可见光诱导TiO2光催化及其机理研究进展

简述了二氧化钛的光催化机理。针对其禁带宽度较大,只能被小于387nm的紫外光所激发的缺点,综述了近年来国内外针对纳米TiO2可见光催化的改性方法和改性机理研究进展,包括离子掺杂、半导体复合、表面光敏化等方法。最后展望了提高纳米TiO2可见光光催化活性研究的前景。     

Site-specific multi-stage CVD of large-scale arrays of ultrafine ZnO nanorods

Multi-stage growth of ZnO nanorod arrays has been carried out by Au-assisted chemical vapor deposition (CVD) in order to better understand and more precisely control the growth behaviors. It is evidenced that Au-catalyzed vapor-liquid-solid (VLS) growth only dominates the initial site-specific nucleation of the nanorods, while the subsequent growth is governed by a vapor-solid (VS) epitaxy mechanism. The sequential VLS and VS behaviors permit the fabrication of large-scale highly ordered arrays of ZnO nanorods with precisely tunable diameters and embedded junctions by controlling reactant concentration and nanorod top morphology. Based on the above results, two routes to fabricate ultrafine ZnO nanorod arrays are proposed and stepwise nanorod arrays with ultrafine top segment (~10 nm in diameter) have been achieved. Temperature-dependent photoluminescence (PL) and spatial resolved PL were carried out on the nanorod arrays and on individual nanorods, indicating high quality optical properties and tunable light emission along the length of the stepwise nanorods.     

Controllable synthesis and photoluminescence properties of ZnO nanorod and nanopin arrays

Well-aligned ZnO nanorods and nanopins are synthesized on a silicon substrate using a one-step simple thermal evaporation of a mixture of zinc and zinc acetate powder under controlled conditions. A self-assembled ZnO buffer layer was first obtained on the Si substrate. The structure and morphology of the as-synthesized ZnO nanorod and nanopin arrays are characterized using X-ray diffraction, and scanning and transmission electron microscopies, energy-dispersive X-ray spectroscopy, and photoluminescence spectroscopy. The influence of the background atmosphere on the two ZnO nanostructures has been studied. Two different growth mechanisms are mentioned to interpret the formation of ZnO nanorod and nanopin arrays in our work. The room-temperature PL features the ZnO nanorods exhibit only sharp and strong ultraviolet (UV) emission emissions, which confirms the better crystalline and optical quality than the ZnO nanopins.     

A novel, substrate independent three-step process for the growth of uniform ZnO nanorod arrays

We report a three-step deposition process for uniform arrays of ZnO nanorods, involving chemical bath deposition of aligned seed layers followed by nanorod nucleation sites and subsequent vapour phase transport growth of nanorods. This combines chemical bath deposition techniques, which enable substrate independent seeding and nucleation site generation with vapour phase transport growth of high crystalline and optical quality ZnO nanorod arrays. Our data indicate that the three-step process produces uniform nanorod arrays with narrow and rather monodisperse rod diameters (∼ 70 nm) across substrates of centimetre dimensions. X-ray photoelectron spectroscopy, scanning electron microscopy and X-ray diffraction were used to study the growth mechanism and characterise the nanostructures.     

ZnO纳米棒Al掺杂和A1,N共掺杂的制备技术与光致发光性能

采用水热法首先合成了Al掺杂ZnO(AZO)纳米棒,在此基础上通过550℃的氨气氛中退火制备了Al,N共掺杂ZnO(ANZ())纳米棒.运用X射线衍射(XRD),场发射扫描电镜(FESEM),透射电子显微镜(TEM),X射线能谱(EDS)和光致发光(PL)对样品进行了表征与分析.结果表明,制备的AZO和ANZ()纳米棒...     

低温水热法生长ZnO纳米棒阵列的电子结构及光学特性(英文)

使用低温水热法在Si衬底上生长ZnO纳米棒阵列.通过X射线衍射和扫描电子显微镜对ZnO纳米棒的结晶性和形貌进行观测.结果表明,六棱柱形ZnO纳米棒沿c轴方向的阵列性良好,且均匀致密的生长在衬底上.室温光致发光谱表明应用低温水热法可以得到光学性质良好的ZnO纳米棒阵列.使用同步辐射对ZnO纳米棒阵列的氧K带边进行X射线吸收近带边谱测量,研究了不同半径ZnO纳米棒阵列的局部电子结构及其半径对电子结构的影响.另外,对ZnO纳米棒及ZnO薄膜的局部电子结构进行了对比研究.     

Mg掺杂ZnO纳米棒阵列的场发射性能研究

采用水热法在硝酸锌(Zn(NO3)2·6H2O)与硝酸镁(Mg(NO3)2·6H2O)的生长液中制备了Mg掺杂的Mg/ZnO(MZO)纳米棒,其中生长液中Mg2+的物质的量浓度c(Mg2+)分别为0.05 mol/L、0.10 mol/L、0.25 mol/L和0.50 mol/L.利用场发射电子显微镜(FESEM)、X射线光电子能谱仪(XPS)、X射线衍射仪(XRD)、光致发光谱(PL)测试及场发射测试对所制备的MZO纳米棒的表面形貌、成分、晶体结构、光学性能及场发射性能进行了研究.结果表明:随着生长液中c(Mg2+)的增加,MZO纳米棒的直径逐渐减小、缺陷逐渐增加;且掺入的Mg含量与c(Mg2+)并不成正比关系;当生长液中的c(Mg2+)为0.10 mol/L时,所制备的MZO纳米棒的场发射性能最好,其开启场强为2.85 V/μm.     

ZnO纳米棒阵列膜的制备及其光电化学性能研究

采用化学溶液沉积法,在ZnO纳米颗粒膜修饰的FTO导电玻璃基底上,制备了ZnO纳米棒阵列。用X射线衍射仪（XRD）、场发射扫描电子显微镜（FESEM）、透射电子显微镜（TEM）对样品进行表征。研究结果表明所制备的ZnO纳米棒为六方纤锌矿相单晶结构,沿c轴择优取向生长,平均直径约为40nm,长度约为900nm;ZnO纳米棒阵列生长致密,取向性较一致。以曙红Y敏化的ZnO纳米棒阵列膜为光阳极制作了染料敏化太阳能电池原型器件,在光照强度为100mW/cm2下,其开路电压为0.418V,短路电流为0.889mA/cm2,总的光电转换效率为0.133%。     

Effects of Mg-contents and substrate parameters on structure and optical properties of Mg-doped ZnO nanorods fabricated by hydrothermal method

Mg-doped ZnO nanorods with different contents have been fabricated on various substrates by hydrothermal method. The effects of Mg-contents and different substrates on structural and optical properties are analyzed by scanning electron microscopy, X-ray diffraction, photoluminescence (PL) spectra, energy dispersive X-ray spectroscopy and Raman spectroscopy. The results reveal that the Mg-doped ZnO nanorods possess good crystalline quality and morphology when the molar ratio of Mg/Zn is 1. The PL spectra show that the UV emissions have an obvious blue shift with the increase of Mg-content. The results of investigation for the samples grown on different substrates show that the crystal quality and morphology of the samples grown on ZnO layer are perfect, and the UV emission also occurs blue shift owing to the effects of different substrates.     

Vertically aligned Fe-doped ZnO nanorod arrays by ultrasonic irradiation and their photoluminescence properties

A facile sonochemical route was demonstrated for the direct fabrication of Fe-doped ZnO nanorod arrays on a Si substrate under ambient conditions. By adding Fe³⁺ ions in reaction solution, Fe is readily in situ doped into ZnO nanorod arrays via ultrasound irradiation. The morphology and structural characteristic of the Fe-doped ZnO nanorods were investigated using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). And crystal structure was characterized by X-ray diffraction (XRD) spectroscopy. Inductively-coupled plasma atomic emission spectroscopy (ICP-AES) confirmed the Fe-doping of ZnO nanorod arrays with a concentration of 0.9 wt.%. In addition, Fe-doped ZnO nanorod showed the enhancement of photoluminescence (PL) intensity in green-yellow emission.     

Microstructural and optical characteristics of solution-grown Ga-doped ZnO nanorod arrays

Highly oriented Ga-doped zinc oxide (ZnO) nanorod arrays have been prepared on a ZnO-buffered silicon substrate in an aqueous solution, which is a mixture of methenamine (C(6)H(12)N(4)), zinc nitrate hexahydrate (Zn(NO(3))(2)·6H(2)O), and gallium nitrate hydrate (Ga(NO(3))(3)·xH(2)O). The microstructure characteristics and optical properties of the nanorod arrays were analyzed using different characterization techniques including field-emission scanning electron microscopy (FESEM), x-ray photoelectron spectroscopy (XPS), and photoluminescence (PL). The experimental results show that the morphology, density, and surface compositions of ZnO nanorod arrays are sensitive to the concentration of gallium nitrate hydrate. The PL spectra of all ZnO nanorod arrays show three different emissions, including UV (ultraviolet), yellow, and NIR (near infrared) emissions. With the increase in the Ga doping level, the luminescence quality of ZnO nanorods has been improved. The peak of UV emission has a small redshift, which can be ascribed to the combined effect of size and Ga doping. Furthermore, Ga doping has caused defects that respond to NIR emission.     

Defect induced room temperature ferromagnetism in well-aligned ZnO nanorods grown on Si (100) substrate

In this work, we report the fabrication of high quality single-crystalline ZnO nanorod arrays which were grown on the silicon (Si) substrate using a microwave assisted solution method. The as grown nanorods were characterized using X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), photo-luminescence (PL) and magnetization measurements. The XRD results indicated that the ZnO nanorods are well oriented with the c-axis perpendicular to the substrate and have single phase nature with the wurtzite structure. FE-SEM results showed that the length and diameter of the well aligned rods is about ~ 1 μm and ~ 100 nm respectively, having aspect ratio of 20-30. Room-temperature PL spectrum of the as-grown ZnO nanorods reveals a near-band-edge (NBE) emission peak and defect induced green light emission. The green light emission band at ~ 583 nm might be attributed to surface oxygen vacancies or defects. Magnetization measurements show that the ZnO nanorods exhibit room temperature ferromagnetism which may result due to the presence of defects in the ZnO nanorods.     

Synthesis of two kinds of ZnO nanostructures by vapor phase method

Radial and quasi-aligned ZnO nanorod arrays were prepared on Si(111) substrates by a simple vapor phase method using Zn and zinc acetate dihydrate (ZA) as the source materials. X-ray diffraction, field emission scanning electron microscopy, Raman scattering and photoluminescence were used to characterize the structural and optical properties of the obtained nanostructures. The growth mechanisms of the two kinds of ZnO nanostructures were discussed based on the growth conditions. The different decomposing rate of the ZA plays an important role in the initial nucleation of ZnO nanorods.     

Low-temperature growth and optical properties of Ce-doped ZnO nanorods

Ce-doped ZnO nanorod arrays were grown on zinc foils by a hydrothermal method at 180°C. The effects of Ce-doping on the structure and optical properties of ZnO nanorods were investigated in detail. The characterisation of the rod array with X-ray diffraction and X-ray photoelectron spectroscopy indicated that Ce³⁺ ions were incorporated into the ZnO lattices. There were no diffraction peaks of Ce or cerium oxide in the pattern. From UV-Vis spectra, we observed a red shift in the wavelength of absorption and decreased band gap due to the Ce ion incorporation in ZnO. The photoluminescence integrated intensity ratio of the UV emission to the deep-level green emission (I _UV/I _DLE) was 1.25 and 2.87, for ZnO and Ce-doped ZnO nanorods, respectively, which shows a great promise for the Ce-doped ZnO nanorods with applications in optoelectronic devices.     

Self-organized comb-like ZnO microstructures: Morphologies and defect induced optical emission

Comb-like ZnO microstructures have been synthesized in high yield via catalyst free thermal evaporation at a relatively low temperature. The structural and optical properties of the prepared samples were studied using scanning electron microscopy, transmission electron microscopy, X-ray diffraction, Raman spectrum, photoluminescence (PL) and microscopic PL images. The morphologies of the products show a ribbon like stem and nanorod arrays with square, rectangle and parallelogram cross section aligned along one side of the former. PL spectra and microscopic PL images reveal that the prepared microstructures have strong orange–yellow emission, notably different from the green emission of ZnO nanocombs by only thermally evaporating pure zinc power. The difference of optical emission could be ascribed to the change of defect status resulted from impurity effect during the growth of ZnO microstructures.     

Structure and photoluminescence of S-doped ZnO nanorod arrays

Vertically aligned S-doped ZnO nanorod arrays have been successfully synthesized by hydrothermal method at 90 °C for 2 h. The obtained nanorod is ～ 70 nm in diameter and 1.2 μm in length. The XRD pattern and the Raman spectra indicate that the S-doped nanorod arrays are orientated at [001] and are single crystals with hexagonal wurtzite structure. The photoluminescence (PL) spectra show that S-doped ZnO nanorod arrays exhibit a relative weak ultraviolet (UV) emission, a violet emission and a strong green emission. The effects of S-doping on the structure and photoluminescence of ZnO nanorod arrays are discussed in detail.     

Growth specificity of vertical ZnO nanorods on patterned seeded substrates through integrated chemical process

A simple and cost effective method has been employed for the random growth and oriented ZnO nanorod arrays over as-prepared and patterned seeded glass substrates by low temperature two step growth process and growth specificity by direct laser writing (DLW) process. Scanning electron microscopy (SEM) images and X-ray diffraction analysis confirm the growth of vertical ZnO nanorods with perfect (0 0 2) orientation along c-axis which is in conjunction with optimizing the parameters at different reaction times and temperatures. Transmission electron microscopy (TEM) images show the formation of vertical ZnO nanorods with diameter and length of ∼120 nm and ∼400 nm respectively. Photoluminescence (PL) spectroscopic studies show a narrow emission at ∼385 nm and a broad visible emission from 450 to 600 nm. Further, site-selective ZnO nanorod growth is demonstrated for its high degree of control over size, orientation, uniformity, and periodicity on a positive photoresist ZnO seed layer by simple geometrical (line, circle and ring) patterns of 10 μm and 5 μm dimensions. The demonstrated control over size, orientation and periodicity of ZnO nanorods process opens up an opportunity to develop multifunctional properties which promises their potential applications in sensor, piezoelectric, and optoelectronic devices.     

ZnO nanorod/CdS nanocrystal core/shell-type heterostructures for solar cell applications

ZnO/CdS core/shell nanorod arrays were fabricated by a two-step method. Single-crystalline ZnO nanorod arrays were first electrochemically grown on SnO(2):F (FTO) glass substrates. Then, CdS nanocrystals were deposited onto the ZnO nanorods, using the successive ion layer adsorption and reaction (SILAR) technique, to form core/shell nanocable architectures. Structural, morphological and optical properties of the nanorod heterojunctions were investigated. The results indicate that CdS single-crystalline domains with a mean diameter of about 7 nm are uniformly and conformally covered on the surface of the single-crystalline ZnO nanorods. ZnO absorption with a bandgap energy value of 3.30 ± 0.02 eV is present in all optical transmittance spectra. Another absorption edge close to 500 nm corresponding to CdS with bandgap energy values between 2.43 and 2.59 eV is observed. The dispersion in this value may originate in quantum confinement inside the nanocrystalline material. The appearance of both edges corresponds with the separation of ZnO and CdS phases and reveals the absorption increase due to CdS sensitizer. The photovoltaic performance of the resulting ZnO/CdS core/shell nanorod arrays has been investigated as solar cell photoanodes in a photoelectrochemical cell under white illumination. In comparison with bare ZnO nanorod arrays, a 13-fold enhancement in photoactivity was observed using the ZnO/CdS coaxial heterostructures.     

Fabrication of ZnS/ZnO hierarchical nanostructures by two-step vapor phase method

A simple two-step vapor phase method is presented to fabricate ZnS/ZnO hierarchical nanostructures in bulk quantities. That is ZnS nanobelts were first synthesized and then used as substrate for growth of ZnO nanorod arrays. Investigation results demonstrate that the polar surfaces of ZnS nanobelts could induce a preferred asymmetric growth of ZnO nanorods on the side surfaces. But it is believed that if the local concentration of ZnO was high enough, ZnO nanorods could also grow symmetrically on the top/bottom surface of the ZnS nanobelts. The optical property of the products was also recorded by means of photoluminescence (PL) spectroscopy.     

Structural and magnetic properties of Mn-doped ZnO nanorod arrays grown via a simple hydrothermal reaction

High density Mn-doped ZnO nanorod arrays were vertically grown on ITO substrate via hydrothermal reaction at relatively low temperature of 95 °C. The microstructure and magnetism of the arrays have been examined. Field emission scanning electron microscopy shows that the nanorods of 100 nm diameter and 1 μm length grow along the [001] direction. X-ray photoemission spectroscopy demonstrates that Mn is successfully doped into the nanorods. Meanwhile, all the Mn-doped ZnO nanorod arrays are ferromagnetic at room temperature. It is also found that the value of the saturation magnetization (M_s) of the ZnO nanorod arrays firstly increases with increasing the Mn concentration and then decreases. The higher M_s value is 0.11emu/g, which is obtained in the 5 at.% Mn-doped ZnO nanorod arrays. The ferromagnetism comes from the ferromagnetic interaction between the Mn ions, which partly replace Zn ions.