In-situ and ex-situ ZnO nanorod growth on ZnO homo-buffer layers

Vertically well-aligned ZnO nanorods were fabricated in-situ and ex-situ on ZnO homo-buffer layers using catalyst-free metal-organic chemical vapor deposition. Field-emission electron microscopy measurements demonstrated that the nanorods were well aligned and had a uniform diameter of 70–100 nm depending on the growth temperature, irrespective of growth conditions, in-situ and ex-situ. X-ray diffraction measurements demonstrated that the ZnO nanorods and the ZnO buffer layers had a wurtzite structure, and that the crystal quality of the nanorods grown on a smooth surface was better than that of the nanorods grown on a rough surface. Field-emission transmission electron microscopy measurements revealed the presence of a disordered layer at the interface of the nanorod and the buffer layer.     

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.     

Synthesis and microstructural properties of ZnO nanorods on Ti-buffer layers

This study examined the structural properties of ZnO nanorods grown on Ti-buffer layers with different surface roughnesses of 1.5 and 4.0 nm. Vertically aligned ZnO nanorods were synthesized on Al₂O₃ substrates with a Ti-buffer layer by metal-organic chemical vapor deposition. X-ray diffraction revealed the ZnO nanorods grown on a smooth surface to have higher quality and better alignment in the ab-plane than those grown on the rough surface. Field-emission transmission electron microscopy (FE-TEM) measurements revealed a disordered layer at the ZnO/Ti interface. FE-TEM demonstrated that the Ti-buffer layer contained a mixture of ordered and amorphous phases. Energy dispersive spectroscopy (EDS) analysis revealed the Ti-buffer layers to be entirely oxides.     

Growth and conductivity enhancement of N-doped ZnO nanorod arrays

A simple two-step process was developed for growing the nitrogen-doped ZnO (NZO) nanorod arrays on glass substrates. ZnO particles serve as a seed layer deposited by the electrostatic spray deposition method for the growth of NZO nanorods in aqueous solution. FE-SEM images revealed that nanorods have approximately uniform length distribution with hexagon end planes and grow vertically along the c-axis, which was also confirmed by X-rays diffraction. In addition, NZO nanorods had an average diameter of 140±20 nm and an average length of 1.2 to 2.7 μm with a wurtzite-type structure of ZnO. N doping had no prominent effect on the structure and crystal orientation, but it helps to increase the length and reduction in the diameter of nanorods. Moreover, electrical resistivity was found to decrease first and then increase with further nitrogen doping due to the decrease of mobility and increase of carrier concentration. Also the transmittance increased initially, but at higher nitrogen contents it decreased. Annealing the nanorods imparts no effect on the morphology, but there was a significant decrease in electrical resistivity due to the formation of oxygen vacancies. The realization of p-type ZnO nanorod arrays with durable and controlled transport properties is important for the fabrication of nanoscale electronic and optoelectronic devices.     

Seed-mediated synthesis of uniform ZnO nanorods in the presence of polyethylene glycol

Large quantities of ZnO nanorods have been synthesized by the seed-mediated method in the presence of polyethylene glycol at 90 °C. The products are characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy and high-resolution transmission electron microscopy. The as-grown ZnO nanorods are uniform with a diameter of 40–70 nm and length about 2 μm. The nanorods grew along the [0 0 1] direction. Possible roles of ZnO seeds and polymer in the growth of ZnO nanorods are also discussed.     

Enhancement of the emission from TeO2 nanorods by encapsulation with ZnO

TeO₂‐core/ZnO‐shell nanorods were synthesized by a two–step process comprising thermal evaporation of Te powders and atomic layer deposition of ZnO. Scanning electron microscopy images exhibit that the core‐shell nanorods are 50 ‐ 150 nm in diameter and up to a few tens of micrometers in length, respectively. Transmission electron microscopy and X‐ray diffraction analysis revealed that the cores and shells of the core‐shell nanorods were polycrystalline simple tetragonal TeO₂ and amorphous ZnO with ZnO nanocrystallites locally, respectively. Photoluminescence measurement revealed that the TeO₂ nanorods had a weak broad violet band at approximately 430 nm. The emission band was shifted to a yellowish green region (∼540 nm) by encapsulation of the nanorods with a ZnO thin film and the yellowish green emission from the TeO₂‐core/ZnO‐shell nanorods was enhanced significantly in intensity by increasing the shell layer thickness. The highest emission was obtained for 125 ALD cycles (ZnO coating layer thickness: ∼15 nm) and its intensity was much higher than that of the emission from the uncapsulated TeO₂ nanorods. The origin of the enhancement of the emission by the encapsulation is discussed in detail. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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.     

Sonochemical synthesis and characterization of ZnO nanorod/Ag nanoparticle composites

A simple sonochemical route for the synthesis of Ag nanoparticles on ZnO nanorods is reported. Ultrasonic irradiation of a mixture of ZnO nanorods, Ag(NH₃)₂⁺, and formaldehyde in an aqueous medium yields ZnO nanorod/Ag nanoparticle composites. The powder X‐ray diffraction of the ZnO/Ag composites shows additional diffraction peaks corresponding to the face‐center‐cubic structured Ag crystalline, apart from the signals from the ZnO nanorods. Scanning electron microscopy and transmission electron microscopy images of the ZnO/Ag composites reveal that the ZnO nanorods are coated with Ag nanoparticles with a mean size of several tens nanometer. The absorption band of ZnO/Ag composites is distinctly broadened and red‐shifted, indicating the strong interfacial interaction between ZnO nanorods and Ag nanoparticles. This sonochemical method is simple, mild and readily scaled up, affording a simple way for synthesis of other composites. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Microemulsion synthesis and characterization of aluminum doped ZnO nanorods

Aluminium doped ZnO (AZO) nanorods were synthesized by microemulsion method with different types of surfactants. Scanning electron microscopy observations show that the ZnO nanorods have diameters around about 80 nm and lengths up to several micrometers. The room temperature photoluminescence (PL) spectrum of AZO nanorods exhibited a sharp and strong ultraviolet bandgap at 383 nm and a relatively weaker emission associated with the defect level. AZO nanorods synthesized with sodium benzene sulfonate (SBS) surfactant showed lower resistivity than aluminum doped ZnO nanorods synthesized with dodecyl benzene sulfonic acid sodium salt (DBS) surfactant. Resistivity of AZO nanorods synthesized with SBS surfactant showed 2.8×10³ Ωcm. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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.     

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.     

铟镓共掺杂对n-ZnO纳米棒/p-GaN异质结生长行为和光电性能的影响

利用低温水热法在p-GaN薄膜上生长了铟(In)和镓(Ga)共掺杂的ZnO纳米棒。X射线衍射(XRD)、X射线光电子能谱(XPS)和X射线能量色谱仪(EDS)结果表明,In和Ga已固溶到ZnO晶格中。扫描电子显微镜(SEM)结果表明, ZnO纳米棒具有良好的c轴取向性,随着In和Ga共掺杂浓度的增加,纳米棒的直径减小,密度增加。XRD结果表明,In和Ga共掺杂引起ZnO晶格常数增大,导致(002)衍射峰向低角度方向偏移。同时,ZnO的光学性质受到In和Ga共掺杂的影响。与纯ZnO相比, 共掺杂ZnO纳米棒的紫外发射峰都出现轻微红移,这是表面共振和带隙重整效应综合作用的结果。I-V特性曲线表明,随着In和Ga共掺杂浓度的增加,n-ZnO纳米棒/p-GaN异质结具有更好的导电性。     

Low temperature hydrothermal growth and optical properties of ZnO nanorods

Well‐faceted hexagonal ZnO nanorods have been synthesized by a simple hydrothermal method at relative low temperature (90°C) without any catalysts or templates. Zinc oxide (ZnO) nanorods were grown in an aqueous solution that contained Zinc chloride (ZnCl₂, Aldrich, purity 98%) and ammonia (25%). Most of the ZnO nanorods show the perfect hexagonal cross section and well‐faceted top and side surfaces. The diameter of ZnO nanorods decreased with the reaction time prolonging. The samples have been characterized by X‐ray powder diffraction (XRD) and scanning electron microscopy (SEM) measurement. XRD pattern confirmed that the as‐prepared ZnO was the single‐phase wurtzite structure formation. SEM results showed that the samples were rod textures. The surface‐related optical properties have been investigated by photoluminescence (PL) spectrum and Raman spectrum. Photoluminescence measurements showed each spectrum consists of a weak band ultraviolet (UV) band and a relatively broad visible light emission peak for the samples grown at different time. It has been found that the green emission in Raman measurement may be related to surface states. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

CuInS2量子点敏化ZnO基光阳极的制备与性能研究

采用两步法在导电玻璃(FTO)基板上制备纯氧化锌(ZnO)纳米棒和钇掺杂的氧化锌(ZnO∶Y)纳米棒,采用连续离子层吸附反应法(SILAR)在所制备的ZnO及ZnO∶Y纳米棒上沉积CuInS₂量子点制备ZnO/CuInS₂和ZnO∶Y/CuInS₂光阳极。利用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、电子探针能谱仪(EDS)、紫外-可见分光光度计(UV-Vis)、电流密度-电压(J-V)曲线等技术手段对不同光阳极样品的晶相结构、微观形貌、化学组成、光吸收性能和太阳电池性能进行了表征。实验结果表明:所制备的ZnO纳米棒和ZnO∶Y纳米棒为六方纤锌矿结构。CuInS₂量子点敏化的ZnO纳米棒薄膜的光学带隙从3.22 eV减小为2.98 eV。CuInS₂量子点敏化ZnO∶Y太阳能电池的短路电流密度和光电转换效率比未掺杂的ZnO纳米棒组装的太阳能电池分别提高了6.5%和50.4%。     

Synthesis and optical properties of ZnO nanorods

ZnO nanorods were prepared on the silicon (100) substrates using the chemical solution deposition method (CBD) without catalyst under a low temperature (90°C). The cool water was used to dissolve the mixture of zinc nitrate hexahydrate (Zn (NO₃)₂·6H₂O) and methenamine (C₆H₁₂N₄) in order to decrease the size of ZnO nanorods. From the X‐ray diffraction (XRD) results, it can be seen that the growth orientation of the as‐prepared ZnO nanorods was (002). Scanning electron microscopy (SEM) results illustrated that the nanorods had a hexagonal wurzite structure and average diameter of about 120nm. The average diameter of nanorods prepared by the cool water process was much smaller than that by the room‐temperature (RT) water process we always used. Photoluminescence (PL) measurements were also carried out. The result showed that a blue shift in UV emission band appeared in the PL spectrum of the sample grown with cool water process, which was mainly due to the reduction of tensile strain when the diameter of the ZnO nanorods decreased. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

不同形貌的纳米氧化锌粉的光学性能研究

本文采用水热和溶剂热法制备了粒状、棒状、片状、管状纳米氧化锌粉体,并对四种不同形貌的氧化锌粉的光学性能进行了对比研究.结果表明:氧化锌纳米粒,纳米片和纳米管在200~400 nm区域的反射率均低于8;,而氧化锌纳米棒在200~400 nm区域的反射率大约为18;.氧化锌纳米管对甲基橙的光催化降解效果最好,在距离30 cm 的30 W紫外灯条件下进行照射,8 h完全降解,而氧化锌纳米棒对甲基橙的光催化降解效果最差,在相同的实验条件下,氧化锌纳米棒的降解率仅为70;.     

Synthesis of ZnO nanorods by the thermal reduction process of a mixture of ZnO and Al powder

Single‐crystalline Zinc oxide (ZnO) nanorods were firstly synthesized on gold‐coated Si substrate via a simple thermal reduction method from the mixture of ZnO and Al powder. The growth process was carried out in a quartz tube at different temperature (550‐700 °C) and at different oxygen partial pressure. Their structure properties were investigated by X‐ray diffraction (XRD), scanning electron microscope (SEM), X‐ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The length of the as‐prepared ZnO nanorods was up to several micrometers and their diameters were about 130 nm. The X‐ray diffraction patterns, transmission electron microscopic images, and selective area electron diffraction patterns indicate that the one‐dimensional ZnO nanorods are a pure Single‐crystal and preferentially oriented in the [0001] direction. The reaction mechanism of ZnO nanorods was proposed on the basis of experimental data. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

A facile method for the synthesis of tapered ZnO:Cu nanorod arrays and its secondary growth

A facile thermal diffusion method has been employed to synthesize tapered ZnO:Cu nanorod arrays. The plain hexagonal ZnO nanorods gradually turned into round cylinder and then tapered nanorods during thermal treatment. The shape evolution was explained by the terrace–ledge–kink model. Moreover, a small amount of copper has been incorporated into the nanorods during high temperature thermal treatment. Both X-ray photoelectron spectrum and photoluminescence results indicated that a number of oxygen vacancies exist in copper diffused samples. In addition, a catalyst free secondary growth was achieved on the tapered ZnO:Cu nanorod arrays. High resolution transmission electron microscope result showed that the tapered nanorods after secondary growth remained as a single crystal and the thinner section was epitaxially grown on the tip.     

The effect of ZnO buffer layer on structural and optical properties of ZnO nanorods

A low‐temperature synthetic route was used to prepare oriented arrays of ZnO nanorods on ITO conducting glass substrate coated with buffer layer of ZnO seeds in an aqueous solution. The corresponding growth behavior and optical properties of ZnO nanorod arrays were studied. It was found that the nature of the buffer layer had effect on the microstructures and optical properties of the resultant ZnO nanorod arrays. X‐ray diffraction (XRD) results showed the nanorods were preferentially grown along (002) direction, but the diameter of the nanorods prepared with the buffer layer was much smaller than the without one, which can be clearly seen from the scanning electron microscopy (SEM) results. And it also found that the buffer layer was not only enhanced the density of overall coverage but also beneficial to grown the oriented arrays. Photoluminescence spectroscopy (PL) results indicated that the all the samples had the better optical behaviors. By computation, the relative PL intensity ratio of ultraviolet emission (I_UV) to deep level emission (I_DLE) of ZnO nanorods grown with the pure substrate was much higher than that of the sample with the buffer layer. The defects on the surface increased with the size reduction of nanorods caused by the buffer layer may be the main reason for it. And the small shift in the UV emission was caused by the rapid reduction in crystal size and compressive stress from Raman spectra results. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of growth temperature on the structure and optical properties of ZnO nanorod arrays grown on ITO substrate

ZnO nanorod arrays have been successfully prepared on ITO substrate by a chemical‐bath deposition method at different growth temperatures. The influence of the growth temperature on the morphology and microstructure of the ZnO nanorods was investigated by scanning electron microscopy (SEM) and X‐ray diffraction (XRD). The results showed that the diameter of the ZnO nanorods decreased and the size of the nanocrystals increased with increasing growth temperature. Optical absorption measurements showed the absorption band edge has shifted to a lower‐energy region due to the quantum size effect. Green emission and UV emission bands were observed and they are found to be temperature dependent, which indicates that the deep‐level emission and band‐edge emission of ZnO nanorods is closely related to the rod diameter, and the related mechanism is discussed.