Surface tension and fluid flow driven self-assembly of ordered ZnO nanorod films for high-performance field effect transistors

Colloidal nanorods of inorganic semiconductors are of interest for a range of optoelectronic devices. The ability to self-assemble these materials into ordered arrays by solution-processing techniques is crucial for achieving adequate device performance. Here we show that uniform ZnO nanorod films with defined nanorod alignment can be solution-deposited over large areas by controlling the surface energy of the nanorods through the choice of suitable ligands and by the fluid flow direction during growth. ZnO nanorods with long carbon chain ligands exhibit a smaller surface free energy than those with short carbon chain ligands resulting in better in-plane alignment and large domain sizes up to dozens of micrometers in spin-coated films. A model is presented to rationalize the observed self-assembly behavior. It is based on the formation of a lyotropic liquid crystalline phase on the surface of the liquid film which is facilitated by enhanced segregation of nanorods with low surface tension to the surface. Alignment of the nanorods is controlled by radial and vertical liquid flows in the drying solution. The ability to control the orientation of the nanorods and to achieve large domain size results in significant device performance improvement. Field-effect transistors with mobilities of up to 1.2-1.4 cm2/V.s are demonstrated in spin-coated, in-plane aligned ZnO nanorod films subject to postdeposition hydrothermal growth.     

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.     

The effect of hydrothermal growth temperature on preparation and photoelectrochemical performance of ZnO nanorod array films

Highly oriented ZnO nanorod arrays with controlled diameter and length, narrow size distribution and high orientation consistency have been successfully prepared on ITO substrates at different growth temperatures by using a simple hydrothermal method. XRD results indicate that the nanorods are high-quality single crystals growing along [001] direction with a high consistent orientation perpendicular to the substrate. SEM images show that the nanorods have average diameters of about 30-70 nm by changing growth temperature. The thin films consisting of ZnO nanorods with controlled orientation onto ITO substrates allow a more efficient transport and collection of photogenerated electrons through a designed path. For a sandwich-type cell, the relatively high overall solar energy conversion efficiency reaches about 2.4% when the growth temperature is at 95 °C.     

氧化锌纳米棒微结构光电极的制备

通过两步法,即首先热分解醋酸锌制备氧化锌晶种层,在晶种的诱导下,再采用低温水热法在氟掺杂的SnO₂导电玻璃(fluorine-doped tin oxide, FTO)基底导电面上成功制备出高取向性的氧化锌纳米棒阵列光电极。系统研究了前驱液浓度、溶液pH值、反应时间等实验条件对光电极微结构的影响。实验结果表明在一定变化范围内,随着前驱液浓度和溶液pH值的增大,纳米棒的直径增大;随着反应时间的延长,纳米棒的长度增长。将氧化锌纳米棒阵列薄膜制作成染料敏化太阳电池(dye-sensitized solar cell, DSSC)的光电极,并对电池的I-V特性进行了表征。     

水热法制备高度取向的氧化锌纳米棒阵列

氧化锌的激子结合能(60meV)及光增益系数(300cm^-1)比GaN的(25meV,100cm^-1)还高,这一特点使它成为紫外半导体激光发射材料的研究热点。最近,Yang等成功地观测到规则的ZnO纳米线阵列的激光发射现象,更加激起了人们合成一维高度有序ZnO纳米结构的热情,由于一维ZnO     

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.     

化学溶液沉积法制备单分散氧化锌纳米棒阵列

在由溶胶凝胶法制备的纳米ZnO薄膜基底上, 采用化学溶液沉积法制备了单分散、高度取向的ZnO纳米棒阵列膜. 通过控制纳米ZnO薄膜的制备工艺, 可以调节氧化锌纳米棒的直径. 利用FESEM, TEM, HRTEM, SAED和XRD表征了氧化锌纳米棒阵列的形貌和晶体结构. ZnO纳米棒的室温PL谱具有很高的紫外带边发射峰, 在可见光波段无发射峰, 表明该方法制备的ZnO纳米棒晶体结构完整, 晶体中O空位的浓度很低.     

Simple solvothermal route to synthesize ZnO nanosheets, nanonails, and well-aligned nanorod arrays

ZnO nanosheets, nanonails, and well-aligned nanorods were fabricated on Zn foils by a solvothermal approach using ethanol as the solvent. A lower synthesis temperature and a shorter time period favor the formation of nanosheets. By optimizing the synthesis temperature and time period, ZnO nanonails with a hexagonal cap and a long stem could be produced. A higher temperature was not favorable to produce uniform and smooth nanorods. Well-aligned ZnO nanorod arrays were produced with diameters within 100-250 nm and lengths up to approximately 6 microm when NaOH was added to the solvent. By optimizing the reaction parameters, the morphology, size, and orientation of the nanoforms could be tailored. The ZnO nanorods exhibit an excitonic strong UV emission and a defect-related broad green emission at room temperature. The defect-related green emission band decreased with the improvement of the degree of alignment of the nanorods.     

ZnO纳米棒阵列到纳米管结构的自转化机制及其在相变封装材料中的应用

In the emerging field of nanoscience, tubular structures have been attracting remarkable interest due to their well-defined geometry, high specific area, and exceptional physical and chemical properties. Among them, oriented ZnO tubular arrays are regarded as promising candidates for various applications such as optoelectronics, solar cells, sensors, field emission, piezoelectrics, and catalysis. Although template-directed and selective dissolution synthesizing strategies are commonly used to prepare ZnO nanotubes, repeatability and large scale preparation are still challenging. In this study, ZnO nanotube arrays were controllably prepared by tuning the hydrothermal parameters, without the use of any additives. The mechanism underlying the self-conversion of ZnO nanorods to nanotubes was comprehensively studied based on the surface energy theory. It has been proved that the metastable top surface of the ZnO nanorods dissolves preferentially to reach a stable state during the hydrothermal growth. The specific surface energy of different crystal faces of ZnO nanorods was calculated using molecular dynamics simulation. The top surface of the ZnO nanorod, the Zn-terminated [0001] face, demonstrated much higher surface free energy than did the lateral faces, which indicated that the self-dissolution of top face (002) is energetically favorable. The self-conversion behavior of ZnO nanorod arrays with different diameters was specifically investigated by adjusting the initial precursor concentration, density of the crystal seed layers, and growth time. The dissolution-crystallization equilibrium concentration, determined by crystal surface energy, was found to be a key factor for the formation of the tubular structure. Notably, the critical equilibrium conditions for the self-conversion of ZnO nanorods to nanotubes, including zinc ion concentration and pH, have been identified by studying parameters corresponding to the dissolution-crystallization equilibrium for the metastable top surface of the ZnO nanorods. The preparation of the ZnO nanotube arrays was successfully accelerated and simplified via two-step procedure: (1) preparation of ZnO nanorod arrays and (2) self-conversion of ZnO nanorods to nanotubes. The preparation method based on the self-conversion mechanism from rods to tubes for polar oxides is simpler and more easily controllable as compared to the reported methods involving variety of additives. Because of the advantages of adaptability to a wide range of substrates, excellent conducting properties, and filling ability, the prepared ZnO nanotube array films were used in encapsulating phase-change materials. The encapsulated phase-change material exhibited excellent heat storage/release properties and heat conductivities. This indicates the potential application of precision devices for temperature control.     

Synthesis of ZnO nanorods and their application in quantum dot sensitized solar cells

ZnO nanorod thin films of different thicknesses and CdS quantum dots have been prepared by chemical method. X-ray diffraction pattern reveals that the CdS quantum dot and ZnO nanorods are of hexagonal structure. Field emission scanning electron microscope images show that the diameter of hexagonal shaped ZnO nanorods ranges from 110 to 200 nm and the length of the nanorod vary from 1.3 to 4.7 μm. CdS quantum dots with average size of 4 nm have been deposited onto ZnO nanorod surface using successive ionic layer adsorption and reaction method and the assembly of CdS quantum dot with ZnO nanorod has been used as photo-electrode in quantum dot sensitized solar cells. The efficiency of the fabricated CdS quantum dot-sensitized ZnO nanorod-based solar cell is 1.10 % and is the best efficiency reported so far for this type of solar cells.     

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。     

Tuning the Dimensions of ZnO Nanorod Arrays for Application in Hybrid Photovoltaics

ZnO nanorod arrays are a very eligible option as electron acceptor material in hybrid solar cells, owing to their favorable electrical properties and abundance of available, easy, and low‐cost synthesis methods. To become truly effective in this field, a major prerequisite is the ability to tune the nanorod dimensions towards optimal compatibility with electron‐donating absorber materials. In this work, a water‐based seeding and growth procedure is used to synthesize ZnO nanorods. The nanorod diameter is tuned either by modifying the zinc concentration of the seeding solution or by changing the concentration of the hydrothermal growth solution. The consequences of this morphological tailoring in the performance of hybrid solar cells are investigated, which leads to a new record efficiency of 0.82 % for hydrothermally grown ZnO nanorods of size 300 nm in combination with poly(3‐hexylthiophene‐2,5‐diyl) (P3HT). This improvement is attributed to a combined effect of nanorod diameter and orientation, and possibly to a better alignment of the P3HT backbone resulting in improved charge transport.     

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。     

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.     

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.     

Growth and Characterization of [001] ZnO Nanorod Array on ITO Substrate with Electric Field Assisted Nucleation

This paper reports direct growth of [001] ZnO nanorod arrays on ITO substrate from aqueous solution with electric field assisted nucleation, followed with thermal annealing. X-ray diffraction analyses revealed that nanorods have wurtzite crystal structure. The diameter of ZnO nanorods was 60–300 nm and the length was up to 2.5 μm depending on the growth condition. Photoluminescence spectra showed a broad emission band spreading from 500 to 870 nm, which suggests that ZnO nanorods have a high density of oxygen interstitials. Low and nonlinear electrical conductivity of ZnO nanorod array was observed, which was ascribed to non-ohmic contact between top electrode and ZnO nanorods and the low concentration of oxygen vacancies.     

Fabrication and evaluation of ZnO nanorods by liquid-phase deposition

The ZnO nanorod growth mechanism during liquid-phase deposition (LPD) has been investigated, with results considered in the context of phase stabilization, LPD chemical processes, and Gibbs free energy and entropy. Zinc oxide (ZnO) possesses unique optical and electronic properties, and obtaining ZnO species with high specific surface area is important in ZnO applications. Highly c-axis-oriented ZnO films are expected to be utilized in future optical and electrical devices. ZnO nanorods were synthesized using an aqueous solution deposition technique on a glass substrate with a free-standing ZnO nanoparticle layer. ZnO nanorod growth was easily controlled on the nanoscale by adjustment of the immersion time (15-210 min). X-ray diffraction, field-emission scanning electron microscopy (FE-SEM), and film thickness measurements were used to characterize the crystalline phase, orientation, morphology, microstructure, and growth mechanism of the ZnO nanorods. FE-SEM images were analyzed by image processing software, which revealed details of the of ZnO nanorod growth mechanism.     

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.     

Electrical investigation and ultraviolet detection of ZnO nanorods encapsulated with ZnO and Fe-doped ZnO layer

Encapsulated ZnO nanorod arrays were fabricated using a two-step method; hydrothermal followed by dip-coating. Intensity of X-ray diffraction peaks of ZnO nanorod films increased by encapsulation with ZnO and Fe doped ZnO layer. Encapsulation process increased diameter of the rods in a range of 20–40 nm. The optical studies indicated that the band-gap decreased with increment of the nanorod diameter, and increased with Fe doping in the ZnO layer. The electrical resistance of the samples demonstrated a remarkable reduction due to encapsulation, especially in the sample encapsulated with Fe doped-ZnO layer. The photoresponse behavior of ZnO nanorod films was investigated under different powers of ultraviolet illumination. The photoresponsivity was improved for encapsulated nanorods as compared to bare nanorods.     

Hydrothermal growth of well-aligned ZnO nanorod arrays: Dependence of morphology and alignment ordering upon preparing conditions

Well-aligned ZnO nanorod arrays were prepared on substrates by hydrothermal growth under different conditions. The effect of preparing conditions on the deposition of ZnO nanorods was systematically studied by scanning electron microscopy, X-ray diffraction and photoluminescence spectroscopy. It is demonstrated that the growth conditions such as pre-treatment of the substrates, growth temperature, deposition time and the concentration of the precursors have great influence on the morphology and the alignment ordering of ZnO nanorod arrays. Pre-treatment of substrates, including dispersion of ZnO nanoparticles and subsequent annealing, not only plays a main role in governing the rod diameter, but also greatly improves the rod orientation. Although the rod diameter and its distribution are mainly determined by pre-coated ZnO nanoparticles, they can also be monitored to some extent by changing the concentration of the precursors. The growth temperature has a little influence on the orientation of nanorods but it has great impact on their aspect ratio and the photoluminescent property. Kinetic studies show that the growth of ZnO nanorods contains two distinct step: a fast steps within the first hour, in which the nanorods tend to be short and wide, and a slow step, in which long rods with high aspect ratio are obtained.