常温直接沉淀法制备ZnO纳米棒

在常温下, 以PEG-400(聚乙二醇400)为表面活性剂, 采用直接沉淀法合成了ZnO纳米棒. 产物用XRD, TEM, SAED和 HRTEM等进行了表征. 结果表明, 所得ZnO为一维的纳米棒, 属于六方纤维矿的单晶结构. ZnO纳米棒的直径在20~40 nm之间, 长度在300~800 nm范围. (0001)面为ZnO纳米棒的生长方向. 讨论了ZnO相的生成和ZnO纳米棒的形成机理以及PEG-400在其形成过程中的作用.     

具有核壳结构的ZnO纳米棒@Ni-Co双氢氧化物复合物纳米片阵列的制备及其电化学性能

通过两步水热合成法制备了具有核壳结构的ZnO纳米棒@Ni-Co双氢氧化物复合材料纳米片阵列.首先,以碳布为基底,水热法生成的ZnO沉积在碳布上形成ZnO纳米棒花簇.其次,以ZnO纳米棒为模板,水热法生成的Ni-Co双氢氧化物纳米片沉积在ZnO纳米棒表面,形成ZnO纳米棒@Ni-Co双氢氧化物纳米片复合材料阵列.形貌、结构分析和电化学性能测试表明,以碳布为基底,成功地合成了以ZnO纳米棒为模板并具有核壳结构的ZnO纳米棒@Ni-Co双氢氧化物复合材料纳米片阵列,该复合材料纳米片阵列具有较大的纵横比,且分散均匀.合成的ZnO纳米棒@Ni-Co双氢氧化物复合材料纳米片阵列具有良好的电化学性能,当电流密度为1 A/g时,其比电容值可达531.6 F/g,该复合材料在超级电容器电极材料领域具有良好的应用前景.     

基底对电沉积制备ZnO纳米棒阵列的影响

采用恒电位电沉积方法, 在未经修饰的ITO导电玻璃基底上通过控制实验条件制备出不同形貌的纳米ZnO结构, 而在经过ZnO纳米粒子膜修饰后的ITO导电玻璃基底上, 制备出透明、高取向、粒径小于30 nm的ZnO纳米棒阵列. 用扫描电子显微镜(SEM)、X射线衍射(XRD)以及透射光谱对制备出的ZnO纳米棒阵列的结构、形貌和透明性进行了表征. 测试结果表明, ZnO纳米棒阵列的平均直径为21 nm, 粒径分布窄, 约18～25 nm, 择优生长取向为[001]方向, 垂直于基底生长. 当入射光波长大于400 nm时, ZnO纳米棒阵列的透光率大于95%.     

纳米氧化锌的标准摩尔生成焓

采用微乳液-水热辅助法合成了尺寸、形貌均匀的ZnO纳米棒,其长度约400 nm,直径约50 nm。基于将纳米ZnO与块体ZnO的标准摩尔生成焓相关联,依据热力学势函数法设计热化学循环,获得了纳米ZnO与块体ZnO标准摩尔生成焓的关系。结合微量热技术求算出了下所制备的ZnO纳米棒在298.15 K下的标准摩尔生成焓为(-331.70±0.42)kJ.mol-1。     

Co掺杂ZnO纳米棒的水热法制备及其光致发光性能

以Zn(NO3)2·6H2O 和Co(NO3)2·6H2O为原料, 通过水热法在较低温度下制备了纯ZnO和Co掺杂的ZnO(ZnO:Co)纳米棒. 利用XRD、EDS、TEM和HRTEM对样品进行了表征, 结合光致发光(PL)谱研究了样品的PL性能. 结果表明, 水热法制备纯ZnO和ZnO:Co纳米棒均具有较好的结晶度. Co2+是以替代的形式进入ZnO晶格, 掺入量为2%(原子分数)左右. 纯的ZnO纳米棒平均直径约为20 nm, 平均长度约为180 nm; 掺杂样品的平均直径值约为15 nm, 平均长度约为200 nm左右; Co掺杂轻微地影响ZnO纳米棒的生长. 另外, Co掺杂能够调整ZnO纳米棒的能带结构、提高表面态含量, 进而使得ZnO:Co纳米棒的紫外发光峰位红移, 可见光发光能力增强.     

微波法合成氧化锌纳米棒

以氯化锌为锌源,碳酸钠为矿化剂,水为溶剂,微波辐照10 min制备了结晶性好的半导体ZnO纳米棒.经XRD,FESEM,TEM和SAED表征,ZnO纳米棒直径为40 nm～80 nm,长度为300 nm～500 nm,沿着c轴择优取向生长.对ZnO纳米棒生长机制进行了分析.     

以CuC2O4微球为模板可控合成一维CuC2O4/ZnO异质结构

以CuC2O4纳米微球为模板,通过水热法在120 ℃、1 h时成功合成了一维CuC2O4/ZnO异质结构。 采用热重分析（TGA）、场发射扫描电子显微镜（FE-SEM）、能量散射Ｘ射线谱（EDX）、透射电子显微镜(TEM)和Ｘ射线粉末衍射(XRD)等测试技术对产物的结构和形貌进行了表征。 结果表明,所得产物为一维CuC2O4/ZnO纳米棒束,长约1 μｍ,直径约500 nm。 每个棒束由许多纳米棒沿同一方向组装而成。 TEM照片和EDX光谱表明,CuC2O4和ZnO形成了均匀的异质结构。     

ZnO纳米棒阵列在TiO2介孔薄膜上的生长及其表征

通过低温水热法成功地将ZnO纳米棒阵列定向生长在了介孔锐钛矿TiO2纳米晶薄膜上,并主要利用X射线衍射、场发射扫描电子显微镜和光致发光光谱等对其进行了表征。所制备的纳米棒具有六边形的端面,纳米棒的尺寸及端面边长分布范围窄,并且沿c轴方向(002)表现出了明显的择优化生长。此外,相比于玻璃基底或TiO2纳米颗粒薄膜,生长在介孔TiO2薄膜上的ZnO纳米棒阵列表现出了较好的取向生长,表明基底的表面结构和组成对ZnO纳米棒阵列的生长有显著的影响。根据基底有序的多孔结构,讨论了纳米棒阵列可能的生长机理。所得到的ZnO纳米棒阵列在室温下分别表现出了以370 nm为中心的强近紫外光和以530 nm为中心的弱绿光两条荧光谱带。     

一种在固体基底上制备高度取向氧化锌纳米棒的新方法

采用廉价、低温的方法，在修饰过ZnO纳米粒子膜的ITO基底上成功制备出具有 高长径比、高度取向的ZnO纳米棒阵列，用扫描电子显微镜(SEM)，X射线衍射(XRD) ，高分辨透射电子显微镜(HRTEM)以及拉曼光谱对制备出的ZnO纳米棒的结构和形貌 进行了表征，测试结果表明，ZnO纳米棒是单晶，属于六方晶系，与基底直，上仍 沿(001)晶面择优生长的特征，并且ZnO纳米棒基本上无氧空位的存在，统计结果显 示，水热反应2h后90%以上的ZnO纳米棒直径为120～190nm，长度为4μm     

Ag掺杂对n-ZnO纳米棒/p-GaN异质结结构和发光性能的影响

利用简单的水热合成法在p-GaN薄膜上制备了Ag掺杂的一维ZnO纳米棒(ZnO NRs),并且研究了Ag掺杂对于ZnO NRs结构和形貌以及n-ZnO NRs/p-GaN异质结发光特性的影响。结果表明,不同Ag掺杂浓度的ZnO纳米棒截面均呈六边形的棒状结构,且纳米棒的取向垂直于衬底;XRD分析结果表明,随着Ag掺杂浓度的增加,ZnO纳米棒(0002)晶面的峰位向衍射角减小的方向移动,表明Ag+置换了ZnO晶格中的部分Zn2+后使其晶格常数略增加;随着Ag掺杂浓度的增加,ZnO纳米棒近带边发光峰发生一定的红移并且强度逐渐减弱,黄带发光峰逐渐增强,n-ZnO NRs/p-GaN异质结具有更好的传输效率。     

ZnO纳米棒阵列的同步法制备及其PL性能研究

在较低温度下，采用化学法在Zn片和玻璃片上同步制备了ZnO纳米棒阵列。利用XRD、FESEM和HRTEM对样品进行了表征，并且通过光致发光谱研究了阵列的光致发光(PL)性能。结果表明，ZnO纳米棒阵列较为致密、取向性较好。纳米棒为六方纤锌矿相，沿c轴生长，平均直径约为60 nm。同步法制备的2种ZnO纳米棒阵列均具有较好的紫外和橙红色发光性能，但发光特性却存在一定差异，这可能主要是由于2种阵列中纳米棒的缺陷含量不同所致。     

纳米结构ZnO在TiO_2薄膜上的电化学沉积及其表征

在三电极体系中,以硝酸锌水溶液作为电解液,采用阴极还原电沉积法成功实现了一维纳米结构ZnO阵列在TiO2纳米粒子/ITO导电玻璃薄膜基底上的沉积,并通过XRD、SEM、EDS和PL光谱等方法对样品进行了表征.重点研究了薄膜基底、电解液浓度、沉积时间、六次亚甲基四胺(HMT)的引入对ZnO沉积及其发光性质的影响.结果显示:与ITO玻璃基底相比,ZnO更易于在TiO2纳米粒子薄膜上实现电化学沉积.ZnO属于六方晶系的铅锌矿结构,并且沿着c-轴方向表现出明显的择优化生长,以形成垂直于基底的ZnO纳米棒阵列.延长沉积时间、增加电解液浓度和引入一定量的HMT等均对ZnO的生长有促进作用,进而使其纳米棒的结晶度和取向程度提高,进而解释了所得的薄膜分别约在375和520nm处表现出ZnO的强而窄的带边紫外光发射峰和弱而宽的表面态绿光发射带.     

Electrochemical deposition of nano-structured ZnO on the nanocrystalline TiO2 film and its characterization

One-dimensional structure of ZnO nanorod arrays on nanocrystalline TiO₂/ITO conductive glass substrates has been fabricated by cathodic reduction electrochemical deposition methods in the three-electrode system, with zinc nitrate aqueous solution as the electrolyte, and were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) and photoluminescence (PL) spectra. The effects of film substrates, electrolyte concentration, deposition time, and methenamine (HMT) addition on ZnO deposition and its luminescent property were investigated in detail. The results show that, compared with on the ITO glass substrate, ZnO is much easily achieved by electrochemical deposition on the TiO₂ nanoparticle thin films. ZnO is hexagonally structured wurtzite with the c-axis preferred growth, and further forms nanorod arrays vertically on the substrates. It is favorable to the growth of ZnO to extend the deposition time, to increase the electrolyte concentration, and to add a certain amount of HMT in the system, consequently improving the crystallinity and orientation of ZnO arrays. It is demonstrated that the obtained ZnO arrays with high crystallinity and good orientation display strong band-edge UV (375 nm) and weak surface-state-related green (520 nm) emission peaks.     

Controlled growth of well-aligned ZnO nanorod array using a novel solution method

A simple method of synthesizing nanomaterials and the ability to control the size and position of them are crucial for fabricating nanodevices. In this work, we developed a novel ammonia aqueous solution method for growing well-aligned ZnO nanorod arrays on a silicon substrate. For ZnO nanorod growth, a thin zinc metal seed layer was deposited on a silicon substrate by thermal evaporation. Uniform ZnO nanorods were grown on the zinc-coated silicon substrate in aqueous solution containing zinc nitrate and ammonia water. The growth temperature was as low as 60-90 degrees C and a 4-in. wafer size scale up was possible. The morphology of a zinc metal seed layer, pH, growth temperature, and concentration of zinc salt in aqueous solution were important parameters to determine growth characteristics such as average diameters and lengths of ZnO nanorods. We could demonstrate the discrete controlled growth of ZnO nanorods using sequential, tailored growth steps. By combining our novel solution method and general photolithography, we selectively grew ZnO nanorod arrays on a patterned silicon substrate. Our concepts on controlled ZnO nanorod growth using a simple solution method would be applicable for various nanodevice fabrications.     

Low-temperature growth of ZnO nanorods by chemical bath deposition

Aligned ZnO nanorod arrays were synthesized using a chemical bath deposition method at normal atmospheric pressure without any metal catalyst. A simple two-step process was developed for growing ZnO nanorods on a PET substrate at 90-95 degrees C. The ZnO seed precursor was prepared by a sol-gel reaction. ZnO nanorod arrays were fabricated on ZnO-seed-coated substrate. The ZnO seeds were indispensable for the aligned growth of ZnO nanorods. The ZnO nanorods had a length of 400-500 nm and a diameter of 25-50 nm. HR-TEM and XRD analysis confirmed that the ZnO nanorod is a single crystal with a wurtzite structure and its growth direction is [0001] (the c-axis). Photoluminescence measurements of ZnO nanorods revealed an intense ultraviolet peak at 378.3 nm (3.27 eV) at room temperature.     

One-pot hydrothermal synthesis of heterostructured ZnO/ZnS nanorod arrays with high ethanol-sensing properties

ZnO/ZnS heterostructured nanorod arrays with uniform diameter and length were synthesized from zinc substrates in a one-pot procedure by using a simple hydrothermal method. Structural characterization by HRTEM indicated that the heterostructured nanorods were composed of parallel segments of wurtzite-type ZnO and zinc-blende ZnS, with a distinct interface along the axial direction, which revealed the epitaxial relationship, ZnO (1010) and ZnS (111). The as-prepared ZnO/ZnS nanorods showed only two green emissions at around 523?nm and 576?nm. We also found that the nanorods exhibited high sensitivity to ethanol at relatively low temperatures, owing to their smaller size and structure.     

氨水溶液制备ZnO纳米晶阵列的研究

以氨水和硝酸锌为前躯体，采用低温水溶液法在涂敷ZnO晶种层的玻璃衬底上外延生长了ZnO纳米棒晶阵列。应用SEM、TEM、SAED和XRD表征了ZnO纳米晶的形貌和结构。讨论了该组成体系水溶液法纳米棒外延生长的机理及其对棒晶形貌的影响。通过对水溶液pH值的原位二次调整，制备出了ZnO纳米管和表面绒毛状的棒晶阵列，基于生长机理探讨了它们的形成原因，为实现不同形貌ZnO纳米晶阵列的优化控制提供了可能的技术途径。结果表明，不同形貌的ZnO均属沿c轴择优取向的六方纤锌矿结构。     

Theoretical analysis of growth of ZnO nanorods on the amorphous surfaces

Semiconductor nanorod arrays on a substrate have a preferential alignment orientation that minimizes the excessive free energy of the system. In the case of wet chemically synthesized zinc oxide (ZnO) nanorod on the amorphous surfaces, the thermodynamic driving force determines the orientation to be normal to the surface. Among the various kinds of amorphous surfaces, the spherical seed layer composed of ZnO precursors gives isotropic radially aligned arrays. For other surfaces, such as wrinkled and planar ZnO precursor thin film, nanorod arrays are aligned to be perpendicular to the tangential line of the surface. The maximum value of the aspect ratio of the nanorod is determined by the thermodynamic relationship. The number density of nanorods per unit precursor particles decreases with increasing contact angle of the seed particles.     

Preparation and Photoluminescence of ZnO Comb-Like Structure and Nanorod Arrays

A large quantity of Zinc oxide (ZnO) comb-like structure and high-density well-aligned ZnO nanorod arrays were prepared on silicon substrate via thermal evaporation process without any catalyst. The morphology, growth mechanism, and optical properties of the both structures were investigated using XRD, SEM, TEM and PL. The resulting comb-teeth, with a diameter about 20 nm, growing along the 0001 direction have a well-defined epitaxial relationship with the comb ribbon. The ZnO nanorod arrays have a diameter about 200 nm and length up to several micrometers growing approximately vertical to the Si substrate. A ZnO film was obtained before the nanorods growth. A growth model is proposed for interpreting the growth mechanism of comb-like zigzag-notch nanostructure. Room temperature photoluminescence measurements under excitation wavelength of 325 nm showed that the ZnO comb-like nanostructure has a weak UV emission at around 384 nm and a strong green emission around 491 nm, which correspond to a near band-edge transition and the singly ionized oxygen vacancy, respectively. In contrast, a strong and sharp UV peak and a weak green peak was obtained from the ZnO nanorod arrays.