掺银氧化锌纳米棒的水热法制备研究

利用水热法在直流磁控溅射制备的掺铝氧化锌 (AZO) 种子层上制备了不同形貌和光学性能的掺银ZnO纳米棒, 并采用XRD、扫描电镜、透射谱、光发射谱和EDS谱详细研究了Ag离子与Zn离子的摩尔百分比 (R_Ag/Zn) 及AZO种子层对掺银ZnO纳米棒的结构和光学性质的影响. 随着R_Ag/Zn的增加, 掺银ZnO 纳米棒的微结构和光学性质的变化与银掺杂诱导的纳米棒的端面尺寸变化有关. 平均端面尺寸的变化归结于种子层颗粒大小和颗粒数密度不同导致掺入的Ag离子的相对比例不同. 溅射15 min的AZO种子层上生长的ZnO纳米棒由于缺陷增多导致在可见光区的发光峰明显强于溅射10 min 的AZO种子层上、相同R_Ag/Zn 条件下生长的ZnO纳米棒. Ag掺杂产生的点缺陷增多导致可见光区PL波包较宽. 纯ZnO纳米棒的微结构与种子层厚度导致的结晶度和颗粒大小有关. 关键词： ZnO纳米棒 水热法 Ag掺杂 直流磁控溅射     

醋酸锌热解温度对ZnO纳米棒的结构及光学性质的影响

采用水热法在普通载玻片上热解醋酸锌生成的ZnO种子层上制备ZnO纳米棒, 采用 X射线衍射仪、扫描电镜、分光光度计等测试手段详细研究了醋酸锌热解温度对 ZnO纳米棒的结构和光学性质的影响. 结果表明: 纳米棒的结晶质量、端面尺寸、宏观应力和透射率与醋酸锌热解温度有密切关系. 随着热解温度的增加, ZnO纳米棒具有的c轴择优取向性先增强后减弱, 拉应力先减小后增大, 可见光区的平均透射率先增大后减小. 热解温度为350 ℃时, ZnO纳米棒c轴择优取向性最强, 拉应力最小, 平均透射率最大. 端面尺寸诱导的表面散射 是影响ZnO纳米棒可见光区平均透射率的主要机制. 关键词： 醋酸锌 水热法 ZnO纳米棒     

Tunable surface wettability of ZnO nanorods prepared by two-step method

Zinc oxide (ZnO) nanorods were deposited on silicon substrate by two-step method. The crystal structure, surface morphology and water contact angle (WCA) were measured by X-ray diffractometer (XRD), field emission scanning electron microscopy (FESEM), and water contact angle apparatus. It is demonstrated that the WCA of the as-grown ZnO nanorods varies between 136° and 43° and the contact angle reduction rate of ZnO nanorods changes rapidly with increasing growth time. The variation of contact angle in the as-grown samples and contact angle reduction rate has been attributed to the combined effects of the proportion of nonpolar planes in the outermost surface, the area fraction of vapor on the surface and the increase of surface energy of ZnO nanorods.     

Low-temperature growth of ZnO nanorods on PET fabrics with two-step hydrothermal method

An effective low-temperature growth method to fabricate hexagonally oriented ZnO nanorod arrays onto PET fabrics is reported. The effect of substrate pre-treatment and C₆H₁₂N₄ concentration on the structure of ZnO nanorod arrays were investigated in details by X-ray diffraction (XRD), FE-SEM and ultraviolet protection factor (UPF). The results show that substrate pre-treatment, C₆H₁₂N₄ concentration indeed have great influence on the growth of ZnO nanorod arrays. It is indispensable to introduce a ZnO seed layer on the substrate and under growth condition of n(C₆H₁₂N₄):n[Zn(NO₃)₂] = 1:1, T = 90 °C, t = 3 h, the well-aligned ZnO nanorod arrays with 40-50 nm in diameter and 300-400 nm in length were achieved on the pre-treated PET fabrics. The ZnO nanorods grown on PET fabrics possessed an ultrahigh ultraviolet protection factor of 480.52 in this study, indicating an excellent protection against ultraviolet radiation in comparison with the untreated PET fabrics.     

水热反应中籽晶层对ZnO纳米棒的影响

以Zn(NO3)2·6H2O/HMT为反应物,通过低温水热反应过程,在籽晶衬底上制备了ZnO纳米棒,分别用场发射扫描电子显微镜和X射线衍射仪对ZnO纳米棒形貌与晶体结构进行了表征,并研究了不同方法制备的ZnO籽晶层以及籽晶层厚度对ZnO纳米棒形貌及结晶质量的影响.结果表明磁控溅射籽晶衬底上生长的ZnO纳米棒结晶质量最好,而籽晶层的厚度对ZnO纳米棒的垂直取向性有一定的影响.     

Room temperature synthesis of needle-shaped ZnO nanorods via sonochemical method

Single crystalline needle-shaped zinc oxide nanorods were synthesized via sonochemical methods using zinc acetate dihydrate and sodium hydroxide at room temperature. Morphological investigation revealed that the nanoneedles are of hexagonal surfaces along the length. The typical diameter and length vary from 120 to 160 nm and 3 to 5 μm, respectively. Sonication time appears to be a critical parameter for the shape determination. Detailed structural characterization confirmed that the nanorods are single crystalline with wurtzite hexagonal phase. A standard peak of zinc oxide was observed at 520 cm⁻¹ from the Fourier transform infrared spectroscopy. The ultra-violet visible and room temperature photoluminescence (PL) spectroscopic results demonstrate that the synthesized material has good optical properties.     

Fast piezoresistive sensor and UV photodetector based on Mn‐doped ZnO nanorods

A low cost hydrothermal synthesis method to synthesize Mn‐doped ZnO nanorods (NRs) with controllable morphology and structure has been developed. Ammonia is used to tailor the ammonium hydroxide concentration, which provides a source of OH^– for hydrolysis and precipitation during the growth instead of HMT. The morphological, chemical composition, structural, and electronic structure studies of the Mn‐doped ZnO NRs show that the Mn‐doped ZnO NRs have a hexagonal wurtzite ZnO structure along the c‐axis and the Mn ions replace the Zn sites in the ZnO NRs matrix without any secondary phase of metallic manganese element and manganese oxides observed. The fabricated PEDOT:PSS/Zn_0.85Mn_0.15O Schottky diode based piezoresistive sensor and UV photodetector shows that the piezoresistive sensor has pressure sensitivity of 0.00617 kPa^–1 for the pressure range from 1 kPa to 20 kP and 0.000180 kPa^–1for the pressure range from 20 kPa to 320 kPa with relatively fast response time of 0.03 s and the UV photodetector has both relatively high responsivity and fast response time of 0.065 A/W and 2.75 s, respectively. The fabricated Schottky diode can be utilized as a very useful human‐friendly interactive electronic device for mass/force sensor or UV photodetector in everyday living life. This developed device is very promising for small‐size, low‐cost and easy‐to‐customize application‐specific requirements. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

ZnO纳米棒的低温溶液法制备、光电特性研究及其在有机/无机复合电致发光中的应用

利用水热法制备了垂直于衬底的定向生长的ZnO纳米棒,利用扫描电子显微镜及光致发光的方法对其形貌及光学特性进行了表征,利用场发射性能测试装置对ZnO纳米棒的场发射性能进行了测试.结果表明:利用水热法在较低的温度(95 ℃) 下生长了具有较好形貌和结构的ZnO纳米棒,并表现出了较好的场发射特性,当电流密度为1 μA/cm²时,开启电场是2.8 V/μm,当电场为6.4 V/μm时,电流密度可以达到0.67 mA/cm²,场增强因子为3360.稳定性测试表明,在5 h内,4.5 V/μm的电场下,其波动不超过25%.将制备的ZnO纳米棒应用到有机/无机电致发光中,其中ZnO纳米棒为电子传输层,m-MTDATA(4,4',4″-tris{N,(3-methylphenyl)-N-phenylamino}-triphenylamine) 为空穴传输层,得到了ZnO的342 nm的紫外电致发光,此发光较ZnO纳米棒光致发光的紫外发射有约40 nm的蓝移. 关键词： ZnO纳米棒 场发射 水热法 有机/无机复合电致发光     

The super hydrophobicity of ZnO nanorods fabricated by electrochemical deposition method

Electrochemical deposition method was employed to fabricate ZnO nanorods on zinc foil substrate in this paper. The structural observations of ZnO nanorods with different aspect ratios were carried out by field-emission scanning electron microscopy. The microstructures of ZnO nanorods were also characterized by X-ray diffraction and the changes in surface hydroxyls with electrochemical deposition time were analyzed by X-ray photoelectron spectroscopy. The study results show the aspect ratios of ZnO nanorods and the density of their surface hydroxyls are responsible for their superhydrophobicity. The fluorinated polymer coated ZnO nanorods showed an excellent superhydrophobic behavior with 167° contact angle of water droplet, which is larger than that of fluorinated polymer flat surface. The more the surface hydroxyls are, the more hydrophilic the surfaces are. Meanwhile, the larger the aspect ratio of ZnO nanorod arrays is, the larger its drophobicity is. The results of this study might pave a simple and feasibility pathway to the fabrication of superhydrophobic cleaning materials used in engineering fields.     

Synthesis and properties of boron doped ZnO nanorods on silicon substrate by low-temperature hydrothermal reaction

Boron doped ZnO nanorods were fabricated by hydrothermal technique on silicon substrate covered with a ZnO seed layer. It is found that the concentration of boric acid in the reaction solution plays a key role in varying the morphology and properties of the products. The growth rate along the [0 0 0 1] orientation (average size in diameter) of the doped ZnO nanorods decreased (increased) with the increase of boric acid concentration. Based on the results of XRD, EDX and XPS, it is demonstrated that the boron dopants tend to occupy the octahedral interstice sites. The photoluminescence of the ZnO nanorods related to boron doping are investigated.     

X-ray analysis of ZnO nanorods grown by microwave irradiation heating on ZnO films

Utilizing microwave irradiation heating, 100-nm-diameter ZnO nanorods were grown from aqueous solution on sputtered ZnO films on glass substrates. Its out-of-plane X-ray diffraction (XRD) measurement indicated that the ZnO nanorods were grown with c-axis orientation, similar with the underlying ZnO films. In the in-plane XRD measurement, intensity of the () diffraction was comparable with that of the () one, suggesting their intensity ratio would contain useful information on nanorods density.     

Characteraction of Ag-doped ZnO thin film synthesized by sol–gel method and its using in thin film solar cells

Pure 2% and 4% Ag-doped ZnO thin films have been synthesized on glass substrates by sol–gel method. The structure, morphology and optical properties of the samples have been studied by X-ray diffractometer (XRD), scanning probe microscope, UV–vis spectrophotometer, respectively. The XRD result shows that the pure ZnO has a wurtzite hexagonal structure, no phase segregation is observed. The surface morphology of pure ZnO thin film shows that the grains are growing preferentially along the c-axis orientation perpendicular to the substrates. The transmittance spectra reveal that all samples have high transmittance above 90% in visible region. With Ag doping content increase, a red shift is observed. The performance of Ag-doped ZnO films using in thin film solar cells are simulated. The results show that 4% Ag-doped ZnO thin film can greatly improve the absorption of the cells. Compare to pure ZnO, solar cell's energy conversion efficiency improvement of 2.47% is obtained with 4% Ag doped ZnO thin film.     

Optical properties of ZnO nanorods realised by aqueous chemical growth

Photoluminescence investigations of ZnO nanorods realised by an advanced two-step aqueous chemical growth process have been carried out revealing well-resolved near-band-edge emission accompanied by phonon replicas. The optical properties of nanorods with different lengths and diameters are quite similar indicating a good control of the growth process without influencing the optical properties even on plastic substrate. The near-band-edge emission has a very broad line-width of 10 meV. Annealing in Ar atmosphere reduces the deep-level emission with a corresponding increase of the near-band-edge emission.     

Enhancement of the ultraviolet emission of ZnO nanorods by terphenyl liquid-crystalline ligands modification

We have developed a novel method to modifying the surface of ZnO nanorods (ZnO NRs) using p-hexoxyterphenylol (HTph-OH) as liquid crystal ligands. The structure and morphology of the modified ZnO NRs were characterized using Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and atomic force microscopy (AFM). AFM measurement showed that the dispersion of ZnO NRs could be dramatically improved by the surface modification of HTph-OH and further annealing treatment at its liquid crystal state temperature (150 °C). The remarkable decrease of the annealed composite film roughness is because the HTph-OH chains self-organize into more ordered structure induced by mesogens after annealing treatment, which may push the ZnO NRs to form oriented nano-dispersing structure. The optical properties of the modified ZnO NRs were investigated by UV-vis absorption spectroscopy and photoluminescence spectroscopy (PL). Markedly enhanced band-edge ultraviolet photoluminescence and significantly reduced defect-related emission were observed. We attribute this observation to the nearly perfect surface passivation of the ZnO NRs by the HTph-OH molecules. Meanwhile, UV emission of modified ZnO NRs could be further enhanced by increasing the concentration of HTph-OH and annealing treatment at its liquid crystal state temperature.     

Preparation of ZnO nanorods on cellulose fiber paper and their charge‐generating application for waste paper recycling

Zinc oxide (ZnO) nanorod arrays (NRAs) were well integrated on the cellulose fibers (CFs) of waste paper via a facile hydrothermal method. By mechanically blending the waste paper with de‐ionized water, abundant CFs were obtained and used as a sufficient platform for integrating ZnO NRAs. After coating a thin ZnO seed layer onto the surface of CFs and subsequent thermal treatment, the ZnO NRAs were densely grown, exhibiting high crystallinity and good photoluminescence properties. Their sizes were readily controlled by changing the concentration of the growth solution. To test the feasibility of an energy harvesting application using the prepared samples, the piezoelectric charge generation was explored under an external pushing force for the fabricated devices with polydimethylsiloxane‐shielded ZnO NRAs on CFs for good contact to two electrodes (i.e., gold and indium tin oxide). This nanotechnology of recycling waste paper could be considered as a promising candidate for implementation in cost‐effective and environment‐friendly advanced materials and energy production. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Self-catalyst synthesis of aligned ZnO nanorods by pulsed laser deposition

High-density well-aligned ZnO nanorods were successfully synthesized on ZnO-buffer-layer coated indium phosphide (InP) (100) substrates by a pulsed laser deposition (PLD) method. Scanning electron microscopy images show that the ZnO buffer layer formed uniform drip-like structure and ZnO nanorods were well-oriented perpendicular to the substrate surface. The sharp diffraction peak observed at 34.46° in X-ray diffraction scanning pattern suggests that the ZnO nanorods exhibit a (002)-preferred orientation. The PL spectra of ZnO samples shows a strong near band edge emission centered at about 380 nm and a weak deep level emission centered at around 495 nm, and it demonstrates that the ZnO nanorods produced in this work have high optical quality, which sheds light on further applications for nanodevices. Supported by the National Natural Science Foundation of China (Grant No. 50532080), the Science & Technology Foundation for Key Laboratory of Liaoning Province (Grant No. 20060131), and the Doctoral Project by China Ministry of Education (Grant No. 20070141038)     

Water-dispersible hydroxyapatite nanorods synthesized by a facile method

A simple and effective method, using calcium nitrate and triammonium phosphate as starting materials, for the preparation of water-dispersible hydroxyapatite nanorods (HAp) was reported. The process primarily involves the preparation of HAp with the addition of sodium citrate (NaC) and the exchange of absorbed ions (NaC) with sodium hexame taphosphate (NaP). The end products were investigated using various means in order to confirm the particles’ crystal phase and morphology and to understand how to improve their stability. The results demonstrate that the resulting HAp at 90 °C is rod-like with length of 300-400 nm and width of 40-60 nm. The zeta potential values of pure HAp, HAp-NaC, HAp-NaC/NaP are from −15.20, −30.89 to −44.84 mV. The settling time test shows the HAp-NaC/NaP could keep stable above 7 months without any creaming or visible sedimentation. The amount of NaC and the reaction temperature play significant roles in the whole process due to the formation of Ca containing precipitates.     

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.     

Synthesis and optical properties of ZnO nanorods on indium tin oxide substrate

ZnO nanorods with uniform diameter and length have been synthesized on an indium-tin oxide (ITO) substrate by using a simple thermal evaporation method which is suitable to larger scale production and without any catalyst or additives. The samples were characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet-vis (UV-vis) absorption spectrum, photoluminescence (PL) spectrum and Raman spectrum. The single-phase ZnO nanorods grow well-oriented along the c-axis of its wurtzite structure on ITO substrate. The ZnO nanorods shows sharp and strong UV emission located at 380 nm without notable visible light emission in the PL spectrum, which suggests the good crystallinity of the nanorods, which was also testified by their Raman spectrum. The photodegradation of methylene orange (MO) in aqueous solution reveals that the well-arranged c-axis growth of ZnO nanorods possess evidently improved photocatalytic performance and these properties enable the ZnO nanorods potential application in UV laser.