ZnO纳米线的合成与生长机理

采用化学气相沉积系统制备ZnO纳米线,以覆盖一层约5nm厚的Ag薄膜的单晶Si(001)为衬底,纳米线的生长遵循气-液-固(VLS)机理。对得到的样品采用X射线衍射(XRD)和扫描电镜(SEM)进行晶体结构和形貌的表征。XRD结果表明衬底温度在600~700℃时生长的ZnO纳米线具有六方结构和统一的取向。通过扫描电子显微镜分析,比较了生长温度对纳米线直径和长度的影响。实验表明我们可以通过催化剂和温度来实现ZnO纳米线生长的可控。与传统的VLS生长方式不同的是在我们制备的ZnO纳米线顶端并没有看到催化剂颗粒,表明纳米线的生长方式是底部生长,我们对其生长机理进行了研究。     

异质结型CuO/ZnO复合纳米线的制备及光催化性能

在室温下,通过溶液法在Cu衬底上制备了CuO纳米线,然后采用溶剂热法在CuO纳米线表面生长ZnO纳米颗粒以构建CuO/ZnO复合纳米线异质结构。利用扫描电镜、透射电镜、X射线衍射仪和X射线光电子能谱分析了样品的形貌、结构和元素组成。结果显示CuO/ZnO复合纳米线由ZnO纳米颗粒和CuO纳米线组成。在模拟太阳光照射下,以亚甲基蓝溶液为模拟污染物研究了样品的光催化性能。结果表明,相比纯CuO纳米线,CuO/ZnO复合纳米线能够使亚甲基蓝溶液的光降解效率达到40%,在相同条件下具有更优异的光催化活性。光催化机理研究表明CuO/ZnO纳米复合材料光催化活性的增强主要是由于CuO与ZnO结合形成的p-n异质结有效促进了光生载流子的分离。     

ZnO纳米线二极管发光器件制备及特性研究

运用液相法生长成ZnO纳米线薄膜,并利用肖特基型异质结的发光原理,构造成功肖特基型ZnO纳米线二极管发光器件.在大于6V直流电压驱动下,观察到近紫外波段392nm处和可见光波段525nm的发射谱带.从单向导电特性及ZnO纳米线材料的能带结构等方面探讨了该种器件的电致发光机理. 关键词： ZnO纳米线 肖特基二极管 电致发光     

锡催化剂助生长法制备孪晶ZnO纳米线及其结构表征

用SnO和Zn的均匀混合物在高温下共烧通过VLS机制制备出孪晶ZnO纳米线的均匀结构。SEM图像显示孪晶ZnO纳米线的直径在100~200nm之间,长度在几十微米到几百微米之间的范围内,有的甚至达到了毫米级,产率也非常的高。TEM图像中ZnO孪晶纳米线顶端的金属Sn颗粒表明了孪晶结构的Sn催化生长。高分辨电子图谱显示了氧化锌纳米线孪晶结构的特征。电子衍射分析发现孪晶氧化锌的晶带轴的方向是[0110],孪晶面为(1013),并且通过明场像和暗场像分析了孪晶纳米线的晶格关系,确定了孪晶纳米线的汽-液-固(VLS)生长机制。     

高分子软模板法自组装生长ZnO纳米线及其光学性能

采用自组装技术,利用均聚极性高分子(聚丙烯酰胺、聚乙烯醇等)长分子链作为自组装模板在半导体硅衬底上自组装生长出ZnO纳米线。采用扫描电镜(FE-SEM)和透射电镜(HRTEM)对样品的表面形貌和结构分析表征的结果表明,ZnO纳米线直径约50~80nm、长度大于4μm,具有六方纤锌矿单晶结构,且沿c轴方向择优取向生长。采用室温下光致发光(PL)谱和紫外吸收(UV)光谱对制得的ZnO纳米线的光学性能研究表明,其PL光谱上有较强的紫外发射和较弱的蓝光发射,UV吸收光谱表明样品在紫外区有强的宽带吸收,且随着纳米线粒径的减小,吸收峰出现了蓝移现象。研究探讨了高分子诱导ZnO纳米线自组装定向生长机制、发光机理及其与工艺条件的内在联系。     

ZnO纳米线双绝缘层结构电致发光器件制备及特性研究

在利用液相法生长ZnO纳米线薄膜的基础上，构造成功基于ZnO纳米线双绝缘层结构的交流电致发光器件.此器件呈现出良好的阻容特性，在室温下以一定频率的交流电压驱动，可观察到近紫外波段387 nm处和可见光波段552 nm处的发射谱带.从阻容结构的导电特性及ZnO纳米线材料的能带结构等方面探讨了这种器件的电致发光机理及频率特性.     

ZnO纳米线二极管发光器件制备及特性研究

运用液相法生长成ZnO纳米线薄膜，并利用肖特基型异质结的发光原理，构造成功肖特基型ZnO纳米线二极管发光器件.在大于6V直流电压驱动下，观察到近紫外波段392nm处和可见光波段525nm的发射谱带.从单向导电特性及ZnO纳米线材料的能带结构等方面探讨了该种器件的电致发光机理.     

Pd颗粒表面修饰ZnO纳米线阵列的制备及其气敏特性

采用化学气相沉积(CVD)方法在SiO_2/Si衬底生长了ZnO纳米线阵列,纳米线长约为15μm,直径为100~500 nm。通过改变溅射沉积时间(0~150 s),在ZnO纳米线表面包覆了不同厚度的Pd薄膜。在Ar气氛中,经800℃高温退火后,制备出Pd颗粒表面修饰的ZnO纳米线阵列并对其进行了气敏测试。对于乙醇而言,所有传感器最佳工作温度均为280℃。溅射时间的增加(3~10 s)导致ZnO纳米线表面Pd纳米颗粒数量及尺寸增加,传感器响应值由2.0增至3.6。过长的溅射时间(30~150 s)将导致Pd颗粒尺寸急剧增大甚至形成连续膜,传感器响应度显著降低。所有传感器对H2均表现出相对较好的选择性,传感器具有较好的响应-恢复特性和稳定性。最后,探讨了Pd颗粒表面修饰对ZnO纳米线阵列气敏传感器气敏特性的影响机制。     

树形结构Si/ZnO纳米线阵列的制备及光学性能

用一种低成本的方法制备出了树形结构Si/ZnO纳米线阵列。首先在室温条件下用金属辅助化学腐蚀法在Si(100)衬底上制备了Si纳米线阵列,Si纳米线的直径尺寸及分布都很均匀,通过改变腐蚀时间,能够得到高度不同的Si纳米线阵列。利用磁控溅射在Si纳米线表面制备一层ZnO薄膜,然后利用水热法在Si纳米线阵列上生长了ZnO纳米线。通过扫描电子显微镜(SEM)、能谱分析仪(EDS)和光致发光(PL)测试对样品进行了表征。通过这种方法制备的Si/ZnO复合结构在太阳能电池、光催化等领域有潜在应用价值。     

衬底位置对化学气相沉积法制备的磷掺杂p型ZnO纳米材料形貌和特性的影响

采用化学气相沉积方法,在无催化剂的条件下,通过改变衬底位置在Si(100)衬底上制备出了高取向的磷掺杂ZnO纳米线和纳米钉.测试结果表明,当衬底位于反应源上方1.5 cm处时,所制备的样品为钉状结构,而当衬底位于反应源下方1 cm处时样品为线状结构.对不同形貌磷掺杂ZnO纳米结构的生长机理进行了研究.此外,在ZnO纳米结构的低温光致发光谱中观测到了一系列与磷掺杂相关的受主发光峰.还对磷掺杂ZnO纳米结构/n-Si异质结I-V曲线进行了测试,结果表明,该器件具有良好的整流特性,纳米线和纳米钉异质结器件的开启电压分别为4.8和3.2 V.     

Nanostructure size evolution during Au-catalysed growth by carbo-thermal evaporation of well-aligned ZnO nanowires on (100)Si

We report the structural and morphological properties of well-aligned ZnO nanowires grown at 750 °C on Au-deposited and annealed (100)Si substrates using carbo-thermal evaporation. As-grown nanowires are made of wurtzite ZnO, have cylindrical shape and carry droplet-like nanoparticles (NPs) at their tips, as expected for vapour–liquid–solid (VLS) growth. Grazing incidence X-ray diffraction measurements demonstrate that the NPs are made of pure fcc Au. No secondary Au/Zn alloy phases were detected. Bragg diffraction patterns confirmed that the nanowires were grown with their crystal c-axes parallel to the [100] direction of Si (i.e. normal to the substrate surface), while Au NPs are mostly (111)-oriented. The diameter distribution of ZnO nanowires mimics that of the Au NPs at their tips. A quantitative study of the nanostructure size distribution after sequential annealing and growth steps evidences the occurrence of three nanoscale processes: (i) Ostwald ripening and/or coalescence of Au NPs before nanowire nucleation, (ii) Au-catalysed VLS nucleation and axial growth of ZnO nanowires and (iii) radial growth of nanowires by a vapour–solid process. These processes originate the NP and nanowire size evolution during the experiments. The present findings are interpreted in terms of Zn vapour pressure changes during carbo-thermal evaporation. PACS 61.46.+w; 68.65.-k; 81.16.Dn     

Growth of Pure Zinc Blende GaAs Nanowires: Effect of Size and Density of Au Nanoparticles

Pure zinc blende GaAs nanowires were grown by metal organic chemical vapor deposition on GaAs（111）B substrates via Au catalyzed vapor-liquid-solid mechanism. The diameter, size distribution, and density of Au particles can be changed by varying the Au film thickness. We find that the grown nanowires are of rod-like shapes and pure zinc blende structure; moreover, the growth rate depends on the density of Au particles and it is independent of its diameters. It can be concluded that the nanowire was grown with main contributions from the direct impingement of vapor species onto the Au-Ga droplets and contributions from adatom diffusion can be negligible. The results indicate that the droplet acts as a catalyst rather than an adatom collector.     

ZnO–SnO2 branch–stem nanowires based on a two-step process: Synthesis and sensing capability

ZnO–SnO₂ branch–stem nanostructures were realized on a basis of a two-step process. In step 1, SnO₂-stem nanowires were synthesized. In step 2, ZnO-branch nanowires were successfully grown on the SnO₂-stem nanowires through a simple evaporation technique. We have pre-deposited thin Au layers on the surface of SnO₂ nanowire stems and subsequently evaporated Zn powders on the nanowires. The ZnO branches, which sprouted from the SnO₂ stems, had diameters in a range of 30–35 nm. As-synthesized branches were of single crystalline hexagonal ZnO structures. Since the branch tips were comprised of Au-containing nanoparticles, the Au-catalyzed vapor–liquid–solid growth mechanism was more likely to control the growth process of the ZnO branches. To test a potential use of ZnO–SnO₂ branch–stem nanostructures in chemical gas sensors, their sensing performances with respect to NO₂ gas were investigated, showing the promising potential in chemical gas sensors.     

Optical and structural properties of Eu-diffused and doped ZnO nanowires

Single crystal ZnO nanowires diffused with europium (Eu) from a solid source at 900 °C for 1 h or doped with Eu during growth have been characterized. The ZnO nanowires were grown by chemical vapor deposition on Si substrates employing Au as a catalyst. The diameter of the resulting nanowires was 200 nm with a length of 1 μm. Photoluminescence spectra excited by a He–Cd laser at room temperature showed the green luminescence at 515 nm in Eu-diffused nanowires. A small red shift of near-band-edge emission of ZnO nanowires was observed in the diffused wires, but sharp emission from Eu³ ions was not present. Transmission electron microscopy shows crystalline Eu₂O₃ formation on the diffused nanowire surface, which forms a coaxial heterostructure system. When Eu was incorporated during the nanowire growth, the sharp ⁵D_O–⁷F₂ transition of the Eu³⁺ ion at around 615 nm was observed.     

单根砷掺杂氧化锌纳米线场效应晶体管的电学及光学特性

采用化学气相沉积（CVD）的方法在砷化镓基底上合成直径为20 nm左右、长约数十微米的氧化锌纳米线,然后采用热扩散的方法,将生长于砷化镓基底之上的氧化锌纳米线通过600 ℃,30 min的有氧退火处理后,获得了砷掺杂的氧化锌纳米线.将获得的掺杂后的氧化锌纳米线采用电子束曝光以及真空溅射镀膜的方法将钛/金合金作为接触电极引出,从而构建成场效应晶体管.文中研究了单根氧化锌纳米线砷掺杂前后的电学特性,证实了通过砷掺杂来获得p型的氧化锌纳米线的可行性.构建的p型砷掺杂氧化锌场效应晶体管的跨导为35 nA/V,载流 关键词： p型ZnO纳米线 砷掺杂 场效应晶体管 光致发光     

Control of ZnO nanowire arrays by nanosphere lithography (NSL) on laser-produced ZnO substrates

Nanosphere lithography (NSL) is a successful technique for fabricating highly ordered arrays of ZnO nanowires typically on sapphire and GaN substrates. In this work, we investigate the use of thin ZnO films deposited on Si by pulsed laser deposition (PLD) as the substrate. This has a number of advantages over the alternatives above, including cost and potential scalability of production and it removes any issue of inadvertent n-type doping of nanowires by diffusion from the substrate. We demonstrate ordered arrays of ZnO nanowires, on ZnO-coated substrates by PLD, using a conventional NSL technique with gold as the catalyst. The nanowires were produced by vapor phase transport (VPT) growth in a tube furnace system and grew only on the areas pre-patterned by Au. We have also investigated the growth of ZnO nanowires using ZnO catalyst points deposited by PLD through an NSL mask on a bare silicon substrate.     

金辅助催化方法制备GaAs和GaAs/InGaAs纳米线结构的形貌表征及生长机理研究

利用金（Au）辅助催化的方法,通过金属有机化学气相沉积技术制备了GaAs纳米线及GaAs/InGaAs纳米线异质结构.通过对扫描电子显微镜（SEM）测试结果分析,发现温度会改变纳米线的生长机理,进而影响形貌特征.在GaAs纳米线的基础上制备了高质量的纳米线轴、径向异质结构,并对生长机理进行分析.SEM测试显示,GaAs/InGaAs异质结构呈现明显的“柱状”形貌与衬底垂直,InGaAs与GaAs段之间的界面清晰可见.通过X射线能谱对异质结样品进行了线分析,结果表明在GaAs/InGaAs轴向纳米线异质结构样品中,未发现明显的径向生长.从生长机理出发分析了在GaAs/InGaAs径向纳米线结构制备过程中伴随有少许轴向生长的现象.     

Growth and characterization of type-II ZnO/ZnTe core-shell nanowire arrays for solar cell applications

Large area, well-aligned type-II ZnO/ZnTe core-shell nanowire arrays have been fabricated on an a-plane sapphire substrate. The ZnO nanowires were grown in a furnace by chemical vapor deposition with gold as catalyst and then were coated with a ZnTe shell on the ZnO nanowires surface by a metal-organic chemical deposition chamber. The morphology and size distribution of the ZnO/ZnTe core-shell nanowire arrays were studied by scanning electron microscopy (SEM) and the crystal structure was examined by x-ray diffraction (XRD). Transmission measurement was used to study the optical properties of the core-shell nanowires. The results indicated that the ZnO/ZnTe core-shell nanowire arrays have good crystalline quality. In addition, it was found that the nanowire arrays have good light absorption characteristics and these properties make it suitable for making photovoltaic devices.     

Self-assembled periodical polycrystalline-ZnO/a-C nanolayers on Zn nanowire

Zn nanowires with an epitaxial thin surface layer of zinc oxide were dispersed onto amorphous carbon films and stored at room temperature. After 1500 h, a self-organized equal-spaced zinc oxide (approximately 2 nm)/carbon (approximately 2.5 nm) multilayer structure was found to form outside the Zn nanowire, taking the place of the original ZnO surface layer. We carried a systematic study to clarify the self-formation mechanism of the periodical multilayers outside the Zn nanowire and found out that such a configuration originated from a chemical reaction between Zn and CO2 and were formed via a gas phase diffusion-interfacial chemical reaction-phase separation process.     

Photoluminescence of ZnO nanowires dependent on O2 and Ar annealing

High-purity ZnO nanowires have been synthesized on Si substrates without the presence of a catalyst at 600 °C by a simple thermal vapor technique. Photoluminescence (PL) spectra of the annealed samples at 900 °C under oxygen and argon gases have been investigated. After O₂ or Ar annealing, the PL visible-emission intensity that is related to intrinsic defects (oxygen vacancies) is greatly reduced compared with as-grown ZnO nanowires because the oxygen-gas ions or oxygen interstitials diffuse into the oxygen vacancies during annealing process. The blue-band peak of the O₂- or Ar-annealed ZnO naonowires is also smaller than the green-band peak in the visible broadband because of the reduction of oxygen vacancies. Therefore, the main intrinsic defects (oxygen vacancies) of as-grown ZnO nanowires can be reduced by O₂ or Ar annealing, which is an important procedure for the development of advanced optoelectronic ZnO nanowire devices.