硅基ZnO纳米棒阵列异质结太阳能电池的水热合成及其光伏性能

通过低温水热法,在图案化的p型硅衬底上合成氧化锌（ZnO）纳米棒阵列薄膜,制备出具有p-Si/n-ZnO纳米棒（NR）阵列结构的异质结太阳能电池（HSCs）。通过直流磁控溅射技术,分别在前后面板溅射沉积ITO和Al膜接触电极层。研究ZnO籽晶层的退火温度、ZnO纳米棒阵列水热合成的时间等因素对ZnO纳米棒阵列的晶体结构、表面形貌和光学性能的影响。p-Si/n-ZnO纳米棒阵列HSCs的最佳短路电流密度和总能量转换效率分别为11.475 mA·cm^-2和2.0%。相比p-Si/n-ZnO薄膜HSCs,p-Si/n-ZnO纳米棒阵列HSCs的光伏性能得到了有效提高。     

Growth of ZnO nanorod arrays on soft substrates by hydrothermal process

ZnO nanorod arrays with quite homogeneous size and shape were fabricated by introducing ZnO seed-layer as nucleation centers on the soft ITO substrates prior to the hydrothermal reaction. The samples were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction and photoluminescence method. After the ZnO seed-layer is introduced, the resulting deposits on the substrates develop into nanorods, and the diameter decreases obviously to about 100 nm. Influences of the coated nanocrystal seed nuclei on the morphology of ZnO nanorod arrays were discussed. The results show that each nanorod is monocrystalline with wurtzite-type structure and oriented in c-axis direction. The increase of the intensity ratio of ultraviolet to visible emissions in room-temperature photoluminescence spectra and the decrease of the ultraviolet PL linewidths show the improvement of the quality of ZnO nanorods. A simple and effective method to synthesize ZnO nanorod arrays with fairly uniform size and shape on soft substrates is dip-coating ZnO nanocrystals prior to hydrothermal reaction, and it may be also feasible for the fabrication of other small-size metal oxide nanostructures on soft substrates.     

钛基表面PDLLA/ZnO纳米阵列材料的制备及生物学性能

采用水热生长法,在钛基表面制备高度有序、尺寸可控的氧化锌纳米棒阵列,再通过静电吸附的方法在其表面自组装一层具有良好生物相容性的聚乳酸生物涂层。利用SEM,MTT,LDH方法对细胞形态和生物活性进行表征。结果表明,氧化锌阵列上细胞形态呈圆形,无铺展现象。而经聚乳酸修饰过的材料表面MC3T3细胞外基质铺展较好,细胞分泌的丝状伪足嵌入了阵列结构的空隙中,并且表面细胞数量最多,细胞活性明显高于氧化锌纳米棒及纯钛片。结果表明,聚乳酸涂层提高了氧化锌阵列的生物相容性,为细胞生长提供适宜的微环境,有效促进了细胞的黏附与增殖。     

Oriented growth of ZnO nanostructures on Si and Al substrates

Aligned ZnO nanorod arrays and oriented ZnO nanoplates were synthesized on Si and Al substrates, respectively, using a hydrothermal method without any surfactant. The process involved the deposition of ZnO seeds on the substrate and the oriented growth of ZnO nanostructure in aqueous solution. The ZnO seeds were indispensable for the alignment of ZnO nanorods and TEM and XRD analysis confirmed that the ZnO rods are single crystalline grown along [001] direction. Al substrate caused formation of (001) surface dominated ZnO nanoplates, in which ZnO preferential growth direction was suppressed. The photoluminescence spectra of the as-grown ZnO products were measured to indicate their structural and optical quality. These oriented ZnO nanostructures are expected to be prospectively applied in nanodevices fabrication.     

Formation of ZnO nanorod arrays on polytetraflouroethylene (PTFE) via a seeded growth low temperature hydrothermal reaction

ZnO nanorod arrays were formed by a low temperature hydrothermal process on seeded polytetraflouroethylene (PTFE) sheets. The seed layer was formed using thermal oxidation of a thin evaporated Zn film on the PTFE sheet at 300 °C in air for 10 min. The formation of ZnO nanorod arrays in the hydrothermal reactive bath consisting of hexamethylamine (HMT) and Zn ions occurred via the reaction of hydroxyl ions released during the thermal degradation of HMT with the Zn ions. The seed layer provided a template for the nucleation of the ZnO and HMT which also acted as a chelating agent that promoted growth of the ZnO along the c-axis, leading to the formation of exclusively (0 0 2) ZnO nanorods. The effect of exposure time of the seeded PTFE to the reactive solution on the formation of the nanorods was investigated. Well aligned, relatively uniform tapered 300 nm long nanorods can be formed after 8 h of exposure. Longer exposure times to 24 h resulted in the formation of more uniform nanorods with base diameter averaged of ∼100 nm and the tip diameter of ∼50 nm. XRD analysis showed that the ZnO nanorod array had a hexagonal wurtzite structure. This result is in agreement with HR-TEM observations and Raman scattering analysis. Photoluminescence study showed that a strong UV emission peak was obtained at 380 nm and a small peak at 560 nm, which is associated with green emission. The optical band gap measured from these plots was at 3.2 eV on average.     

The effect of seed layer on morphology of ZnO nanorod arrays grown by hydrothermal method

Well-aligned ZnO nanorod arrays were synthesized by hydrothermal method on Si substrates that were covered with pre-deposited ZnO films as seed layers. The ZnO seed layers were deposited by RF magnetron sputtering. It is found that the seed layers prepared under different oxygen partial pressure sputtering parameters and annealing treatment have a great influence on the morphology of the ZnO nanorod arrays grown subsequently on them. Furthermore, growth positions of nanorod/microrod arrays were selectively controlled on the lithography-assist ZnO seed layer.     

Field emission enhancement of ZnO nanorod arrays with hafnium nitride coating

Vertically well-aligned single crystal ZnO nanorod arrays were synthesized and enhanced field electron emission was achieved with hafnium nitride (HfN_x) coating under proper sputtering condition. HfN_x films with various composition have been coated on ZnO nanorod arrays using a reactive direct current (DC) magnetron sputtering system. Morphology and crystal configuration of the ZnO nanorod arrays were investigated by scanning electron microscopy and X-ray diffraction. The field emission properties of the coated and uncoated ZnO nanorod arrays were characterized. The as-grown ZnO nanorod arrays showed a turn-on electric field of 6.60 V μm^− 1 at a current density of 10 μA cm^− 2 and an emission current density of 1 mA cm^− 2 under the field of 9.32 V μm^− 1. While the turn-on electric field of the coated ZnO nanorod arrays sharply decreased to 2.42 V μm^− 1, an emission current density of 1 mA cm^− 2 under the field of only 4.30 V μm^− 1 can be obtained. A method to accurately measure the work function of the coated films was demonstrated.     

Effects of pretreatment of substrates on the preparation of large scale ZnO nanotube arrays

Well-aligned hexagonal ZnO nanotubes (NTs) arrays were synthesized on pretreated indium fin oxide (ITO) substrates by a simple hydro-thermal method. The morphology and structure of the products were characterized by scanning electron microscopy (SEM) and X-my dif-fraction analysis (XRD). A new method of substrate pretreatment was introduced to prepare ZnO coated films. The size of ZnO seeds and the formation rote of ZnO NTs were investigated. Further, the mechanism of the preparation of ZnO NTs was discussed. The photoluminescence (PL) spectrum measurement shows fairly internal defects existing in ZnO nanotubes.     

水热法制备高定向掺铝氧化锌纳米棒阵列

为了制备高定向光电性能优异的掺铝氧化锌(ZAO)纳米棒阵列,采用溶胶-凝胶法在玻璃基片上制备掺铝氧化锌薄膜,以ZAO薄膜为种子层,通过控制掺铝量、稳定荆等工艺参数,采用水热法制备出了高定向ZAO纳米棒阵列.实验表明,铝掺杂量为2%,直径在50nm左右的ZAO纳米棒阵列薄膜具有最好的光致发光性能,表面活性剂可以促进ZAO纳米结构的棒状生长,形成高定向ZAO纳米棒阵列.     

垂直生长于锌基底的Co掺杂ZnO纳米棒阵列显著室温铁磁性能

通过简单的水热合成法在锌片基底上一步制备了Co掺杂的ZnO纳米棒阵列。纳米棒在基底上均匀分布,取向一致,垂直于基底大面积生长。样品结构均为六方纤锌矿结构,具有高结晶质量,不含其它杂相。随着Co掺杂浓度的增加,紫外发射峰强度逐渐下降,近带隙发射峰的半峰宽也较纯ZnO变宽。拉曼光谱显示Co的掺杂使纳米棒出现了氧空位和锌填隙本征缺陷。随着Co浓度的增加这些缺陷也随之增加。掺杂纳米棒阵列的磁滞回线表明样品具有明显的铁磁特征,并有较大的矫顽力Hc~660 Oe。这种ZnO基稀磁半导体纳米棒阵列是一种在自旋电子器件中具有应用潜力的纳米材料。     

Ag-TiO2纳米棒阵列的抗菌性和光催化性能研究

目的：制备一种高抗菌性和高光催化活性的Ag掺杂TiO2（Ag-TiO2）纳米棒阵列。方法通过磁控溅射与水热复合处理法,在钛箔片表面制备出Ag掺杂TiO2（Ag-TiO2）纳米棒阵列,酸化处理过的试样在500℃下煅烧2 h。采用X射线衍射（XRD）进行物相分析,利用场发射扫描电子显微镜（SEM）、场发射透射电子显微镜（TEM）、能量分散谱仪(EDS)观察试样的表面、截面形貌、微观结构和组成,并探究其对大肠杆菌和金黄色葡萄球菌的杀菌性能和对亚甲基蓝的光催化降解能力。结果该工艺下制备的 Ag-TiO2纳米棒大小均匀,取向明显,主要由锐钛矿型 TiO2相组成。Ag-TiO2纳米棒对大肠杆菌和金黄色葡萄球菌具有优异的杀菌效果,杀菌率几乎达到100%。Ag-TiO2纳米棒能有效地提高亚甲基蓝的降解率。结论磁控溅射与水热复合处理法在钛箔片表面成功制备出Ag-TiO2纳米棒阵列,此阵列具有优异的杀菌能力、高抗菌和光催化降解性能。     

Oriented growth of ZnO nanostructures on different substrates via a hydrothermal method

Well-oriented ZnO nanorod arrays are successfully fabricated on different substrates. They are formed on different substrates at low temperature via a hydrothermal method, without adding any catalysts or templates. This approach is convenient and inexpensive. The morphologies of ZnO crystals could be controlled and transformed to other morphologies successfully by using different substrates. The effects of the substrates on the ZnO nanorod arrays have been systematically studied by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The characterizations of XRD and scanning electron microscopy (SEM) reveal that these products are pure single-crystal and the structure is uniform. The photoluminescence property has been detected by photoluminescence (PL) spectrum and Raman spectrum. Photoluminescence measurements show that each spectrum consists of the ultraviolet (UV) band and a relative broad visible light emission peak. But substrates play roles in the intensity of ultraviolet and visible light emission peak. The green emission in Raman measurement may be related to the surface states.     

Effect of ammonia solution on properties of sprayed ZnO thin films consisting of nano-pyramids

Hexagonal wurtzite zinc oxide (ZnO) thin films were deposited at substrate temperatures from 300 to 500 °C with surfactant of ammonia solution. The effect of ammonia on the structural, surface morphology, compositional, optical and electrical properties of ZnO thin films was studied. X-ray diffraction shows that the all films are polycrystalline in nature and have a hexagonal wurtzite structure with a high preferential orientation (002) plane for ammonia solution. High-resolution SEM studies reveal the formation of ZnO films consisting of nano-pyramids with uniformly distributed grains over the entire surface of the substrates. Photoluminescence studies indicate the presence of two emission peaks: (a) a sharp ultra-violet near band edge ～392 nm, (b) a sharp visible deep-level green emission peak ～564 nm. The optical properties show that the direct band gap energy values increase with increasing substrate temperatures.     

Low-temperature synthesis and photoluminescence of ZnO nanostructures by a facile hydrothermal process

We reported a facile route to large-scale ZnO nanostructures by a poly (styrene-alt-maleic acid sodium) (PSMA)-assisted hydrothermal process. Various nanostructures including nanowires, nanobelts and nanorod arrays were fabricated depending on the experimental conditions. The structural studies reveal that all the nanostructures are single crystal with hexagonal phase and preferentially grow along [0 0 0 1]. The organic additive PSMA offers a spatial template for the one-dimensional (1D) growth of ZnO. The photoluminescence (PL) spectra of these nanostructures exhibit coexistence properties of ultraviolet (UV) and green emission. The nanorod arrays and nanobelts exhibit the strongest UV performance and green emission, respectively. We deduce that quantity of surface defects should be responsible for the difference in PL properties of these nanostructures.     

Growth and optical properties of ZnO nanorods prepared through hydrothermal growth followed by chemical vapor deposition

We report on the synthesis of high-quality ZnO nanorods by combining hydrothermal growth (HG) and chemical vapor deposition (CVD) processes. Vertically aligned and closely packed ZnO nanorods were grown by HG on a sputtered ZnO seed layer on a SiO₂/Si (0 0 1) substrate. The top surface of the HG-prepared ZnO nanorods showed very flat surfaces compared with that of the sputtered ZnO seed layer. Therefore, the HG-prepared ZnO nanorods were used as a new alternative seed material for the CVD growth of the ZnO nanorods. Vertical ZnO nanorods were grown by CVD on both the new HG-prepared nanorod seed material and the sputtered ZnO seed layer. The CVD-prepared ZnO nanorods on new HG-prepared nanorod seed material showed better crystalline quality and superior optical properties than the CVD-prepared ZnO nanorods on sputtered seed layer. The former showed negligible deep-level emissions at room temperature photoluminescence measurements. The intensity ratio of near-band-edge emissions to deep-level emissions from the former was about 910, but that from the latter was about 151. This implies that the HG-prepared ZnO nanorods can be used as a promising new seed material for nanostructure synthesis.     

A study on crystallization, optical and electrical properties of the advanced ZITO thin films using co-sputtering system

Multi-functions (conductor, semiconductor and insulator) ZnInSnO (ZITO) transparent oxide thin films have been obtained by a co-sputtering system using ITO target and ZnO target with oxygen gas contents (0-8%). The ZITO film containing a small ITO content had the lowest resistivity (good electron mobility) and higher optical transmittance. In addition, the influences of thermal treatments (post-annealing and substrate temperature) on electrical properties and optical transmittance of ZITO films were studied. Photoluminescence (PL) of the ZITO film confirmed the contribution of ITO content and oxygen gas content on the photo-emission. The ZITO film with zinc atomic concentration of 58 at.% was a good candidate for TCO material (3.08 × 10⁻⁴ Ω cm). Under the substrate temperature of 100 °C or post-annealing temperature of 200 °C, the properties of ZITO film could be improved.     

Photoinduced absorption of Ag nanoparticles deposited on ITO substrate

Substantial changes of absorption after illumination by 300 mW continuous wave green laser at 532 nm were observed. The effect of indium tin oxide (ITO) substrate was explored versus Ag nanoparticles (AgNPs) size, their regularity and surface plasmon resonance. The ITO substrate features play a crucial role for the formation of homogenous AgNPs. The attachments of AgNPs on ITO surface as well as their homogeneity are significantly changed under the influence of the laser treatment. We study the Ag NP deposited on the two different substrates which play a crucial role in the photoinduced absorption. The dependence of the photoinduced absorption versus the time of optical treatment is explained within a framework of the photopolarization of the particular trapping levels on the borders between the ITO substrate and the Ag NP.     

Role of Substrate Roughness in ZnO Nanowire Arrays Growth by Hydrothermal Approach

The role of substrate roughness in ZnO nanowire(NW) arrays hydrothermal growth has been systematically studied.Six silicon substrates with different roughness by chemical etching have been selected to grow ZnO NW arrays hydrothermally after sputtering 5-nm-thick ZnO seed layer as catalyst.The as-grown samples reveal that average diameters and number densities of ZnO NW arrays are inversely proportional to the increasing substrate roughness observed by atomic-force microscopy and scanning electron microscopy.Furthermore,the theoretically derived equations based on nucleation with the Gibbs free energy to describe relations of substrate roughness versus average NW diameter and NW number density match well with experimental results.Research results in this paper can be used to control the number density and the average diameter of ZnO NW arrays by alternating substrate roughness.     

Spray Pyrolysis Deposition of ZnO Thin Films from Zinc Chloride Precursor Solution at Different Substrate Temperatures

ZnO films were prepared at different substrate temperatures through spraying pyrolysis deposition of zinc chloride precursor onto glass substrate. Substrate temperature affects surface morphology of films and therefore their optical and electrical properties. All films are polycrystalline with Wurtzite crystal structure and preferentially grow along c-axis direction. Formation of ZnO rods start at about 500 °C. The diameter and length of rods deposited at 500 °C are350–500 and 550–700 nm, respectively. By increasing substrate temperature, film becomes more coverage and diameter of the rods reduces to 250–300 nm but their length increases to 1,000–1,200 nm, respectively. Optical transmission in visible region decreases with increasing substrate temperature. An ultraviolet emission and two visible emissions at 2.82 and2.37 eV are observed for photoluminescence spectra at room temperature. The resistivity of ZnO films increases with increasing substrate temperature due to surface morphology.     

Filtered vacuum arc deposition of undoped and doped ZnO thin films: Electrical, optical, and structural properties

Filtered vacuum (cathodic) arc deposition (FVAD, FCVD) of metallic and ceramic thin films at low substrate temperature (50-400 °C) is realized by magnetically directing vacuum arc produced, highly ionized, and energetic plasma beam onto substrates, obtaining high quality coatings at high deposition rates. The plasma beam is magnetically filtered to remove macroparticles that are also produced by the arc. The deposited films are usually characterized by their good optical quality and high adhesion to the substrate. Transparent and electrically conducting (TCO) thin films of ZnO, SnO₂, In₂O₃:Sn (ITO), ZnO:Al (AZO), ZnO:Ga, ZnO:Sb, ZnO:Mg and several types of zinc-stannate oxides (ZnSnO₃, Zn₂SnO₄), which could be used in solar cells, optoelectronic devices, and as gas sensors, have been successfully deposited by FVAD using pure or alloyed zinc cathodes. The oxides are obtained by operating the system with oxygen background at low pressure. Post-deposition treatment has also been applied to improve the properties of TCO films.The deposition rate of FVAD ZnO and ZnO:M thin films, where M is a doping or alloying metal, is in the range of 0.2-15 nm/s. The films are generally nonstoichiometric, polycrystalline n-type semiconductors. In most cases, ZnO films have a wurtzite structure. FVAD of p-type ZnO has also been achieved by Sb doping. The electrical conductivity of as-deposited n-type thin ZnO film is in the range 0.2-6 × 10^− 5 Ω m, carrier electron density is 10²³-2 × 10²⁶ m^− 3, and electron mobility is in the range 10-40 cm²/V s, depending on the deposition parameters: arc current, oxygen pressure, substrate bias, and substrate temperature. As the energy band gap of FVAD ZnO films is ∼ 3.3 eV and its extinction coefficient (k) in the visible and near-IR range is smaller than 0.02, the optical transmission of 500 nm thick ZnO film is ∼ 0.90.