A simple electrochemical deposition route for the controllable growth of Ce-doped ZnO nanorods

Here we report that the various Ce⁴⁺-doped ZnO nanorods can be successfully synthesized by electrochemical deposition route, which represents a simple, quick and economical method for the controllable growth of Ce⁴⁺-doped ZnO nanorods. The high-resolution transmission electron microscopy (HRTEM) and the selected area electron diffraction (SAED) both proved that the prepared Ce⁴⁺-doped ZnO nanorods consisted of single crystal with preferential growth in the [0 0 0 1] direction. The morphology and size of the nanorods can be tailored by optimizing the synthetic parameters. Furthermore, the flowerlike Ce⁴⁺-doped ZnO nanorod clusters can also be successfully prepared. An obvious blue-shifted absorption peak of Ce⁴⁺-doped ZnO nanorod compared with that of the bulk ZnO phase was observed.     

Growth of three-dimensional ZnO nanorods by electrochemical method for quantum dots-sensitized solar cells

There-dimensional (3D) superstructure was expected to fabricate high performance photoelectrodes of quantum dot-sensitized solar cells (QDSCs). In this paper, the ZnO 3D superstructure with multi-layer structure (3D ZnO nanorods) was grown on ITO glass by a novel electrochemical method at low temperature (60–90 °C). The 3D ZnO nanorods were composed of close-packed ZnO nanorod bundles with wide dimension distribution ranging from hundreds of nanometers to several micrometers. The effects of some important parameters, such as concentration of Zn(NO₃)₂, deposition temperature and concentration of ZnO nanoparticles (served as growth seeds for ZnO nanorods), on the morphology of 3D ZnO nanorods were also studied by scanning electron microscopy. Once being applied in QDSCs, the 3D ZnO nanorods showed more superior photoelectrochemical performance to ZnO nanorod array. The conversion efficiency of 1.42% achieved by the QDSC based on 3D ZnO nanorods was a very promising value for the QDSCs based on ZnO electrodes.     

Growth of vertically aligned ZnO nanorods using textured ZnO films

A hydrothermal method to grow vertical-aligned ZnO nanorod arrays on ZnO films obtained by atomic layer deposition (ALD) is presented. The growth of ZnO nanorods is studied as function of the crystallographic orientation of the ZnO films deposited on silicon (100) substrates. Different thicknesses of ZnO films around 40 to 180 nm were obtained and characterized before carrying out the growth process by hydrothermal methods. A textured ZnO layer with preferential direction in the normal c-axes is formed on substrates by the decomposition of diethylzinc to provide nucleation sites for vertical nanorod growth. Crystallographic orientation of the ZnO nanorods and ZnO-ALD films was determined by X-ray diffraction analysis. Composition, morphologies, length, size, and diameter of the nanorods were studied using a scanning electron microscope and energy dispersed x-ray spectroscopy analyses. In this work, it is demonstrated that crystallinity of the ZnO-ALD films plays an important role in the vertical-aligned ZnO nanorod growth. The nanorod arrays synthesized in solution had a diameter, length, density, and orientation desirable for a potential application as photosensitive materials in the manufacture of semiconductor-polymer solar cells.

PACS

61.46.Hk, Nanocrystals; 61.46.Km, Structure of nanowires and nanorods; 81.07.Gf, Nanowires; 81.15.Gh, Chemical vapor deposition (including plasma-enhanced CVD, MOCVD, ALD, etc.)     

Growth temperature dependent properties of ZnO nanorod arrays on glass substrate prepared by wet chemical method

In this work, ZnO nanorod arrays were grown on glass substrate by the wet chemical method, and the effect of synthesis temperature on the properties was investigated. The grown nanorods were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), Raman and Photoluminescence (PL) measurements. XRD pattern showed that nanorod prepared at 80 °C and 90 °C has high crystallinity with wurtzite structure and orientated along the c-axis. However, nanorods were not formed at 60 °C and 70 °C due to less energy supply for the growth of the ZnO. FE-SEM results showed that the morphology and the size of ZnO can be effectively controlled. In particular, as the temperature increased, diameter of the nanorod was increased while length decreased. Raman scattering spectra of ZnO nanorod arrays revealed the characteristic E₂^high mode that is related to the vibration of oxygen atoms in the wurtzite ZnO. Room-temperature PL spectra of the ZnO nanorods revealed a near-band-edge (NBE) emission peak. The NBE (UV light emission) band at ~383 nm might be attributed to the recombination of free exciton. The narrow full-width at half-maximum (FWHM) of the UV emission indicated that ZnO nanorods had high crystallinity.     

ZnO纳米棒水热法生长与表征

采用两步法在FTO导电玻璃衬底上制备ZnO纳米棒,首先利用浸渍-提拉法在FTO导电玻璃衬底上制备ZnO晶种层,然后把有ZnO晶种层的FTO衬底放入盛有生长溶液的反应釜中利用水热法制备ZnO纳米棒.研究了生长溶液的浓度、生长温度和生长时间对所制备的对ZnO纳米棒阵列的微结构和光致发光性能的影响,利用X射线衍射(XRD)、扫描电子显微镜(SEM)和光致发光谱(PL)研究了ZnO样品的结构、形貌和光学性质.实验结果表明:所制备的ZnO纳米棒呈现六方纤锌矿结构,沿(002)晶面择优取向生长,纳米棒的平均直径约为100 nm,长度约为2.5 μm.所制备的ZnO纳米棒在390 nm附近具有很强的紫外发光峰和在550 nm附近有较弱的宽绿光发光峰.     

Controllable growth of ZnO nanorod arrays with different densities and their photo-electric properties

ABSTRACT: Since the photo-electric response and charge carriers transport can be influenced greatly by the density and spacing of the ZnO nanorod arrays, controlling of these geometric parameters precisely is highly desirable but rather challenging in practice. Here, we fabricated patterned ZnO nanorod arrays with different density and spacing distance on silicon (Si) substrate by electron beam lithography (EBL) method combined with the subsequent hydrothermal reaction process. By using the EBL method, patterned ZnO seed layers with different areas and spacing distances were obtained firstly. ZnO nanorod arrays with different density and various morphologies were obtained by the subsequent hydrothermal growth process. The combination of EBL and hydrothermal growth process was very attractive and made us could control the geometric parameters of ZnO nanorod arrays expediently. Finally, the vertical transport properties of the patterned ZnO nanorod arrays were investigated through the micro probe station equipment and the I-V measurement results indicated that back-to-back Schottky contacts with different barriers height were formed in dark conditions. Under UV light illumination, the patterned ZnO nanorod arrays showed a high UV light sensitivity, and the response ratio was about 104. The controllable fabrication of patterned ZnO nanorod arrays and understanding for their photo-electric transport properties were helpful to improve the performance of nanodevices based on them.     

Controllable size and photoluminescence of ZnO nanorod arrays on Si substrate prepared by microwave-assisted hydrothermal method

High-quality ZnO nanorod arrays were grown on silicon substrates by microwave-assisted hydrothermal method. A ZnO seed layer deposited by magnetron sputtering was used for promoting nanorod growth. Process optimization indicates that the size and surface density of nanorods can be controlled individually by varying process parameters including precursor concentration, heating temperature, and heating time. The photoluminescence performance of the nanorods is closely dependent on the mean size of the rods. Reducing rod diameter leads to decreased UV emission and visible emission intensity ratio, which has been attributed to the increased impurities or defects on the rod surface. The present results provide a feasible approach to modify the optical properties of transparent ZnO nanorod arrays.     

Farming of ZnO nanorod-arrays via aqueous chemical route for photoelectrochemical solar cell application

A low temperature aqueous chemical route is employed for the synthesis of zinc oxide (ZnO) nanorod arrays onto the soda lime and fluorine-doped tin oxide (FTO) coated glass substrates at various deposition times. Synthesis/farming of ZnO nanorod arrays (ZNRs) consists of the three-step as-ZnO seed forming, ZnO seed sowing followed by ZnO nanorod arrays growing. The length and diameter of ZnO nanorods increased with the reaction time prolonging. The physical, chemical and morphological properties were analyzed by means of X-ray diffraction (XRD), UV–visible spectroscopy (UV–vis), photoluminescence (PL), energy dispersive spectroscopy (EDS) and scanning electron microscopy (SEM) respectively. The XRD pattern revealed wurtzite crystal structures of ZNRs, preferentially orienting in the (002) direction. SEM micrographs show that the ZnO nanorods grew up perpendicular to the substrate and their length increases with increase in deposition time. Finally, the photoelectrochemical (PEC) performance of ZNRs thin films were studied. The junction quality factor upon illumination (n_l), series and shunt resistance (R_s and R_sh), flat-band-potential (V_FB), fill factor (FF) and efficiency (η) have been estimated.     

Microcontact Printing of Organic Self-Assembled Monolayers for Patterned Growth of Well-Aligned ZnO Nanorod Arrays and their Field-Emission Properties

This paper describes a simple method for preparing well-aligned ZnO nanorod arrays in a more tunable fashion, which enables the synthesis of nanorods directly in various patterns and the easy control of the array density. This method is based on a combination of the microcontact printing process for patterning and a solution approach for depositing ZnO nanorods. The growth behavior between the contact and noncontact areas is investigated. Different formation mechanisms are proposed, and it is found that the key difference between nanorod and microrod forms was the ZnO seed layer and the van der Waals force at specific conditions. The role of self-assembled monolayers of octadecyl-trichloro-silane in the reaction solution is also discussed. Wettability of the surfaces is assessed by measuring the water contact angle, and the results show significant variation with surface morphology, from 17.6° to 123.6°. The lowest turn-on applied field strength is 4.65 V/μm at the current density of 10 μA/cm², which is achieved by the lowest array density of nanorods. The field-emission characteristics of the nanorods are found to be highly reproducible. The results could be valuable for the application of field-emission-based devices using ZnO nanorod arrays as cathode materials.     

Selective Growth of Vertical-aligned ZnO Nanorod Arrays on Si Substrate by Catalyst-free Thermal Evaporation

By thermal evaporation of pure ZnO powders, high-density vertical-aligned ZnO nanorod arrays with diameter ranged in 80–250 nm were successfully synthesized on Si substrates covered with ZnO seed layers. It was revealed that the morphology, orientation, crystal, and optical quality of the ZnO nanorod arrays highly depend on the crystal quality of ZnO seed layers, which was confirmed by the characterizations of field-emission scanning electron microscopy, X-ray diffraction, transmission electron microscopy, and photoluminescence measurements. For ZnO seed layer with wurtzite structure, the ZnO nanorods grew exactly normal to the substrate with perfect wurtzite structure, strong near-band-edge emission, and neglectable deep-level emission. The nanorods synthesized on the polycrystalline ZnO seed layer presented random orientation, wide diameter, and weak deep-level emission. This article provides a C-free and Au-free method for large-scale synthesis of vertical-aligned ZnO nanorod arrays by controlling the crystal quality of the seed layer.     

Effect of ZnO seed layers on the solution chemical growth of ZnO nanorod arrays

High density ZnO nanorod arrays were grown on Si substrates coated with ZnO seed layers via aqueous solution route. The ZnO seed layers were deposited on the substrate using DC reactive sputtering and RF magnetron sputtering. It was found that ZnO seed layer with (1 0 3) preferred orientation, prepared using DC reactive sputtering, did not facilitate the formation of ZnO nanorods in the solution grown process. Prior seeding of the surface by ZnO layer with (0 0 2) preferred orientation, deposited using RF magnetron sputtering, leads to nucleation sites on which ZnO nanorod arrays can grow in a highly aligned fashion. ZnO nanorods with well-defined hexagonal facets (0 0 2) were grown almost vertically over the entire substrate. The uniformity and alignment of the nanorod arrays are strongly related to the properties of underneath ZnO seed layers.     

Seedless Pattern Growth of Quasi-Aligned ZnO Nanorod Arrays on Cover Glass Substrates in Solution

A hybrid technique for the selective growth of ZnO nanorod arrays on wanted areas of thin cover glass substrates was developed without the use of seed layer of ZnO. This method utilizes electron-beam lithography for pattern transfer on seedless substrate, followed by solution method for the bottom-up growth of ZnO nanorod arrays on the patterned substrates. The arrays of highly crystalline ZnO nanorods having diameter of 60 ± 10 nm and length of 750 ± 50 nm were selectively grown on different shape patterns and exhibited a remarkable uniformity in terms of diameter, length, and density. The room temperature cathodluminescence measurements showed a strong ultraviolet emission at 381 nm and broad visible emission at 585–610 nm were observed in the spectrum.     

Broadband anti-reflective properties of grown ZnO nanopyramidal structure on Si substrate via low-temperature electrochemical deposition

Anti-reflection coatings (ARCs) are widely used in various optical and optoelectronic devices to minimize the reflection of light. In this study, we demonstrated the fabrication of ZnO nanopyramidal structures on Si substrate via low-temperature electrochemical deposition. We also investigated the anti-reflection (AR) properties of these nanostructures compared with nanorods and planar ZnO texture on Si substrates. We changed the growth conditions, namely, growth temperature and applied current density, to modify the shape of the ZnO nanorod tips. Nanopyramidal structures with continuously varying refractive index profiles in a single layer were obtained. Reflectance spectra show that the nanopyramid-based texture reduced the reflection of light in a broad spectral range from 380 nm to 1000 nm and is much more effective than nanorod and planar textures. For nanopyramid arrays (NPAs) with average tip diameter of 20 nm, we achieved a 6.5% reflectance over a wide range of wavelengths, which is superior to an optimized single-layer ARC such as SiO₂ or TiO₂. These textured ZnO ARCs may be applied to a wide variety of photovoltaic devices and other anti-reflection applications with large areas because of their low temperature, fast growth, and simple fabrication.     

Effect of Aspect Ratio on Field Emission Properties of ZnO Nanorod Arrays

ZnO nanorod arrays are prepared on a silicon wafer through a multi-step hydrothermal process. The aspect ratios and densities of the ZnO nanorod arrays are controlled by adjusting the reaction times and concentrations of solution. The investigation of field emission properties of ZnO nanorod arrays revealed a strong dependency on the aspect ratio and their density. The aspect ratio and spacing of ZnO nanorod arrays are 39 and 167 nm (sample C), respectively, to exhibit the best field emission properties. The turn-on field and threshold field of the nanorod arrays are 3.83 V/μm and 5.65 V/μm, respectively. Importantly, the sample C shows a highest enhancement of factor β, which is 2612. The result shows that an optimum density and aspect ratio of ZnO nanorod arrays have high efficiency of field emission.     

A facile and green strategy for large-scale synthesis of silica nanotubes using ZnO nanorods as templates

Hollow silica nanostructures exhibit important applications in catalysis, sensing, and gene delivery due to their increased surface areas, good biocompatibility, and unique optical features. Here we report a simple and green approach to synthesize silica nanotubes using environment—friendly ZnO nanorods as templates. The ZnO nanorods are first coated with a layer of uniform silica shell by a sol–gel method. Then silica nanotubes are derived from the ZnO@SiO₂ nanohybrids after removal of the ZnO nanorod cores in diluted hydrochloric acid solution. The samples at different stages were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, Energy-dispersive X-ray spectroscopy, and Transmission electron microscopy. By controlling the structure of the ZnO@SiO₂ nanohybrids, such as shell thickness, and the diameter and length of ZnO nanorods, size controllable SiO₂ nanotubes can be expected.     

Electrochemical deposition of branched hierarchical ZnO nanowire arrays and its photoelectrochemical properties

Branched hierarchical ZnO nanowire arrays are synthesized on fluorine-doped tin oxide (FTO) substrate via a two-step electrochemical deposition process, which involves the electrodeposition of ZnO nanowire arrays on conductive glass substrate, followed by the electrochemical growth of ZnO nanorod branches on the backbones of the primary ZnO nanowires. The formation mechanism of the branched hierarchical nanostructure is discussed. It is demonstrated that coating the primary nanowire arrays with ZnO nanoparticles seed layer plays a key role in synthesising the branched hierarchical ZnO nanostructure. By adjusting the concentration of Zn(CH₃COO)₂ colloid in coating process and the reaction time of the second-step deposition, the density and the length of the secondary nanorod branches in the hierarchical nanostructures can be both varied. Moreover, the photoelectrochemical properties of the dye-sensitized solar cell (DSSC) based on branched hierarchical ZnO nanowire arrays are investigated. Due to the enlargement of the internal surface area within the branched nanostructure photoelectrode, the DSSC consisting of branched hierarchical ZnO nanowire arrays yields a power conversion efficiency of 0.88%, which is almost twice higher than that of the DSSC fabricated using bare ZnO nanowire arrays.     

ZnO-capped nanorod gas sensors

This paper reports on the synthesis of pristine α-Fe₂O₃ nanorods and Fe₂O₃–ZnO core–shell nanorods using a combination of thermal oxidation and atomic layer deposition (ALD) techniques; the completed nanorods were then used for ethanol sensing studies. The crystal structure and morphology of the synthesized nanostructures were examined by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The sensing properties of the pristine and core–shell nanorods for gas-phase ethanol were examined using different concentrations of ethanol (5–200 ppm) at different temperatures (150–250 °C). The XRD and SEM revealed the excellent crystallinity of the Fe₂O₃–ZnO core–shell nanorods, as well as their uniformity in terms of shape and size. The Fe₂O₃–ZnO core–shell nanorod sensor showed a stronger response to ethanol than the pristine Fe₂O₃ nanorod sensor. The response (i.e., the relative change in electrical resistance R_a/R_g) of the core–shell nanorod sensor was 22.75 for 100 ppm ethanol at 200 °C whereas that of the pristine nanorod sensor was only 3.85 under the same conditions. Furthermore, under these conditions, the response time of the Fe₂O₃–ZnO core–shell nanorods was 15.96 s, which was shorter than that of the pristine nanorod sensor (22.73 s). The core–shell nanorod sensor showed excellent selectivity to ethanol over other VOC gases. The improved sensing response characteristics of the Fe₂O₃–ZnO core–shell nanorod sensor were attributed to modulation of the conduction channel width and the potential barrier height at the Fe₂O₃–ZnO interface accompanying the adsorption and desorption of ethanol gas as well as to preferential adsorption and diffusion of oxygen and ethanol molecules at the Fe₂O₃–ZnO interface.     

Effects of dye etching on the morphology and performance of ZnO nanorod dye-sensitized solar cells

Dye-sensitized solar cells based on electrodeposited ZnO nanorod arrays were fabricated and tested. Field-emission scanning electron microscopy (FESEM) and X-ray powder diffraction (XRD) were used to identify the characters of ZnO nanorod arrays. The effects of dye etching on the morphology and performance of ZnO nanorod dye-sensitized solar cells were studied. It was found that the surfaces of ZnO nanorods were both etched by dye solutions, no matter N3 or N719. Compared with N3, N719 had a larger damage to the structure of ZnO nanorod photoanode, and the photoelectric conversion efficiency of cells decreased quickly with the sensitizing time increasing. In a certain range, the increasing length of ZnO nanorods can clearly improve the photoelectric conversion efficiency of cells.     

Fabrication and characterization of silicon wire solar cells having ZnO nanorod antireflection coating on Al-doped ZnO seed layer

In this study, we have fabricated and characterized the silicon [Si] wire solar cells with conformal ZnO nanorod antireflection coating [ARC] grown on a Al-doped ZnO [AZO] seed layer. Vertically aligned Si wire arrays were fabricated by electrochemical etching and, the p-n junction was prepared by spin-on dopant diffusion method. Hydrothermal growth of the ZnO nanorods was followed by AZO film deposition on high aspect ratio Si microwire arrays by atomic layer deposition [ALD]. The introduction of an ALD-deposited AZO film on Si wire arrays not only helps to create the ZnO nanorod arrays, but also has a strong impact on the reduction of surface recombination. The reflectance spectra show that ZnO nanorods were used as an efficient ARC to enhance light absorption by multiple scattering. Also, from the current-voltage results, we found that the combination of the AZO film and ZnO nanorods on Si wire solar cells leads to an increased power conversion efficiency by more than 27% compared to the cells without it.     

Polystyrene sphere monolayer assisted electrochemical deposition of ZnO nanorods with controlable surface density

In this paper we report the zinc oxide nanorods (ZnO NRs) growth by electrochemical deposition onto polycrystalline gold electrodes modified with assemblies of polystyrene sphere monolayers (PSSMs). Growth occurs through the interstitial spaces between the hexagonally close packed spheres. ZnO NRs nucleate in the region where three adjacent spheres leave a space, being able to grow and projected over the PSSMs. The nanorod surface density (N_NR) shows a linear dependence with respect to a PS sphere diameter selected. XRD analysis shows these ZnO NRs are highly oriented along the (0 0 2) plane (c-axis). This open the possibility to have electronic devices with mechanically supported nanometric materials.