PLD制备的籽晶层对ZnO纳米棒形貌及性能的影响

本文研究了脉冲激光沉积法(PLD)制备的不同籽晶层对水热生长ZnO纳米棒的形貌及发光性能的影响,通过比较得出,籽晶层是获得高度取向,排列有序的ZnO纳米棒的基础.电子回旋共振(ECR)氧等离子体参与沉积,有利于获得表面均匀且光滑平整的籽晶层,进而得到形貌及结晶质量较好的ZnO纳米棒.籽晶层的厚度不仅能够改变纳米棒的疏密程度,而且还能够改善纳米棒的取向性.通过调节籽晶层的退火温度可以调节纳米棒直径的大小,恰当的籽晶层退火温度也是获得形貌优良的ZnO纳米棒的一个关键因素.     

水热蒸汽法制备ZnO纳米棒的研究

采用新发展的水热蒸汽法,通过乙二胺蒸汽制备了高长径比的ZnO纳米棒.采用XRD、SEM、PL谱和拉曼光谱对产物进行了表征.结果表明ZnO纳米棒为六方柱形结构,纳米棒整体排列整齐,高度有序.ZnO纳米棒具有高度的取向性,沿c轴择优生长,大部分的ZnO纳米棒都垂直于基底.ZnO纳米棒在385 nm有一个本征发光峰,在433 nm、481 nm、520 nm之间有明显的缺陷发光峰,可能是由于氧空位和锌空位引起的.在生长温度为150℃的时候,450 ～ 550 nm之间发光峰强度远大于其他温度,可能是温度太高,生长速度太快,缺陷相对较多.ZnO纳米棒在437.61 cm-处特征峰明显,其峰值较高,结晶度较好,由于衬底存在微小的晶格失配,所以存在压应力.在120℃的生长温度,生长时间为12 h下,制备出的ZnO纳米棒长度为24 μm,直径为180 nm,长径比达到130:1.     

Co掺杂浓度对ZnO纳米棒结构和光学性能影响研究

采用水热法以不同浓度Co掺杂合成了具有六方纤锌矿结构的ZnO纳米粉体,通过X-射线衍射(XRD)、扫描电镜(SEM)、拉曼光谱、X射线光电子光能谱分析法(XPS)、(光致发光)PL谱等分别对样品的形貌、结构、光学性能进行了测试和表征.结果 表明:随着Co掺杂浓度的增大,纤锌矿ZnO的晶体结构没有改变,且Co以二价离子Co2+的形式掺杂进入ZnO晶格;同时花状ZnO纳米棒的均匀性变差,不同浓度Co掺杂ZnO纳米棒中均出现了少量且尺寸较小的单根纳米棒.PL光谱显示:随着Co掺杂浓度增大,样品的紫外发光峰没有明显地变化,而可见发光峰的强度先减小再增大,说明样品的缺陷先降低再提高.当Co掺杂的浓度为2.0;时,所制备的ZnO花状纳米棒可见发光峰相对最低,其具有较小的缺陷.     

水热法制备类花状MoS2纳米纸微球

采用水热合成技术,以钼酸钠、硫脲为反应剂,草酸为助还原剂,去离子水为溶剂,合成了类花状结构的MoS2纳米纸微球,采用X射线衍射仪(XRD)、拉曼光谱、透射电镜(HRTEM)、扫描电子显微镜(SEM)和X射线能量色散谱(EDS)对样品的结构、形貌和成分进行分析,重点研究了草酸浓度对MoS2纳米纸微球的形貌和结构的影响规律.结果表明:在适当的反应剂浓度下,合成的MoS2是由大量厚度约30 nm左右的纳米纸花瓣聚集在一起形成的类花状微球组成的.MoS2微球具有2H型六方晶系结构,而每片纳米纸花瓣是单晶结构的层状MoS2.反应前驱液中草酸的浓度对微球的大小、形貌和结晶度有显著的影响.最后讨论了类花状结构的MoS2纳米纸微球的生长机理.     

ZnO纳米颗粒团聚微球的生长机理研究

采用化学浴沉积法,以Zn(CH3COO)2和TEA为反应体系,制备了ZnO纳米颗粒团聚微球,并对不同陈化时间阶段下的产物分别进行了物相、形貌、热重以及傅里叶红外吸收光谱表征,同时研究了不同TEA含量对最终产物的影响.结果表明:在恒温陈化过程中,首先会生成纳米片状的Zn5(OH)8Ac2·2H2O,同时它们之间相互连接为花状结构.其次随着陈化时间的增加,花状的Zn5(OH)8Ac2·2H2O不断分解为ZnO纳米颗粒,最后ZnO纳米颗粒会进一步自组装为一定尺寸的微米球.     

电沉积法制备ZnO纳米棒阵列及其发光特性

本文以掺F的SnO2导电玻璃为基板,以硝酸锌水溶液为电解液,采用三电极恒电位体系电沉积制备ZnO纳米棒阵列,系统考察了硝酸锌浓度和沉积电位等工艺参数对ZnO纳米棒阵列的微观形貌及其发光性能的影响规律.结果表明,硝酸锌浓度和沉积电位对纳米棒阵列的形貌有显著影响,控制适宜的工艺条件可以制备出直径分布均匀、结晶性好且纯度高的六方纤锌矿ZnO纳米棒阵列.荧光光谱分析表明,电沉积制备出的ZnO纳米棒阵列在385 nm附近有一个强荧光发射峰,且发光性能稳定、对纳米棒阵列微观形貌的细微变化不敏感,使其在发光二极管和激光器等领域具有广阔的应用前景.     

化学浴沉积法制备多级结构ZnO微球及其电池性能

以三乙醇胺(TEA)和二水乙酸锌(Zn(CH3COO)2·2H2O)为原料,采用化学浴沉积法制备多级结构ZnO微球,并将获得的多级结构ZnO微球粉应用于染料敏化太阳能电池(DSSCs)光阳极.主要研究了TEA量和反应时间对产物形貌和电池性能的影响.采用SEM和XRD分析对多级结构ZnO微球进行形貌和物相表征,采用Ⅰ-Ⅴ测试仪和电化学工作站对电池性能进行了分析.结果表明:反应温度80℃,反应时间2h,TEA/水为0.15时所制备的多级结构ZnO微球粉组装成电池性能最佳,其光电转化率为3.18;,开路电压为0.64V,短路电流为9.36 mA·cm-2,填充因子0.53.     

柔性有序ZnO纳米棒/TiO2纳米粒子复合薄膜的制备及其光电转换性能研究

采用电沉积法,在柔性不锈钢网基底上制备了ZnO纳米棒阵列,随后旋涂P25浆料,最终经退火后得到了ZnO纳米棒阵列/TiO2纳米粒子的复合结构薄膜,详细探讨了TiO2纳米粒子的填充,初级ZnO纳米棒阵列的形貌,P25浆料的旋涂次数以及表面活性剂PEG添加量等制备条件对复合结构光阳极形貌及光电性能的影响.研究表明:TiO2纳米粒子的引入能有效提高光阳极的比表面积,增强半导体与染料的耦合能力,ZnO纳米棒阵列能够为电子提供快速传输的通道.最佳制备条件为:初级ZnO纳米棒沉积次数为两次,浆料浓度为1 g/50 mL,旋涂浆料次数为三次,PEG添加量为4g/100 mL,制备的复合结构DSSC的光电转换效率较单一纳米棒阵列有一定的提高.     

Ti离子注入对ZnO纳米棒阵列性能的影响

本文研究了Ti离子注入对ZnO纳米棒阵列结构、形貌、光学特性和疏水性的影响.XRD测试表明注入前后ZnO纳米棒均为六方纤锌矿晶体结构.然而,随着对ZnO纳米棒阵列注入剂量的增加,样品沿(002)晶面优先生长的趋势降低,而且当注入剂量达到5×1017/cm2时,甚至出现ZnTiO3( 104)晶面衍射峰,说明了这种物质的存在,而后面的XPS表征也进一步证明了Ti-Zn-O化学键的存在.样品形貌测试表明,离子注入后由于受刻蚀和溅射的作用,不仅使得ZnO纳米棒表面形貌发生了很大的变化,透光率也显著下降.离子注入后ZnO纳米棒表面疏水性受形貌变化的影响也发生了改变,使得其疏水性增强,当Ti离子注入量为1×1017/cm2时ZnO纳米棒表面接触角达到了151.4°.总之,离子注入作为一种较新颖的表明改性方法,通过对ZnO纳米棒阵列改性处理可以明显扩展其潜在应用价值.     

水热合成法制备纳米氧化锌粉

采用水热法合成了氧化锌纳米棒,研究了不同合成条件对ZnO纳米晶的影响.采用碱式碳酸锌作为前驱体,水为水热介质,可获得氧化锌纳米棒,水热时间的延长和水热温度的提高都使氧化锌纳米棒的长径比减小,其紫外发射光和近红外发射强度增大.当在体系中加入聚乙二醇时,可获得片状氧化锌结晶.当以0.5 mol/L的碳酸钠水溶液为水热介质,可得到长径比超过20,直径为500 nm左右分散均匀的纳米氧化锌棒.以氢氧化锌为前驱体,也能得到氧化锌纳米棒,其长径比为15左右.     

氧化锌纳米棒的制备及其光电性能的研究

以硝酸锌Zn(NO3)2·6H2O和六次甲基四胺(HMT)为原料,通过水热法制备出氧化锌纳米棒,研究了反应时间和冷却时间对产物形貌和尺寸的影响.采用扫描电子显微镜(SEM)、X射线衍射(XRD)、光致发光谱(PL)、紫外-可见光谱、红外光谱(FT-IR)表征产物的结构和性能.结果表明,反应时间为6 h和急速冷却至室温条件下合成样品为六方纤锌矿氧化锌纳米棒,平均直径为300 nm;样品具有良好的结晶质量和发光性能,样品在200～400nm有较强的紫外吸收性能;FT-IR图谱表明产物在430 cm-1左右出现了Zn-O特征吸收峰,并有所红移;样品的开启场强为2.2 V/μm,场增强因子为2550,当场强为4.75 V/μm时,电流密度可以达到0.7 mA/cm2,是一种性能优良的冷阴极电子发射源.     

梳子状ZnO纳米棒阵列的制备及表征

采用水热法在HTlc-ZnAlCO3纳米片上对称生长出平行排列的梳子状ZnO纳米棒.利用X射线衍射(XRD)、场发射扫描电子显微镜(FESEM)对得到的样品进行表征.揭示ZnO纳米棒的可控生长规律,在此基础上对其生长机理进行初步探讨.     

钇掺杂多孔结构氧化锌纳米棒的制备与性能研究

采用两步法在二氧化锡掺氟(SnO2:F,FTO)导电玻璃基板上制备出钇(Y)掺杂多孔结构氧化锌(ZnO)纳米棒,首先利用浸渍-提拉法在FTO导电玻璃基板上制备ZnO晶种层,然后利用水热法在ZnO晶种层上生长Y掺杂ZnO纳米棒.研究了不同浓度Y掺杂ZnO纳米棒的晶相结构、微观形貌、化学组成及光学性能.实验结果表明:所制备的Y掺杂ZnO纳米棒为沿c轴择优取向生长的六方纤锌矿结构,随着Y掺杂浓度的增加,ZnO纳米棒(002)衍射峰强度先增大后减小,纳米棒的平均长度由1.3μm增加到2.6μm.ZnO纳米棒的形貌由锥状结构向柱状结构演化,纳米棒侧面的孔洞分布密度增加.所制备的Y掺杂ZnO纳米棒具有一个较弱的紫外发光峰和一个较强的宽可见发光峰.所制备样品的光学带隙随着Y掺杂浓度的增加而减小,其光学带隙在3.29～3.21 eV之间变化.利用Y掺杂ZnO纳米棒作为量子点敏化太阳能电池的光阳极可极大提高太阳电池的光电转换效率.     

聚乙烯醇对ZnO纳米棒结构和光学性能的影响

以六水硝酸锌为锌源,聚乙烯醇(PVA)为分散剂,制备了纳米氧化锌(ZnO).利用X射线衍射(XRD)和电子扫描电镜(SEM)对氧化锌的晶体结构、形貌和尺寸进行了表征.利用吸收光谱对氧化锌的吸收率进行了测量.结果表明,所制备的氧化锌属于六方纤锌矿单晶结构,呈棒状结构.通过改变PVA含量,氧化锌纳米棒的长度可以从400nm到2μm可调.吸收光谱表明,随着PVA含量增加,吸收光谱发生红移.讨论了PVA作用下氧化锌纳米棒的形成机理.     

Hydrothermal growth of ZnO nanorods on a-plane GaN/sapphire template

ZnO nanorod arrays are grown on a-plane GaN template/r-plane sapphire substrates by hydrothermal technique. Aqueous solutions of zinc nitrate hexahydrate and hexamethylenetetramine were employed as growth precursors. Electron microscopy and X-ray diffraction measurements were carried out for morphology, phase and growth orientation analysis. Single crystalline nanorods were found to have off-normal growth and showed well-defined in-plane epitaxial relationship with the GaN template. The 〈0 0 0 1〉 axis of the ZnO nanorods were observed to be parallel to the 〈1 0 1¯ 0〉 of the a-plane GaN layer. Optical property of the as-grown ZnO nanorods was analyzed by room temperature photoluminescence measurements.     

Surface‐morphology evolution of ZnO nanostructures grown by hydrothermal method

Surface‐morphology evolution of ZnO nanocrystals has been observed by the hydrothermal process. The effects of stirring time and ammonia content on the morphology evolution have been discussed, respectively. Extension of stirring time of the precursor results in morphology transformation from star‐like to wire‐like ZnO nanocrystals. ZnO nuclei aggregation and uniform Zn(OH)₂ precipitation can readily explain these two morphologies, respectively. By increasing the ammonia content in the solution, the morphology of ZnO crystals is transformed from an irregular shape to hexagon sheets to nanorods, and the side length of ZnO crystals is decreased accordingly. Hollow structures are realized at the subsequent solution aging process. Variation of zinc ammonic complex and minimum surface energy can well explain the morphology evolution of ZnO nanostructures.     

Hydrothermal synthesis and characterization of micro/nanostructured ZnSn(OH)6/ZnO composite architectures

Micro/nanostructured ZnSn(OH)₆/ZnO composite architectures were synthesized through a simple one‐step hydrothermal method. Phase structure and morphology of the products were characterized by using X‐ray diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscope (TEM). ZnSn(OH)₆ microcubes and ZnO nanorods with uniform size were interconnected to form the micro/nanostructured architectures. ZnO nanorods preferentially grow at edges and corners of the microcubes. Morphology of the products was susceptible to concentration of the reactants. With increasing reactant concentration, the ZnO nanorods grown on the surfaces of ZnSn(OH)₆ microcubes disappeared. Meanwhile, the smooth surfaces of the ZnSn(OH)₆ microcubes become coarsened and were etched to spherical outlines. Growth mechanism of the micro/nanostructured ZnSn(OH)₆/ZnO composite architectures was discussed and thermal decomposition properties of the micro/nanostructured ZnSn(OH)₆/ZnO composite architectures at high temperature were examined. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Facile synthesis of pencil‐like ZnO nanostructures at low temperature

Pencil‐like ZnO nanostructure was synthesized by directly oxidizing granular Zn films, which was thermal deposited in a nitrogen atmosphere from Zn powder in a horizontal tube furnace. The formation of the pencil‐like structure, including a hexagonal rod and a sharp tip with diameter about 60 nm, highly depend on the thickness of the initial zinc film and the temperature of the oxidizing process. ZnO nanorods were formed in a relatively low temperature, while thicker zinc film was apt to form a dense ZnO film with tubular structures. The different structured ZnO materials showed distinguishing optical properties which indicate the intrinsic defects forming in the different growth conditions. The pencil‐like ZnO structures exhibit a relatively strong green emission attributed to the high concentrations of oxygen vacancies and its taper tip has great prospects in field‐emission devices.     

Optimization of hydrothermal growth ZnO Nanorods for enhancement of light extraction from GaN blue LEDs

In this study, we report on the enhancement in the light extraction efficiency of GaN blue LEDs topped with ZnO nanorods. The ZnO nanorods were grown by a two-step hydrothermal synthesis with pre-coated ZnO nanoparticles under optimized condition to give the appropriate size and quality, giving an increase in the light output efficiency of 66%. This improvement is attributed to the optimal rod size and spacing with improved thermal dissipation as compared to light extraction from plain GaN surface. During the ZnO growth on the LEDs, 0.55 M of NH₃ was added and the ZnO sample was later annealed at 475 °C in N₂ ambient, to drive out interstitial oxygen atoms from the tetrahedral unstable site. As a result, a high ratio of UV to orange defect band emission was achieved. The two-step growth of ZnO nanorods on GaN LEDs was effective in generating array of ZnO nanorods which serve as reflector to enhance light extraction from LEDs.     

The effect of cooling rate during hydrothermal synthesis of ZnO nanorods

The hydrothermal method was employed in order to obtain zinc oxide nanorods directly on Si/SiO₂/Ti/Zn substrates forming brush-like layers. In the final stages of synthesis, the reaction vessel was naturally cooled or submitted to a quenching process. X-ray diffraction results showed that all the nanostructures grew [0 0 0 1] oriented perpendicular to the substrate. The influence of the cooling process over the morphology and dimensions of the nanorods was studied by scanning electron microscopy. High-resolution transmission electron microscopy images of the quenched samples showed that the zinc oxide (ZnO) crystal surfaces exhibit a thin-layered coating surrounding the crystal with a high degree of defects, as confirmed by Raman spectroscopy results. Photodetectors made from these samples exhibited enhanced UV photoresponses when compared to the ones based on naturally cooled nanorods.