influence of [BMIM]HSO4 on electrodeposition and corrosion behavior of Zn coatings from acidic sulfate bath

The effect of 1‐butyl‐3‐methylimidazolium hydrogen sulfate‐[BMIM]HSO₄ on the nucleation and growth of zinc from acidic sulfate bath was investigated at a glassy carbon (GC) electrode using cyclic voltammetry, chronoamperometric and scanning electron microscopy techniques. Dimensionless chronoamperometric current‐time transients for the electrodeposition of zinc on GC from the bath free of [BMIM]HSO₄ were in good accord with the theoretical transients for the limiting case of instantaneous three‐dimensional nucleation with diffusion‐controlled growth of the nuclei. The addition of [BMIM]HSO₄ was found to have a blocking effect on the electrodeposition of zinc and led to decrease of the nucleation and growth rate of nuclei. In addition, the instantaneous nucleation mechanism observed in the additive‐free bath was changed to a more progressive one when [BMIM]HSO₄ was present in the bath. Surface morphology analysis indicated that [BMIM]HSO₄ can induce the formation of finer grained deposits by the adsorption of additive in the first stages of deposition. The corrosion behavior of Q235 steel with coating by a thin layer of zinc in the absence and presence of [BMIM]HSO₄ was examined in 3.5% NaCl solution. The Zn coating obtained from the additive‐containing baths exhibited more excellent protection of the base metal in comparison to the additive‐free one. Copyright © 2012 John Wiley & Sons, Ltd.     

ITO上电沉积Pd的成核机理及电催化性质

采用循环伏安技术和计时电流技术, 研究了ITO上电沉积Pd的过程, 发现Pd在ITO表面的电沉积是过电位成核且为不可逆的扩散控制过程; 根据Cottrell方程计算得到[PdCl₄]^2-的扩散系数为2.19×10^-5 cm²/s; 根据Scharifker的理论模型, 归一化处理电流-时间曲线, 与理论成核曲线对照, 判断Pd 的成核机理. 通过场发射扫描电子显微镜(FESEM)对Pd 的形貌进行分析, 讨论了沉积电位和沉积时间对Pd纳米粒子形貌的影响. 用X射线粉末衍射(XRD)对Pd纳米粒子进行结构分析, 并在0.5 mol/L H₂SO₄溶液中研究了其电化学性质及在碱性条件下乙醇分子的电催化性质.     

ITO导电玻璃表面直接电沉积Au的机理

用循环伏安和电位阶跃法研究Au在氧化铟锡(ITO)透明导电膜玻璃表面的电沉积过程的初期阶段. 发现在ITO表面Au的电沉积经历成核过程以及受[AuCl₄]^-扩散控制的晶核生长过程. 通过改变扫描速率分析循环伏安曲线的变化, 当扫描速率较快时, 发现Au在ITO表面的沉积过程经历[AuCl₄]^-→[AuCl₂]^-→Au两步进行; 当扫描速率较慢时, 受歧化反应作用影响而只表现为一步沉积[AuCl₄]^-→Au. 通过电位阶跃实验, 验证了Au的两步沉积过程, 并求得[AuCl₄]^-的扩散系数为1.3×10^-5 cm²·s^-1. 将成核曲线与理论曲线对照, 得出Au在ITO表面的沉积符合瞬时成核理论. 通过场发射扫描电镜(FE-SEM)对Au核形貌进行分析, 根据扫描电镜图可以得到阶跃时间和阶跃电位对电沉积Au的形貌的影响.     

以光辅助MOCVD法在有取向Ni衬底及LAO单晶衬底上制备YBCO外延膜的比较研究

采用光辅助金属有机物化学气相沉积(MOCVD)法,在生长有CeO2/YSZ/Y2O3(YSZ为Y稳定的ZrO2)缓冲层的双轴取向Ni衬底上进行了YBa2Cu3O7-x(YBCO)外延膜生长,并与LaAlO3(100)[LAO(100)]单晶衬底上的YBCO外延膜生长进行了对比.发现在Ni衬底上c轴取向YBCO外延膜的生长温度比LAO衬底上的生长温度低约30℃,但生长速度更快.经分析认为,这种差别主要是由于Ni衬底的热导率比LAO衬底高造成的.Ni衬底及LAO衬底上生长的c轴取向YBCO外延膜的超导极限电流密度(Jc)分别约为0.5 MA/cm2及1.8 MA/cm2.     

A Series of Mononuclear Complexes Constructed from Transition Metals and Amino Acid Derived Ligands: Syntheses, Structures and Photoluminescence

Eight neutral mononuclear complexes constructed from transition metals （M = Co（Ⅱ）, Ni（Ⅱ）, Cu（Ⅱ）, Zn（Ⅱ）, Cd（Ⅱ）） and ligands N-（2-pyridylmethyl）-L-phenylalanine （L-Hpmpa） and N-（2-pyridylmethyl）-L-tyrosine （L-Hpmtyr） have been synthesized by both hydrothermal and conventional room temperature reactions. Four of them have been structurally characterized by single-crystal X-ray diffractions. They are： [Co（L-pmpa）2·2H2O] 1, [Ni（L-pmpa）2·2H2O] 2, [Cu（L-pmpa）2·2H2O] 3 and [Cu（L-pmtyr）2·2H2O] 4. Single-crystal X-ray analysis, IR and elemental analysis revealed that complexes 1, 2 and 3 are isostructural. Powder X-ray diffraction, IR and elemental analysis revealed that complexes 4, 5 （Zn[L-pmtyr]2·2H2O）, 6 （Cd[L-pmtyr]2·2H2O）, 7 （Co[L-pmtyr]2·2H2O） and 8 （Ni[L-pmtyr]2·2H2O） are isostructural. The photoluminescence properties of L-Hpmtyr ligand, compounds 5 and 6 were also investigated.