Characterisation of ZnO nanorod arrays grown by a low temperature hydrothermal method

In this paper, growth steps of well defined ZnO nanorod arrays deposited on seeded substrates were investigated. To obtain ZnO seed layer on glass substrates, a successive ionic layer adsorption and reaction (SILAR) method was used and then ZnO nanorods were grown on seed layer using a chemical bath deposition (CBD) method. The effects of seed layer and deposition time on morphology, crystallographic structure (e.g. grain size, microstrain and dislocation density) and electrical characteristics of ZnO nanorods were studied. From the SEM micrographs, it could be seen that the ZnO nanorods densely covered the substrate and were nearly perpendicular to the substrate surface. The XRD patterns showed that the ZnO nanorod arrays had a hexagonal wurtzite structure with a preferred orientation along the (002) plane. An increase in deposition time resulted in an increase in the intensity of the preferred orientation and grain size, but a decrease in microstrain and dislocation density. Electrical activation energies of the structures were calculated as 0.15–0.85?eV from current–temperature characteristics. It was concluded that the morphologies of the structures obtained in this study via a simple and fast solution method can provide high surface areas which are important in area-dependent applications, such as solar cells, hydrogen conversion devices, sensors, etc.     

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.     

两步法制备空间取向高度一致的ZnO纳米棒阵列

采用两步法,即先用磁控溅射在Si(100)表面生长一层ZnO籽晶层、再利用液相法制备空间取向高度一致的ZnO纳米棒阵列.用扫描电子显微镜、X射线衍射、高分辨透射电子显微镜和选区电子衍射对样品形貌和结构特征进行了表征.结果表明,ZnO纳米棒具有垂直于衬底沿c轴择优生长和空间取向高度一致的特性和比较大的长径比,X射线衍射的(XRD)(0002)峰半高宽只有0.06°,选区电子衍射也显示了优异的单晶特性.光致发光谱表明ZnO纳米棒具有非常强的紫外本征发光和非常弱的杂质或缺陷发光特性. 关键词： ZnO纳米棒阵列 ZnO籽晶层 两步法 液相生长     

Seed layer-free synthesis and characterization of vertically grown ZnO nanorod array via the stepwise solution route

A novel stepwise method was developed for the deposition of ZnO nanorod array (NRA) from the simple inorganic aqueous solution. Different from the traditional one-pot synthesis route, merely a thin liquid precursor layer adsorbed on the substrate instead of the bulk solution underwent the reaction at elevated temperature in a typical deposition cycle. Sparse and vertically grown wurtzite ZnO NRA was deposited on seed layer-free glass substrate after 20 cycles (in typically 20 min). Each individual ZnO rod possessed the well-defined hexagonal facet, the side length of about 150 nm, the aspect ratio of 2:3, and the small size dispersity. Also the overall ZnO NRA exhibited high ultraviolet photoluminescence and weak blue emission, indicating its good optical properties. Mechanism analysis indicated that, the decrease of the supersaturation degree in solution after the climax in the reaction period of each deposition cycle is the root cause of the sparse nucleation and the vertical growth of ZnO nanorods. The work has opened up a novel stepwise approach toward high quality ZnO NRA, being valuable for extending the synthetic methods of semiconductor nanostructures in mild solutions.     

电化学沉积法制备ZnO纳米柱及自驱动紫外探测性能研究

采用提拉法在ITO衬底上制备种子层,并使用电化学沉积制备高度取向的氧化锌纳米棒,研究了不同提拉次数下籽晶层厚度与电化学沉积电位对氧化锌纳米棒形貌的影响。在此基础上,制备了自驱动型紫外探测器并测试了其光响应谱。结果表明,该探测器可以对部分紫外波段(300~400 nm)有选择性地光响应,峰值响应度为0.012 A/W。     

CdS quantum dot-sensitized ZnO nanorod-based photoelectrochemical solar cells

ZnO nanorods have been grown using ZnO seed layer onto ITO-coated glass substrates. CdS quantum dots have been deposited onto ZnO nanorods using simple precursors by chemical method and the assembly of CdS quantum dots with ZnO nanorod has been used as photo-electrode in quantum dot-sensitized solar cells. X-ray diffraction results show that ZnO seed layer, ZnO nanorods, and CdS quantum dot-sensitized ZnO nanorods exhibit hexagonal structure. The particle size of CdS nanoparticle is 5 nm. The surface morphology studied using scanning electron microscope shows that the top surface of the vertically aligned ZnO nanorods is fully covered by CdS quantum dots. The ZnO nanorods have diameter ranging from 100 to 200 nm. The absorption spectra reveal that the absorption edge of CdS quantum dot-sensitized ZnO nanorods shift toward longer wavelength side when compared to the absorption edge of ZnO. The efficiency of the fabricated CdS quantum dot-sensitized ZnO nanorod-based solar cell is 0.69% and is the best efficiency reported so far for this type of solar cells.     

Solution-based growth of ZnO nanorods for light-emitting devices: hydrothermal vs. electrodeposition

ZnO nanorods have been grown by two inexpensive, solution-based, low-temperature methods: hydrothermal growth and electrodeposition. Heterojunction n-ZnO nanorods/p-GaN light-emitting diodes have been studied for different nanorod growth methods and different preparation of the seed layer. We demonstrate that both the nanorod properties and the device performance are strongly dependent on the growth method and seed layer. All the devices exhibit light emission under both forward and reverse bias, and the emission spectra can be tuned by ZnO nanorod deposition conditions. Electrodeposition of rods or a seed layer results in yellow emission, while conventional hydrothermal growth results in violet emission.     

ZnO nanorod arrays fabrication via chemical bath deposition: Ligand concentration effect study

A new ligand, N,N,N′,N′-tetramethylethylenediamine, has been used to grow ZnO nanorods on silicon substrates via a two steps approach. A preliminary seeding on silicon substrates has been combined with chemical bath deposition using a Zinc acetate–N,N,N′,N′-tetramethylethylenediamine aqueous solution. The used diamino ligand has been selected as Zn²⁺ complexing agent and the related hydrolysis generates the reacting ions (Zn²⁺ and OH⁻) responsible for the ZnO growth. The seed layer has been annealed at low temperature (<200 °C) and the ZnO nanorods have been grown on this ZnO amorphous layer. There is experimental evidence that the ligand concentration (ranging from 5 to 50 mM) strongly affects the alignment of ZnO nanorods on the substrate, their lateral dimension and the related surface density. Length and diameter of ZnO nanorods increase upon increasing the ligand concentration, while the nanorod density decreases. Even more important, it has been demonstrated, as proof of concept, that chemical bath deposition can be usefully combined with colloidal lithography for selective ZnO nanorod deposition. Thus, by patterning the ZnO seeded substrate with polystyrene microsphere colloidal lithography, regular Si hole arrays, spatially defined by hexagonal ZnO nanorods, have been successfully obtained.     

In_2O_3:Sn中间层改善B掺杂ZnO薄膜的性能及其应用研究

金属有机化学气相沉积(MOCVD)法生长的掺硼氧化锌(BZO)薄膜,具有天然的"类金字塔"绒面结构,作为硅基薄膜太阳电池的前电极具有良好的陷光效果.但直接获得的BZO薄膜表面形貌过于尖锐,影响后续硅基薄膜材料生长质量及太阳电池的光电转换效率.本文设计了以一层超薄In2O3:Sn(ITO)薄膜(～4 nm厚度)作为中间层的多层膜,并通过对顶层BZO薄膜的厚度调制,改善BZO薄膜的表面特性,薄膜结构为:glass/底层BZO/ITO/顶层BZO.合适厚度的顶层BZO薄膜有助于获得类似"菜花状"形貌特征,尖锐的表面趋于"柔和",而较厚的顶层BZO薄膜仍然保持"类金字塔状"结构."柔和"的BZO薄膜表面结构有助于提高后续生长薄膜电池的结晶质量.将获得的新型"三明治"结构多层膜应用于p-i-n型氢化微晶硅(μc-Si:H)薄膜太阳电池,相比传统的BZO薄膜,电池的量子效率QE在500—800 nm波长范围提高了～10%,并且电池的Jsc和Voc均有所提高.     

电沉积法制备ZnO纳米柱及其机制研究

采用阴极还原方法,以Zn(NO₃)₂水溶液为电解液制备ZnO纳米柱。分析了不同沉积电位和不同沉积时间的缓冲层对ZnO纳米柱的密度、形貌及取向的影响。通过分析缓冲层在不同沉积时间下的电流密度变化,研究了缓冲层对ZnO纳米柱密度影响的机理。利用扫描电子显微镜(SEM)和X射线衍射(XRD)分析了样品的表面形貌及结构。研究结果表明,缓冲层能够增加ZnO纳米柱的密度及c轴的取向性,当缓冲层的沉积时间为60 s时,可以得到密度最大、取向最好的ZnO纳米柱。     

Enhanced power efficiency of ZnO based organic/inorganic solar cells by surface modification

We present series of strategies to enhance efficiency of ZnO nanorods based organic/inorganic solar cells with spin-coated P3HT:PCBM blend as active layer. The performance of the as-fabricated devices is improved by controlling the size of ZnO nanorods, annealing temperature and time of active layer, surface modification of ZnO with PSBTBT. Optimized device of ITO/ZnO nanorod/P3HT:PCBM/Ag device with PSBTBT surface modification and air exposure reaches an efficiency of 2.02% with a short-circuit current density, open-circuit voltage and fill factor of 13.23 mA cm⁻², 0.547 V and 28%, respectively, under AM 1.5 irradiation of 100 mW m⁻², the increase in efficiency is 7-fold of the PSBTBT surface modified ITO/ZnO nanorods/P3HT:PCBM/Ag device compared with the unmodified one, which is own to the increased interface contact, expanded light absorption, tailored band alignment attributed to PSBTBT. We found exposure to air and surface modification is crucial to improve the device performance, and we discussed the mechanisms that affect the performance of the devices in detail.     

Interfacial engineering of CuO nanorod/ZnO nanowire hybrid nanostructure photoanode in dye-sensitized solar cell

Developing efficient and cost-effective photoanode plays a vital role determining the photocurrent and photovoltage in dye-sensitized solar cells (DSSCs). Here, we demonstrate DSSCs that achieve relatively high power conversion efficiencies (PCEs) by using one-dimensional (1D) zinc oxide (ZnO) nanowires and copper (II) oxide (CuO) nanorods hybrid nanostructures. CuO nanorod-based thin films were prepared by hydrothermal method and used as a blocking layer on top of the ZnO nanowires’ layer. The use of 1D ZnO nanowire/CuO nanorod hybrid nanostructures led to an exceptionally high photovoltaic performance of DSSCs with a remarkably high open-circuit voltage (0.764 V), short current density (14.76 mA/cm² under AM1.5G conditions), and relatively high solar to power conversion efficiency (6.18%) . The enhancement of the solar to power conversion efficiency can be explained in terms of the lag effect of the interfacial recombination dynamics of CuO nanorod-blocking layer on ZnO nanowires. This work shows more economically feasible method to bring down the cost of the nano-hybrid cells and promises for the growth of other important materials to further enhance the solar to power conversion efficiency.     

Al和Sb共掺对ZnO有序阵列薄膜的结构和光学性能的影响

采用水热合成法在预先生长的ZnO种子层的玻璃衬底上制备出Al和Sb共掺ZnO纳米棒有序阵列薄膜. 通过X射线衍射、扫描电镜、透射电镜和选区电子衍射分析表明:所制备的薄膜由垂直于ZnO种子层的纳米棒组成, 呈单晶六角纤锌矿ZnO结构, 且沿[001]方向择优生长, 纳米棒的平均直径和长度分别为27.8 nm和1.02 μm. Al和Sb共掺ZnO纳米棒有序阵列薄膜的拉曼散射分析表明:相对于未掺杂ZnO薄膜的拉曼振动峰(580 cm^-1), Al和Sb共掺ZnO阵列薄膜的E₁(LO)振动模式存在拉曼位移. 当Al和Sb的掺杂量为3.0at%,4.0at%,5.0at%,6.0at%时, Al和Sb共掺ZnO阵列薄膜的拉曼振动峰的位移量分别为3,10,14,12 cm^-1. E₁ (LO) 振动模式位移是由Al和Sb掺杂ZnO产生的缺陷引起的. 室温光致发光结果表明:掺杂Al和Sb后, ZnO薄膜在545 nm处的发光强度减小,在414 nm处的发光强度增加. 这是由于掺杂Al和Sb后, ZnO薄膜中Zn_i缺陷增加, O_i缺陷减少引起的. 关键词： Al和Sb共掺ZnO薄膜 纳米棒有序阵列 结构表征 拉曼散射     

The study of low temperature hydrothermal growth of ZnO nanorods on stents and its applications of cell adhesion and viability

The hydrothermal growths of the ZnO nanorods with the densities ranging from 157 to 73 nanorods/μm² were achieved by diluting the ZnO seed solution. However, the ZnO seed nanocrystals started to agglomerate for the seed solution diluted below 1% of the original nano-crystalline solutions and resulted in the formation of clustered nanorods. With the assistance of a surfactant, Triton X-100, the nanorod density can be further reduced to 4 nanorods/μm². The diameters of the nanorods depended on the concentration of the seed solution and agitation speed of the nanorod growth solution. More diluted seed solution used and less agitation of the growth solution, the larger diameter of the nanorods was obtained. This indicated that the nanorod growth mechanism was controlled by the diffusion of reactants. With sufficient agitation of the growth solution, the nanorod can be uniformly grown with subjects on any arbitrary geometry. We have demonstrated ZnO nanorods growth on both inside and outside of biliary stents as well as on nitinol wires used as metal stents. The effect of nanorod density on the NIH 3T3 and HUVEC cells growth was also investigated in this study and the results suggested nanorod-coating to be a suitable method for controlling cell adhesion and viability on implantable devices.     

Selective growth of ZnO nanorods in aqueous solution

ZnO nanorod arrays find applications in solar energy conversion, light emission and other promising areas. One approach to generate ZnO nanorods is the cost efficient aqueous chemical growth (ACG). Usually the ACG process is based on a nucleation step followed by growth of ZnO nanorods in aqueous solution at temperatures below 95 C.We report on the fabrication of homogeneous, large scale arrays of nanorods on various substrate materials (Si, glass, polymer) by ACG. PL-measurements show surprisingly good optical quality although the rods were grown at low temperature.Even though we have developed patterning of these arrays with photolithographic techniques, a bottom up approach for lateral patterning is important concerning further applications especially for mass-production. The substrates with patterned metal layers were employed to realize selective growth of nanorods. The experiments were carried out on Ti-, Ag- and Pt-patterned substrates. Selective growth on metal structured glass substrates was developed and is described.     

Metal oxide buffer layer for improving performance of polymer solar cells

We report the application of aluminum doped ZnO (ZnO:Al) layer as a buffer on ITO glass for fabrication of non-inverted polymer solar cells. The ZnO:Al thin film was deposited using DC magnetron sputtering, with the thickness being varied from 23 to 100 nm. The devices showed most discernible improvements in their efficiencies when a thin layer of ZnO:Al film of thickness ∼40 nm was introduced. The observed enhancement in short circuit current density and open circuit voltage is likely attributed to the role of the ZnO:Al film as an optical tuner and an interfacial diffusion barrier. The result suggests that a metal oxide layer inserted between ITO and polymer layers can be a route for improving both efficiency and stability of polymer solar cells.     

The influence of using different substrates on the structural and optical characteristics of ZnO thin films

ZnO thin films with thikness d = 100 nm were deposited onto different substrates such as glass, kapton, and silicon by radio frequency magnetron sputtering. The structural analyses of the films indicate they are polycrystalline and have a wurtzite (hexagonal) structure.The ZnO layer deposited on kapton substrate shows a stronger orientation of the crystallites with (0 0 2) plane parallel to the substrate surface, as compared with the other two samples of ZnO deposited on glass and silicon, respectively.All three layers have nanometer-scale values for roughness, namely 1.7 nm for ZnO/glass, 2.4 nm for ZnO/silicon, and 6.8 nm for ZnO/kapton. The higher value for the ZnO layer deposited on kapton substrate makes this sample suitable for solar cells applications. Transmission spectra of these thin films are strongly influenced by deposition conditions. With our deposition conditions the transparent conducting ZnO layer has a good transmission (78-88%) in VIS and NIR domains. The values of the energy gap calculated from the absorption spectra are 3.23 eV for ZnO sample deposited onto glass substrate and 3.30 eV for the ZnO sample deposited onto kapton polymer foil substrate. The influence of deposition arrangement and oxidation conditions on the structural, morphological, and optical properties of the ZnO films is discussed in the present paper.     

准一维深色纳米ZnO的水热方法生长及其结构和光学性能的调变

本文以高纯度金属锌箔为Zn和衬底,利用传统的水热合成方法制备了深色的纳米结构ZnO. 研究发现,改变制备温度可以调变ZnO样品的颜色和光学性能,尤其是提高温度可以显著地降低可见光波段太阳能的活性. 推测这种现象与ZnO纳米棒顶端的尖锥形貌密切相关,这种结构加剧了光在ZnO纳米棒之间的折射和反应. 改善ZnO的光吸收能力对于提升ZnO基太阳电池的效率有重要意义.     

Patterned growth of zinc oxide nanorods using poly(vinyl alcohol)-N-methyl-4(4′-formylstyryl)pyridinium methosulfate acetal and zinc acetate mixture as a seed layer

This paper reports a new method for fabricating two-dimensional ZnO nanorod patterns. A water soluble mixture of poly(vinyl alcohol)-N-methyl-4(4′-formylstyryl)pyridinium methosulfate acetal (PVA-Sbq) and zinc acetate (ZnA) was used as a negative photoresist to produce the desired patterns using conventional photolithography. Hydrothermally-grown ZnO nanorods were grown selectively on the calcined PVA-Sbq/ZnA patterns. The appropriate concentration of PVA-Sbq and ZnA that can produce the desirable seed layer pattern was determined experimentally. Furthermore, the effects of the calcination time on the morphology and vertical alignment of ZnO nanorods were investigated. The vertically-aligned ZnO nanorods were generated by sufficient calcination of the patterned seed layer. On the other hand, the aspect ratio of ZnO nanorods decreased slightly with increasing calcination time. This new approach provides a simple and cost-effective method for fabricating ZnO nanorod patterns which can be beneficial in various solid-state devices and optoelectronic applications.     

Nanoimprint texturing of transparent flexible substrates for improved light management in thin‐film solar cells

We present a nanoimprint based approach to achieve efficient light management for solar cells on low temperature transparent polymer films. These films are particularly low‐priced, though sensitive to temperature, and therefore limiting the range of deposition temperatures of subsequent solar cell layers. By using nanoimprint technology, we successfully replicated optimized light trapping textures of etched high temperature ZnO:Al on a low temperature PET film without deterioration of optical properties of the substrate. The imprint‐textured PET substrates show excellent light scattering properties and lead to significantly improved incoupling and trapping of light in the solar cell, resulting in a current density of 12.9 mA/cm², similar to that on a glass substrate. An overall efficiency of 6.9% was achieved for a flexible thin‐film silicon solar cell on low cost PET substrate. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)