核电站结构材料的锌离子注入电化学研究

应用电化学方法研究了锌离子注入(zinc injection)技术对核电站结构材料,如304L不锈钢、316L不锈钢和600合金在高温水中形成的氧化膜的电化学性能的影响. 锌离子注入压水堆(PWR)一回路技术可有效减少材料应力腐蚀破裂(stress corrosion cracking)和职业辐照. 用动电位扫描法检测材料氧化膜的自腐蚀电位与腐蚀电流,根据Mott-Schottky曲线分析Zn离子注入对材料氧化膜半导体性质的改变. SEM和XPS观察与检测试样表面形貌及其组分. 在Zn离子参与的金属氧化膜生成过程中,可生成Zn-Ni-Cr-Fe 氧化物,从而提高了材料的抗腐蚀能力及改变氧化膜的半导体性质.     

不锈钢钝化膜耐蚀性与半导体特性的关联研究

通过极化曲线、交流阻抗谱和钝化膜半导体特性等电化学测量，研究了经电化学阳极氧化处理的不锈钢钝化膜在0.5 mol•L^-1 NaCl溶液中耐蚀性能与其半导体特性的关系，进一步探索电化学改性处理不锈钢钝化膜的耐蚀机理. 结果表明，不锈钢钝化膜在负于平带电位范围表现为p型半导体，在高于平带电位范围表现为n型半导体，这主要与组成钝化膜的Fe和Cr氧化物半导体性质有关. 与自然条件下形成的不锈钢钝化膜比较，发现经过电化学阳极氧化后不锈钢钝化膜具有较低的施主与受主浓度，平带电位负移，说明阴离子在钝化膜表面发生吸附. 低的施主与受主浓度及钝化膜表面负电荷的增强，可有效排斥侵蚀性Cl^－在钝化膜表面的特性吸附，有利于提高不锈钢的耐局部腐蚀性能.     

高温水中添加微量Zn（2＋）对Inconel600合金氧化膜半导体性质的影响

核电站采用Zn2＋注入技术减少一回路镍基材料的应力腐蚀和辐射污染.向高温水中添加微量Zn2＋制备Inconel600合金表面氧化膜,用光电化学响应技术和容抗测量技术研究Zn2＋对氧化膜半导体性质的影响.光电化学响应结果表明,氧化膜中不同氧化相的特征带隙宽度分别为Fe2O3 2.2 eV,Cr2O3 3.5 eV,Fex...     

n型砷化镓微区光电化学腐蚀过程

在n-GaAs电解液界面,用聚焦He-Ne激光照射, 使n-GaAs表面发生微区光电化学腐蚀, 用计算机控制步进马达, 使试样在X-Y二维方向扫描移动, 能在晶片上得到刻蚀点直径2 μm的刻蚀图案. 研究了激光相对光强, KOH、H_2SO_4、KCl等刻蚀剡的浓度, 光腐蚀的时间, 电极电位等因素对腐蚀点的直径和深度的影响, 通过实验数据找出腐蚀过程的规律, 并用光电化学原理进行解释.     

半导体的化学刻蚀

半导体的化学刻蚀，俗称湿法刻蚀，它是半导体器件制作中的一个重要工艺，按照化学作用的原理，它可分为化学反应刻蚀、电化学刻蚀和光电化学刻蚀，半导体的化学刻蚀是在众多刻蚀方法中最基本和最终不能全部被取代的一种方法，它在高新技术中有着各种挂用途，如选择准刻蚀、各向异性刻蚀和计算机控制无掩模刻蚀等。     

制备条件对PANI/PATP/Au和TiO_2-PANI/PATP/Au膜光电化学性能的影响

应用电化学方法在不同条件下制备聚苯胺 (PANI)膜和TiO2 -PANI复合膜 ,并对其光电化学性能进行研究 .实验表明 ,制备条件是影响膜光电化学性能的重要因素 .对氨基硫酚 (PATP)的组装有利于改善PANI膜的附着力 ;部分氧化态PANI膜的光电化学响应明显优于还原态和氧化态PANI膜的光电化学响应 ;部分氧化态PANI膜的厚度对其光电化学性能有一最佳值 ;热处理虽然有利于改善TiO2 的光电化学性能 ,但温度太高 ,将破坏PANI膜的表面结构 ,对于TiO2 -PANI复合膜有一最佳的热处理温度 .优化制备条件大可改善TiO2 -PANI复合膜和PANI膜的光电化学性能     

阳极氧化AZ91D镁合金在氯化钠稀溶液中的腐蚀行为

利用盐雾实验、极化曲线扫描、电化学阻抗谱和电化学噪声技术等电化学研究方法结合扫描电镜表面观测技术对AZ91D镁合金氧化膜在1%(w)氯化钠溶液中的耐蚀性能进行了评价. 结果表明, 氧化前后的镁合金腐蚀行为发生明显改变, 如未封孔的阳极氧化膜耐中性5%氯化钠盐雾试验时间超过200 h; 氧化后的镁合金自腐蚀电位明显正移, 点蚀诱导期延长; 阳极氧化膜的高频阻抗约为裸露镁合金的数千倍, 这些变化证明阳极氧化处理使镁合金获取了十分优异的耐蚀性能. 首次利用分形维数Df的变化规律初步描述氧化后AZ91D镁合金的腐蚀过程. 可以发现随着浸泡时间的延长, Df呈现出初期快速增长, 随后出现波动, 最后稍有降低的变化过程. 这种现象对应于氧化后AZ91D 镁合金在1%氯化钠溶液中腐蚀的三个阶段.     

阵列微电极研究Nd~(3+)对金属铜在3.5% NaCl溶液中腐蚀电化学行为的影响

利用阵列微电极技术测量了金属铜的自腐蚀电位、阻抗及表面腐蚀产物膜层载流子密度,并结合扫描电子显微镜,研究了Nd3+对金属铜在3.5%(w)NaCl溶液中腐蚀电化学行为的影响.结果表明,加入Nd3+使得金属铜表面生成的腐蚀产物膜层的形貌及结构发生了变化,腐蚀产物膜层变薄,腐蚀产物由片状结构转变为粒状结构,颗粒均匀分散分布;Nd3+的存在使得金属铜表面各区域的电位方差由0.034下降为0.026,阻抗标准方差由32805下降为6940,电位及阻抗分布趋于均匀化,有利于抑制局部腐蚀的发生;并且加入Nd3+将造成金属铜表面绝大部分区域腐蚀产物膜层的半导体类型由n型转变为p型,表面腐蚀产物膜层载流子密度标准方差由1.89×1017上升为4.10×1017,载流子密度分布趋于不均匀.     

玻碳电极电化学活化的原位FTIR反射光谱研究

用电化学原位FTIR反射光谱法研究了玻碳电极电化学活化过程中表面含氧功能团的生成及其表面过程。结果表明,该电极在高电位下氧化时生成了表面含氧功能团,并有一部分进一步氧化成CO_2,表面类醌基在随后的循环伏安扫描过程中部分转化成酚基,最终形成稳定的表面氧化还原对。表面类醌基同羟基之间存在强的氢键相互作用。     

铂微粒弥散的聚2,5—二甲氧基苯胺膜电极在甲醇电氧化中的催经行为

研究了电化学方法制备的铂微粒弥散的聚２，５－二甲氧基苯胺膜电极对甲醇电氧化的摧化行为以及影响催化活性的主要因素，以ＸＰＳ、ＳＥＭ表征了这种电极材料的表面结构。结果表明，在酸性介质中，该膜电极对甲醇电氧化有高的催化活性和稳定性。     

Electroless Deposition of III–V Semiconductor Nanostructures from Ionic Liquids at Room Temperature

Group III–V semiconductor nanostructures are important materials in optoelectronic devices and are being researched in energy‐related fields. A simple approach for the synthesis of these semiconductors with well‐defined nanostructures is desired. Electroless deposition (galvanic displacement) is a fast and versatile technique for deposition of one material on another and depends on the redox potentials of the two materials. Herein we show that GaSb can be directly synthesized at room temperature by galvanic displacement of SbCl₃/ionic liquid on electrodeposited Ga, on Ga nanowires, and also on commercial Ga. In situ AFM revealed the galvanic displacement process of Sb on Ga and showed that the displacement process continues even after the formation of GaSb. The bandgap of the deposited GaSb was 0.9±0.1 eV compared to its usual bandgap of 0.7 eV. By changing the cation in the ionic liquid, the redox process could be varied leading to GaSb with different optical properties.     

GaSb based lasers operating near 2.3 microm for high resolution absorption spectroscopy

The paper describes results obtained with a new type of GaSb based semiconductor distributed feedback multiple quantum well lasers operating in continuous wave mode well above room temperature. The lasers show good tunability both by current and temperature from 0 to +60 degrees C and current from threshold up to 120 mA. They all operate in high power (1-3 mW) single mode regime and can be tuned in the methane and ammonia overtone absorption spectral range over up to 12 cm(-1) and can be used for the detection of these and other gases.     

水溶液中电化学沉积GaSb相变存储薄膜

利用恒电位共沉积技术和热处理的方法成功制备了GaSb薄膜,探索了添加乙二醇溶剂对薄膜结晶性和形貌的影响. 采用循环伏安法初步研究了共沉积GaSb的机理,并用X-射线衍射技术（XRD）、扫描电子显微技术（SEM）和能谱分析（EDS）表征、观察样品. 研究表明,在沉积过程中,SbO⁺先还原成Sb单质,再诱导Ga³⁺发生共沉积;沉积电位对薄膜的结晶性、微观形貌和成分有显著影响;电解液加入乙二醇更利于在较正电位下直接沉积出GaSb,且有效地提高了薄膜的结晶度,改善了薄膜的微观形貌.     

Copper solubility and distribution in doped GaSb single crystals

For the GaSb single crystals doped with copper (grown using the Czochralski method without encapsulant in flowing atmosphere of hydrogen) the distribution coefficient of copper in GaSb,k _eff=0.0021±0.0006 was found and the copper solubility in GaSb was discussed. The region of copper solubility in GaSb was analyzed on the thermodynamic basis using chemical phase diagram in the Sb?Ga?Cu system. Due to a rather low solubility of copper, its excessive amount in GaSb caused probably an increase of the dislocation density at the end of the GaSb single crystals.     

Comparative Thermodynamic Investigation of the Bi–GaSb System

Results of the thermodynamic investigations in the Bi–GaSb system are presented in this paper. Thermodynamic characteristics experimentally determined by Oelsen's calorimetric method were compared with values predicted by different thermodynamic predicting methods (general solution model, Kohler, Muggianu, Toop, Hillert) at the temperature of 1073 K. Also, based on the obtained cooling curves and microstructure analysis of the investigated samples by optical microscopy, phase diagram of the Bi–GaSb system was investigated and compared with literature data. This revised version was published online in July 2006 with corrections to the Cover Date.     

Structure and Chemical Composition of Manganese-Doped GaSb Dislocations

Electron microscopic observations showed that the preparation of magnetic semiconductor GaSb〈Mn〉 by melt quenching is accompanied by discrete manganese precipitation on GaSb dislocations, this precipitation generating inclusions sized from a split micrometer to several micrometers. The chemical composition of microinclusions was determined by electron probe microanalysis. The superposition of the magnetic properties of compounds that are formed in the Mn–Sb system determines the magnetic properties of GaSb〈Mn〉.     

PHOTOELECTROCHEMICAL STUDIES OF ULTRATHIN PHOTOACTIVE (POLYMER) LAYERS VIA SENSITIZATION OF ZnO

–Since photoelectrochemical properties of very thin (< 100 Å) layers of photoactive materials cannot be studied on metal contacts due to energy transfer losses and excessive dark currents through holes, an attempt was made to investigate them in contact with a large gap oxide semiconductor (ZnO). It was expected that electrons excited within the thin layer can be injected into the conduction band of ZnO. Experiments have shown this to be possible with the p-type polymer semiconductor poly(2,5-furylenvinylene) applied at thickness equivalent to 1–50 monolayers. Studies on complementary sensitization with Rhodamine B suggest energy transfer mediated electron transfer across the polymer layer into ZnO. In contrast, sensitization of ZnO by thin layers of n -CdS or rc-FeS₂ (prepared by painting or MOCVD) was not successful. Promises and difficulties of the technique which could also be applied to biological samples are discussed.     

二氧化钛纳米微粒膜光电化学行为的研究

利用不同的制备方法制备出二氧化钛纳米微粒膜，对二氧化钛纳米微粒膜的光电化学材为和产生的机理进行了研究．结果表明；二氧化钛纳米微粒膜除了具有传统半导体的光电化学性质外，还具有不同于传统半导体的光电化学性质这主要是出膜的微粒性引起的，可综合传统半导体和胶粒半导体两种模型来加以解释。     

Photoelectrochemistry of free-base-porphyrin-functionalized zinc oxide nanoparticles and their applications in biosensing

The photoelectrochemical properties of free-base-porphyrin-functionalized zinc oxide nanoparticles were studied. A universal photoelectrochemical biosensing platform was constructed on indium tin oxide (ITO) by using the functional nanohybrid. The nanohybrid was synthesized by means of dentate binding of ZnO nanoparticles with carboxylic groups of 4,4',4',4'-(21H,23H-porphine-5,10,15,20-tetrayl)tetrakis(benzoic acid) (TCPP), and characterized with scanning electron microscopy, contact angle measurement, and spectral techniques. The nanohybrid-coated ITO electrode showed an efficient photocurrent response under irradiation at a wavelength of 360 nm, which could be greatly improved upon addition of cysteine by its oxidation at +0.3 V. The possible mechanism was that cysteine acts as a sacrificial electron donor to scavenge the photogenerated holes that locate on the excited state of TCPP, which then injects the photoexcitation electrons into the conduction band of ZnO nanoparticles, thereby transferring photoinduced electrons to the ITO electrode. Based on this enhanced photocurrent signal, a novel method for photoelectrochemical detection of cysteine was developed with a linear range of 0.6 to 157 μmol L(-1) in physiological media. The detection limit was 0.2 μmol L(-1) at a signal-to-noise ratio of 3. The novel strategy of cysteine analysis could provide an alternative method for monitoring biomolecules and extend the application of porphyrin-functionalized semiconductor nanoparticles.     

结合光电化学和瞬态吸收光谱技术研究光电化学分解水载流子动力学

半导体光电化学制氢是一种重要的、有前景的太阳能应用技术. 其产氢效率取决于光生载流子的产生、分离和传输效率. 深入理解光生载流子的动力学过程对于设计高效的太阳能产氢器件有重要的指导意义. 光电化学和瞬态吸收光谱技术是研究光催化反应微观动力学和机理的强有力手段. 本文介绍作者应用这些技术在半导体光电化学制氢方面所取得的部分最新研究结果, 并对存在的问题和今后研究重点提出了一些看法.