水浴法制备ZnO纳米棒及其场发射性能

用硝酸锌(Zn(NO3)2·6H2O)与六亚甲基四胺(C6H12N4)以等浓度配制成反应溶液,通过水浴法制备出了形貌可控的棒状ZnO纳米结构,讨论了不同反应浓度及衬底对ZnO表面形貌的影响.样品的XRD和扫描电子显微镜分析结果表明,所得产物均为六方纤锌矿结构,在有晶种层的衬底上制备出的ZnO纳米棒沿(001)方向并垂直于衬底表面生长.随着反应浓度的增加,ZnO纳米棒的直径增大,长径比减小.样品的场发射性能测试表明,反应溶液浓度为0.005 mol/L,以铜膜为晶种层的硅衬底上制备出的场发射阴极具有较好的场发射性能.     

晶种分布对氧化锌纳米棒生长的影响

采用水热法在氧化锌晶种修饰的衬底上生长氧化锌纳米棒,利用扫描电子显微镜(SEM)和X射线衍射仪(XRD)系统地分析了晶种分布状态对氧化锌纳米棒排列的影响.SEM结果表明随着晶种密度的增大,氧化锌纳米棒从排列无序向具有高度取向的紧密有序纳米棒阵列转变,反映纳米棒端面垂直生长优化;XRD表征显示,随着晶种密度的增大,(002)峰增强,(110)峰减弱,即端面衍射增强,侧面衍射减弱,与SEM结果相对应.同时在生长的氧化锌纳米棒中存在链状和花状的簇结构,分析表明这些簇结构与晶种在衬底上的特殊分布状态有关.     

实验条件对二氧化钛纳米棒形貌和光电流密度的影响

采用简单的水热合成法,以四异丙醇钛为钛源,制备出整齐有序的二氧化钛纳米棒阵列。探索了钛源浓度、反应液酸度、反应时间、温度等实验条件对纳米棒的形貌和光电流密度的影响。实验结果表明:钛源浓度和反应液酸度对纳米棒的生长有非常大的影响,最佳反应液的组分为10 mL去离子水、10 mL盐酸和0.4 mL钛源。另外,随着反应时间的增加,纳米棒的长度会明显的增加,但纳米棒的直径和光电流密度却变化不大。同时,纳米棒的长度也随着反应温度的增高而增加,其光电流密度随之呈现先增大后减小的趋势,但其直径没有明显改变。     

一维有序ZnO纳米棒阵列的制备与表征

通过改进传统水热法的密闭、高压的条件,在非密闭、常压环境下在氧化铟锡玻璃衬底上自组装生长了取向高度一致并且分散性好的ZnO纳米棒阵列.首先将乙酸锌溶胶旋涂到氧化铟锡玻璃衬底上,经热处理得到致密的ZnO纳米晶薄膜,然后将其垂直放入前驱体溶液中通过化学溶液沉积生长得到ZnO纳米棒阵列.室温条件下,对样品进行了SEM和XRD的测试.表明生成的氧化锌纳米棒阵列沿c轴取向,实现了定向生长,且纳米棒结晶较好,为六方纤锌矿结构,直径约为40 nm,长度达到微米量级.室温下的吸收光谱表明,由此方法得到的纳米棒纯度较高,有强的紫外吸收.室温下,观测到了该有序ZnO纳米棒阵列在387 nm处强的窄带紫外发射,半高宽小于30 nm,在468 nm处还有一强度较弱的蓝光发射峰.     

水热法制备Co掺杂ZnO纳米棒及其光学性能

采用水热法在石英衬底上以Zn(CH3COO)2.2H2O和Co(NO3)2.6H2O水溶液为源溶液,以C6H12N4(HMT)溶液作为催化剂,在较低温度下制备了Co掺杂的ZnO纳米棒。采用X射线衍射(XRD)和扫描电子显微镜(SEM)对所生长ZnO纳米棒的晶体结构和表面形貌进行了表征,考察了Co掺杂对ZnO纳米棒微观结构和对发光性能影响的机制。结果表明:Co掺杂的ZnO纳米棒呈六方纤锌矿结构,具有沿(002)面择优生长特性,Co掺杂使ZnO纳米棒的直径变细;同时室温光致发光(PL)谱检测显示Co掺杂ZnO纳米棒具有很强的近带边紫外发光峰,而与深能级相关的缺陷发光峰则很弱。本研究采用水热法在石英衬底上于较低温度下生长出了具有较高光学质量的Co掺杂ZnO纳米棒。     

基于柔性衬底的二维ZnO压电纳米发电器件

采用二次水溶液法在柔性PET-ITO衬底上生长二维ZnO纳米片状结构,研制出基于二维ZnO纳米片阵列的新型直流压电纳米发电机.SEM图像显示纳米片结构均匀致密地分布在柔性PET-ITO衬底表面,XRD图显示纳米片阵列具有明显的六方纤锌矿结构的特征,对称的I-V特性曲线说明纳米棒阵列与上下电极均形成肖特基接触.压电应变特性表明:纳米发电机输出电流与外力大小有关,随着外力增加,最高输出电流达到300nA.     

联合体驱使生长法制备ZnO纳米棒及其表征

在常压环境下采用联合体驱使生长(Aggregation-driven growth)法在镀有ZnO纳米薄膜的医用盖玻片衬底和锌箔上制备了不同直径、高取向、密集生长的ZnO纳米棒阵列结构,发现平均直径与生长时间呈线性关系。X射线衍射(XRD)谱图中出现了较强的(002)峰,表明制备的纳米棒阵列具有高度c轴择优生长取向;高分辨透射电子显微镜(HRTEM)和选区电子花样衍射图谱(SAED)结果表明我们得到的单根纳米棒为沿(002)生长的单晶结构。分析确定盖玻片上的纳米棒阵列是以ZnO纳米薄膜缓冲层上的ZnO种子颗粒为成核点生长形成的。     

醋酸锌一步溶液法制备的各种形貌ZnO棒

采用一步化学溶液法在玻璃衬底上通过改变溶液浓度、酸碱度等影响因素生长出不同形貌和不同尺寸的ZnO棒。已生长出的ZnO棒的形貌有细长棒形,垂直于衬底的规则六角形,短而粗的六角形,橄榄形,圆头或平头对称双棒和花生米粒形。分析了酸碱度、溶液浓度、催化剂和温度对生成的ZnO样品形貌的影响,以及分析了其生长机理。随着溶液浓度的增加,生成的ZnO棒的长径比随之减小。溶液浓度为0．01mol／L时,细棒的长径比约为20～70,而当溶液浓度为0．5mol／L时,规则六角短棒的长径比约为0．5～1。当溶液浓度为0．1mol／L,可以生成截面十分规则的六角形且端面为平面的棒状ZnO。随着溶液酸碱性的增强,生成的ZnO棒由细长棒（弱酸性条件）过渡到圆头短棒（弱碱性条件）,溶液的碱性继续增强,可以生成橄榄形。当碱性很强时,生成颗粒状。测量了样品的XRD,扫描电镜像和光致发光光谱。     

金纳米颗粒等离激元对不同形貌氧化锌薄膜发光性能的调控

采用化学气相沉积法制备了纳米棒状的氧化锌纳米结构薄膜和没有纳米棒的氧化锌薄膜,通过直流溅射在所制备的有纳米棒和没有纳米棒的氧化锌薄膜上淀积约3 nm厚的金纳米颗粒薄膜,研究了金纳米颗粒对不同表面形貌氧化锌薄膜的发光特性的影响。实验发现金纳米颗粒的存在使具有纳米棒的氧化锌薄膜的紫外发射增强,但使来自缺陷的可见光发射受到很大的抑制。通过比较有纳米棒和没有纳米棒的氧化锌薄膜在镀金纳米颗粒前后的发光特性,发现金表面等离激元对氧化锌发光的调控取决于氧化锌的表面形貌,纳米棒的存在更有利于金纳米颗粒等离激元调控氧化锌的发光特性。     

氧化锌纳米棒的生长过程研究

利用高分子聚乙烯吡咯烷酮(PVP)和乙酸锌的配合物作为前驱体,在300 ℃温度下煅烧,并制备了氧化锌纳米棒。生成的产物用XRD,TEM,SAED等测试方法进行了表征。为了研究氧化锌纳米棒的生长过程,我们通过控制制备前驱体所需原料的比例不变,改变在300 ℃温度下煅烧的时间,分别为0.5, 3, 12和24 h,来观察生成产物的形貌特征。实验发现在110 ℃温度下干燥的前驱体中已经有氧化锌微晶生成;在300 ℃温度下煅烧0.5 h后就出现了明显的由几个纳米大小的微晶所组成的氧化锌纳米棒;煅烧3 h后的产物是结构非常完整的径直单晶ZnO纳米棒;12和24 h煅烧前驱体生成的ZnO纳米棒长度有所增加,ZnO的量基本保持不变。实验发现氧化锌的生长是沿着c轴方向,但是在横向也有生长方向。     

Controllable growth of well-aligned ZnO nanorod arrays by low-temperature wet chemical bath deposition method

Well-aligned ZnO nanorod arrays were synthesized by low-temperature wet chemical bath deposition (CBD) method on Si substrate under different conditions. Results illustrated that dense ZnO nanorods with hexagonal wurtzite structure were vertically well-aligned and uniformly distributed on the substrate. The effects of precursor concentration, growth temperature and time on nanorods morphology were investigated systematically. The mechanism for the effect of preparation parameters was elucidated based on the chemical process of CBD and basic nucleation theory. It is demonstrated that the controllable growth of well-aligned ZnO nanorods can be realized by readily adjusting the preparation parameters. Strong near-band edge ultraviolet (UV) emission were observed in room temperature photoluminescence (PL) spectra for the samples prepared under optimized parameters, yet the usually observed defect related deep level emissions were nearly undetectable, indicating high optical quality ZnO nanorod arrays could be achieved via this easy process chemical approach at low temperature.     

Site‐specific deposition of Ag nanoparticles on ZnO nanorod arrays via galvanic reduction and their SERS applications

A controllable heterostructure consisting of ZnO nanorod arrays with attached Ag nanoparticles at only one end has been synthesized via a facile and convenient galvanic reduction method. Scanning electron microscopic images of these nanostructures showed good selectivity of Ag deposition on the tip of ZnO nanorod arrays. The formation of these regular Ag ZnO heterogeneous nanorod arrays can be explained by a localization of the electrons at the ends of the ZnO nanorods after the electron transfer step. By tuning the reaction time and the concentration of silver nitrate, the density of Ag nanoparticles on the tip of ZnO nanorods can be well controlled. Owing to the introduction of Ag nanoparticles with different densities, the resulting Ag ZnO heterogeneous nanorod arrays have been proved to be a versatile substrate for surface‐enhanced Raman scattering not only for common organic molecules but also for label‐free protein detection. Copyright © 2009 John Wiley & Sons, Ltd.     

Alignment-controlled hydrothermal growth of well-aligned ZnO nanorod arrays

ZnO nanorod arrays (ZNAs) were prepared via a two-step seeding and solution hydrothermal growth process. Effects of preparing parameters such as seed layer, colloid concentration, substrate and precursor concentration, on the alignment control of ZNAs were systematically investigated. The deviation angle of ZnO nanorods was measured to evaluate the alignment of arrays. Results show that seed layer not only controls the vertical orientation of ZNAs, but also the compactness of ZNAs. Altering colloid concentration and substrate can influence the microstructure of ZnO seed layer and affect the ordered alignment of ZNAs. The precursor concentration has an insignificant effect on the alignment of ZNAs but has great impact on the morphology of ZNAs. Alignment-controlled and well-aligned ZnO nanorods with different diameter and aspect ratio can be obtained by properly controlling the preparing parameters. A growth mechanism was proposed for the growth of ZnO nanorods.     

Growth of ZnO nanorods by aqueous solution method with electrodeposited ZnO seed layers

ZnO nanorod arrays on ZnO-coated seed layers were fabricated by aqueous solution method using zinc nitrate and hexamethylenetetramine at low temperature. The seed layers were coated on ITO substrates by electrochemical deposition technique, and their textures were dominated by controlling the deposition parameters, such as deposition potential and electrolyte concentration. The effects of the electrodeposited seed layers and the growing parameters on the structures and properties of ZnO nanorod arrays were primarily discussed. The orientation and morphology of both the seed layer and successive nanorods were analyzed by using X-ray diffraction (XRD), SEM and TEM. The results show that the seed layer deposited at −700 mV has evenly distributed crystallites and (0 0 2) preferred orientation; the density of resultant nanorods is high and ZnO nanorods stand completely perpendicular onto substrates. Meanwhile, the size of nanorods quite also depends on the growth solution, and the higher concentration of growth solution primary leads to a large diameter of the ZnO nanorods.     

硝酸铟诱导的电沉积氧化锌纳米柱光学性质裁剪

为在新型太阳能电池等光电器件中应用ZnO纳米结构,需要对ZnO纳米结构阵列的几何形貌及光电物理性质进行裁剪与操控。采用电化学沉积路线制备ZnO纳米柱阵列,In(NO3)3与NH4NO3两种盐类被溶入在传统Zn(NO3)2主电解液中。对ZnO纳米柱阵列进行扫描电子显微镜、透射反射光谱、光致发光光谱测试,分析其形貌与光电物理性质。随着引入的In(NO3)3浓度的增加,ZnO纳米柱阵列的平均直径随之由57 nm减小至30 nm。同时ZnO纳米柱的阵列密度也可降低,进而增大纳米柱间距至41 nm。由于新的盐类的引入,ZnO纳米柱的光学带隙由3.46 eV蓝移至3.55 eV。随着电解液中In(NO3)3的增加,ZnO纳米柱的斯托克斯位移由198 meV减小至154 meV,ZnO纳米柱中的非辐射复合可以得到一定程度的抑制。通过在主电解液中引入In(NO3)3与NH4NO3两种盐类,可对ZnO纳米柱的直径、密度、间距、透射反射率、光学带隙、近带边发射与非辐射复合进行操控与裁剪。     

Controlling the orientation of ZnO nanorod arrays using TiO<Subscript>2</Subscript> thin film templates dip-coated by sol–gel

The oriented ZnO nanorod arrays have been synthesized on a silicon wafer that coated with TiO₂ films by aqueous chemical method. The morphologies, phase structure and the photoluminescence (PL) properties of the as-obtained product were investigated by field-emission scanning electron microscopy (FE-SEM), X-ray diffractometer (XRD), transmission electron microscope (TEM) and PL spectrum. The nanorods were about 100 nm in diameter and more than 1 μm in length, which possessed wurtzite structure with a c axis growth direction. The room-temperature PL measurement of the nanorod arrays showed strong ultraviolet emission. The effect of the crystal structure and the thickness of TiO₂ films on the morphologies of ZnO nanostructures were investigated. It was found that the rutile TiO₂ films were appropriate to the oriented growth of ZnO nanorod arrays in comparison with anatase TiO₂ films. Moreover, flakelike ZnO nanostructures were obtained with increasing the thickness of anatase TiO₂ films.     

A template-free sol-gel technique for controlled growth of ZnO nanorod arrays

The growth of ZnO nanorod arrays via a template-free sol-gel process was investigated. The nanorod is single-crystalline wurtzite structure with [0 0 0 1] growth direction determined by the transmission electron microscope. The aligned ZnO arrays were obtained directly on the glass substrates by adjusting the temperatures and the withdrawal speeds, without seed-layer or template assistant. A thicker oriented ZnO nanorod arrays was obtained at proper experimental conditions by adding dip-coating layers. Room temperature photoluminescence spectrum exhibits an intensive UV emission with a weak broad green emission as well as a blue double-peak emission located at 451 and 468 nm, respectively. Further investigation results show that the difference in the alignment of nanorods ascribes to the different orientations of the nanoparticles-packed film formed prior to nanorods on the substrate. Well ordered ZnO nanorods are formed from this film with good c-axis orientation. Our study is expected to pave a way for direct growth of oriented nanorods by low-cost solution approaches.     

电沉积法制备ZnO纳米柱及其机制研究

采用阴极还原方法,以Zn(NO₃)₂水溶液为电解液制备ZnO纳米柱。分析了不同沉积电位和不同沉积时间的缓冲层对ZnO纳米柱的密度、形貌及取向的影响。通过分析缓冲层在不同沉积时间下的电流密度变化,研究了缓冲层对ZnO纳米柱密度影响的机理。利用扫描电子显微镜(SEM)和X射线衍射(XRD)分析了样品的表面形貌及结构。研究结果表明,缓冲层能够增加ZnO纳米柱的密度及c轴的取向性,当缓冲层的沉积时间为60 s时,可以得到密度最大、取向最好的ZnO纳米柱。     

Aligned ZnO nanorod arrays fabricated on Si substrate by solution deposition

Aligned ZnO nanorod arrays were fabricated by chemical solution deposition based on Si substrate which was spin coated with ZnO colloid as nucleation seeds. Their microstructures were characterized by X-ray diffraction, scanning electron microscopy, and high-resolution transmission electron microscopy. The results indicated that ZnO nanorods nucleated and grew vertically on Si substrates along the [0 0 1] direction with single-crystalline structure. The diameter of ZnO nanorods was greatly affected by the grain size of ZnO seeds. Room-temperature photoluminescence of nanorods has a strong emission band at about 384 nm.     

Characterisation of ZnO nanorod arrays grown by a low temperature hydrothermal method

In this paper, growth steps of well defined ZnO nanorod arrays deposited on seeded substrates were investigated. To obtain ZnO seed layer on glass substrates, a successive ionic layer adsorption and reaction (SILAR) method was used and then ZnO nanorods were grown on seed layer using a chemical bath deposition (CBD) method. The effects of seed layer and deposition time on morphology, crystallographic structure (e.g. grain size, microstrain and dislocation density) and electrical characteristics of ZnO nanorods were studied. From the SEM micrographs, it could be seen that the ZnO nanorods densely covered the substrate and were nearly perpendicular to the substrate surface. The XRD patterns showed that the ZnO nanorod arrays had a hexagonal wurtzite structure with a preferred orientation along the (002) plane. An increase in deposition time resulted in an increase in the intensity of the preferred orientation and grain size, but a decrease in microstrain and dislocation density. Electrical activation energies of the structures were calculated as 0.15–0.85?eV from current–temperature characteristics. It was concluded that the morphologies of the structures obtained in this study via a simple and fast solution method can provide high surface areas which are important in area-dependent applications, such as solar cells, hydrogen conversion devices, sensors, etc.