Thermal stability of carrier centers in various types of transparent conductive ZnO and Ga-doped ZnO films

We investigated the thermal stability of the transparent conductive properties of undoped ZnO and Ga-doped ZnO (GZO) films when they were annealed in a high vacuum with stepwise increasing temperature. The ZnO samples included V_O-rich and Zn-rich ZnO films; the primary donors were respectively oxygen vacancies (V_O) or Zn atoms highly unsaturated with oxygen atoms. V_O-rich ZnO was the most unstable against annealing; resistivity initially within the 10⁻³ Ω cm range diverged higher than 10 Ω cm when a critical temperature was exceeded. The critical temperature between 350 and 450 °C depended on the film thickness, which indicated that V_O's were diminished through recombination with migrating interstitial oxygen atoms. In contrast, Zn-rich ZnO films remained highly conductive up to 550 °C. They became more and more transparent and their crystallinity improved at higher annealing temperatures, which was the consequence of metallic-like Zn atoms being removed through desorption from the surface or being accommodated into the crystalline lattice. Comparatively, GZO films were more robust against annealing with their resistivities remaining unchanged up to 350 °C.     

Temperature dependence of conduction mechanism of ZnO and Co-doped ZnO thin films

ZnO and Co-doped ZnO thin films have been deposited on the sapphire substrate by ultrasonic assisted chemical vapor deposition technique. The films were annealed in vacuum at 450 °C. All the films were highly c-axis orientated and contained no impurity phase. The temperature dependence of the electrical conductivity has been measured in order to identify the dominant conduction mechanism. In the higher temperature region the dominance of thermally activated band conduction was observed whereas in the low temperature region the hopping conduction was found to dominate. The hopping conduction mechanism in the lower temperature range in the film was Mott's Variable Range Hopping and not the Nearest Neighbor Hopping. The temperature region, where hopping conduction was dominant found to increase by Co doping in ZnO film. The localization length was found to be larger in the Co-doped ZnO film.     

掺铁纳米氧化锌的制备及其光催化性能

采用共沉淀法制备了纯纳米ZnO和掺铁纳米ZnO,并用X射线衍射光谱进行了表征。用紫外灯作为光源,甲基橙溶液为光催化反应模型降解物,研究了ZnO及掺铁ZnO的光催化性能,并考察了前驱体焙烧温度、铁掺杂量、底物浓度、光照时间以及pH对降解率的影响。结果表明,掺杂铁离子提高了ZnO的光催化活性,400℃热处理的掺杂铁0.5%(质量比)的ZnO的光催化性能最好;当甲基橙初始浓度为5mg/L,光照时间3h,掺杂铁0.5%(质量比)的ZnO粉末对甲基橙的降解率达到84%;掺铁纳米ZnO在弱酸性条件下的催化效果比碱性条件下更好。     

ZnO籽晶对ZnO压敏陶瓷微观结构和电性能的影响

本文研究了ＺｎＯ籽晶的制备，探讨了昌对ＺｎＯ压敏陶瓷材料微观结构及压敏电压。通流容量。非线性一系民性能的影响。结果表明，通过掺加ＺｎＯ籽晶，可有效地控制材料中ＺｎＯ昌粒生长入材料微观结构。达到降低材料压敏电压和提高通流容量的目的。     

分级微纳结构氧化锌的制备及其光致发光

采用低温热蒸发法研制出新型的ZnO分级微纳结构,利用场发射扫描电子显微镜和X射线衍射仪对其形貌与结构进行了表征,结果表明,所制备的分级结构为纯六方纤锌矿结构,由主干直径为1-3μm的ZnO微米线和表面的宽度为1μm、厚度约为100nm的晶片组成。用气-固（VS）机制阐明了ZnO分级结构的生长机理。在室温下,用近场光学显微镜测量了ZnO分级结构的光致发光谱,结果显示,在380nm处存在很强的近带隙发光峰,而508nm左右的缺陷发光很弱。     

Low wet etching rates of ZnO films prepared by sputtering of mixed ZnO and AlN powder targets

ZnO films codoped with Al and N have been prepared by radio frequency magnetron sputtering in an Ar atmosphere, using targets of mixtures of ZnO and AlN powders. The Al-doped ZnO films are transparent, whereas the films codoped with Al and N are colored. The Al- and N-concentrations in the colored films are estimated to be 4–7 at.% and 1–2 at.%, respectively. No enhancement of the carrier density is seen in the colored ZnO films, whereas the colored films exhibit lower etching rates of 3–5 nm/s in a 0.1 M HCl solution, in comparison with the Al-doped ZnO films. For the colored film, the anisotropic grain growth occurs, and cubic grains are produced after etching. The low etching rates of the colored films are ascribed to the epitaxial growth of AlN films on the surfaces of ZnO grains, rather than the incorporation of Al–N and Al–O bonds into the ZnO lattice.     

异质结构BiOCl/ZnO光催化剂的绿色合成及其光催化性能

以硝酸锌、硝酸铋、氯化钾和氢氧化钠为原料,利用简单的水浴法在低温下合成了Bi、Zn物质的量比分别为0∶1、1∶1、1∶2、1∶3、1∶4、1∶0的BiOCl/ZnO异质结构复合物。采用X射线粉末衍射(XRD)、扫描电镜(SEM)、紫外可见光谱(UV-Vis)、能谱(EDS)、紫外可见漫反射光谱(UV-Vis DRS)等一系列手段对所制备的光催化剂进行了表征。以氙灯为光源,RhB(罗丹明B)为光催化反应降解模型,进行光催化活性测试,考察了复合ZnO对BiOCl光催化剂反应活性和稳定性的影响。研究结果表明,异质结型BiOCl/ZnO复合光催化剂的光催化性能明显优于纯ZnO和纯BiOCl。当Bi、Zn物质的量比为1∶1时,光催化活性最佳,同时该催化剂在循环使用中具有很好的稳定性。     

ZnO陶瓷靶制备及其薄膜 RF溅射工艺研究

利用固相反应制备了直径为70mm,厚度为10-15mm高质量掺杂Li2CO2的ZnO陶瓷靶材,实验了不同摩尔浓度的Li+掺杂对靶材性能的影响,确定了最佳Li+掺杂量为2．2mol％,同时通过在不同温度烧结实验、不同成型压力实验确定了ZnO靶材制备的最佳工艺,并采用所制备的ZnO-Li2.2％陶瓷靶和RF(射频磁控)技术在Si(100)、玻璃(载玻片)、及Pt(111)／Ti／SiO2／Si(100)基片上制备出高度c轴(002)择优取向的ZnO薄膜,其绝缘电阻率ρ为4．12×108Ω·cm,达到了声表面波器件(SAW)的使用要求．     

氧化锌空心球的制备及光致发光特征

采用水热和硬模板辅助技术,成功制备得到ZnO空心球结构.以葡萄糖和锌盐为原料,首先通过催化葡萄糖聚合-原位离子吸附一步进行(一步法)或葡萄糖聚合成球-离子吸附分步进行(二步法)制备锌/炭复合微球,然后经空气低温氧化制得ZnO空心球.用XRD、SEM、TEM研究产物的组成和结构及形貌,用光致发光光谱(PL)测试产物的室温光致发光性能.研究发现,两种方法得到的空心球壳均属多孔结构,由ZnO纳米粒子构成;与聚合-吸附分步法相比,聚合-原位离子吸附一步法更加简单快捷;制得的ZnO空心球结构材料具有良好的近紫外发光性能.对ZnO空心球结构的形成过程和可能的机制进行了分析和讨论.     

ZnO气敏陶瓷的制备与气敏性能研究

分别用氨水、草酸铵、尿素和碳酸钠做沉淀剂合成了4种不同陶瓷微结构的ZnO气敏材料。用X射线衍射(XRD),透射电子显微镜(TEM)和电子衍射(ED)法研究了其晶体和陶瓷微结构。采用静态配气法测试了其气敏效应。ZnO陶瓷具有四方和六方2种不同的结晶外形,颗粒尺寸为0.1～4μM。ZnO陶瓷对C_2H_5OH具有较好的气敏选择性,通过SnO_2的掺杂,ZnO对C_2H_5OH的选择性可进一步提高。颗粒微细化有助于提高ZnO的气体灵敏度。     

Characterization of ZnO Based Varistor Derived from Nano ZnO Powders and Ultrafine Dopants

Nanosized ZnO powders were prepared with a two-step precipitation method. The average size of ZnO particles was about 80 nm and their size distribution was narrow. Combining with ultrafine additive powders, ZnO base varistor was produced via an oxide mixing route. ZnO varistor derived from normal reagent grade starting materials was investigated for comparison purpose. Outstanding microstructure of the ZnO varistor derived from nanosize ZnO powders and ultrafine dopants was obtained: uniform distribution of fine ZnO grains (less than 3 microns), grain boundary and the dopant position. Higher varistor voltage (U=492 V/mm) and nonlinear coefficient (α=56.2) as well as lower leakage current (TL=1.5 μuA) were achieved. The better electrical properties were attributed to the uniform microstructure, which in turn led to stable and uniform potential barriers. Also this improved technique is more feasible for producing ZnO nanopowders and resulting varistor in large scales.     

Technology of ZnO nanofibers based devices

In the presented work, the possibility of fabrication of ZnO single- and multi-nanofiber structures using a standard microelectronic device technology were studied. An innovative fabrication step, namely, selective wet chemical nanofibers etching through a photoresist mask, was used to define the active area, along with mesa etch in the Si/SiO₂ substrate. Test structures in the configuration of a resistor and Schottky diode with chemically active electrospun ZnO nanofibers were prepared. The Ti/Au ohmic and Pt Schottky contacts were fabricated using a lift-off photolithography process. Optical and scanning electron microscopy studies were done to characterize ZnO nanofibers and topography of contacts. The measurements made for electrical characterization showed linear I–V dependence and saturation of the current for single ZnO nanofiber structures.     

Direct growth of enclosed ZnO nanotubes

To date, wet syntheses of single-crystalline ZnO micro- and nanotubes have been carried out using a two-step indirect approach in which a selective dissolution step is required in order to create the vacant space in the tubular structures. In this work, we develop a direct growth process for preparation of single-crystal ZnO nanotubes and nanorods. We also report that a concave shaped crystal growth front is generally reactive and offers a large surface area for matter deposition during rapid expansion of unidirectional nanomaterials. Depending on the degree of supersaturation of nutrients in solution, the concave growth front can either remain unaltered or undergo a concave-to-convex transformation, leading to the growth of solid nanorods and/or hollow nanotubes. The observed volume inversion should, in principle, also be applicable to the nanoarchitecture of other one-dimensional wurtzite structured nanomaterials, although individual sets of synthesis parameters need to be developed for each target material. Electronic Supplementary Material  Supplementary material is available for this article at and is accessible for authorized users. This article is published with open access at Springerlink.com     

Uniform ZnO nanorods can be used to improve the response of ZnO gas sensor

Uniform ZnO nanorods were synthesized in high-yield by using metal zinc powder as zinc source via a one-step facile hydrothermal process under mild conditions, in which cetyltrimethylammonium bromide (CTAB) with ordered chain structures acted as the conversion of Zn powder into ZnO nanorods. The characterization results show that the as-synthesized products were structurally uniform and have diameters of 40–80 nm. Gas sensing properties studies show that ZnO nanorods exhibit more excellent response and stability to ethanol than that of ZnO nanoparticles. After working continuously for 50 days, the sensitivity of ZnO nanorods still retained 7.3, whereas, the ZnO nanoparticles showed only 1.0. The facile preparation method and the improved properties derived from typical rods-like nanostructure are significant for the future applications of gas sensing material.     

ZnO nanostructured microspheres and grown structures by thermal treatment

Synthesis of flower-shaped ZnO nanostructures composed of ZnO nanosticks was achieved by the solution process using zinc acetate dihydrate, sodium hydroxide and polyethylene glycol-20000 (PEG-20000) at 180°C for 4 h. The diameter of individual nanosticks was about 100 nm. Detailed structure characterizations demonstrate that the synthesized products are wurtzite hexagonal phase, grown along the [001] direction. The infrared (IR) spectrum shows the standard peak of zinc oxide at 571 cm⁻¹. Raman scattering exhibits a sharp and strong E ₂ mode at 441 cm⁻¹ which further confirms the good crystal and wurtzite hexagonal phase of the grown nanostructures.     

Growth and optical applications of centimeter-long ZnO nanocombs

Ultralong ZnO nanocombs have been synthesized on silicon substrates with a high growth rate of ∼7 μm/s using a simple “thermal evaporation and condensation” method promoted by Cu catalysts. The lengths of the ZnO nanocombs range from several millimeters to more than one centimeter and the diameters of the branches are about 300 nm. The growth mechanism of the ultralong nanocombs and the catalytic behavior of the copper are discussed. The nanocombs were readily separated and their applications as optical polarizer and grating were investigated. The results show that the ultralong ZnO nanocombs can act as effective optical components in miniaturized integrated optics systems. This article is published with open access at Springerlink.com     

ZnO单晶体的荧光温度特性

通过变温荧光光谱研究了ZnO激子发光的温度依赖特性。在6K的低温下,其光致发光主要来自束缚激子能量位于3.360eV,半宽为3meV的施主束缚激子发光。而随着测量温度的上升,自由激子及其声子辅助跃迁发光逐渐成为ZnO主要发光机制。文中详细讨论了ZnO荧光随温度的演变过程。特别是自由激子的声子伴线与自由激子发光峰之间的能量间距,随温度的上升逐渐偏离了其特征声子模能量,呈现不断缩小趋势。