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.     

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.     

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.     

Effect of deposition temperature and quality of free-standing diamond substrates on the properties of RF sputtering ZnO films

Highly c-axis oriented ZnO film is often deposited on diamond substrates by RF magnetron sputtering and widely used for high frequency surface acoustic wave (SAW) devices. Deposition temperature is a key factor affecting the quality of the ZnO film. Different quality polished free-standing diamond films prepared by DC Arc Plasma Jet were used as the substrates to deposit ZnO films at different temperatures. Effect of the deposition temperature and the quality of the diamond films on the properties of the ZnO films were investigated by means of scanning electron microscopy (SEM) and X-ray diffraction (XRD). The results show that highly c-axis oriented ZnO films can be much easier deposited on the optical-grade diamond films with < 111> preferred orientation than the tool-grade diamond films with < 220> preferred orientation. The optimal deposition temperature is 200 °C for highly c-axis oriented and lower roughness ZnO films. Acoustic phase velocity of more than 10,000 m/s for the SAW devices based on the ZnO/optical-grade free-standing diamond films was obtained.     

Structural and optical properties of ZnO nanorods by electrochemical growth using multi-walled carbon nanotube-composed seed layers

We reported the enhancement of the structural and optical properties of electrochemically synthesized zinc oxide [ZnO] nanorod arrays [NRAs] using the multi-walled carbon nanotube [MWCNT]-composed seed layers, which were formed by spin-coating the aqueous seed solution containing MWCNTs on the indium tin oxide-coated glass substrate. The MWCNT-composed seed layer served as the efficient nucleation surface as well as the film with better electrical conductivity, thus leading to a more uniform high-density ZnO NRAs with an improved crystal quality during the electrochemical deposition process. For ZnO NRAs grown on the seed layer containing MWCNTs (2 wt.%), the photoluminescence peak intensity of the near-band-edge emission at a wavelength of approximately 375 nm was enhanced by 2.8 times compared with that of the ZnO nanorods grown without the seed layer due to the high crystallinity of ZnO NRAs and the surface plasmon-meditated emission enhancement by MWCNTs. The effect of the MWCNT-composed seed layer on the surface wettability was also investigated.     

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.     

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.     

Facile solution growth of vertically aligned ZnO nanorods sensitized with aqueous CdS and CdSe quantum dots for photovoltaic applications

Vertically aligned single crystalline ZnO nanorod arrays, approximately 3 μm in length and 50-450 nm in diameter are grown by a simple solution approach on a Zn foil substrate. CdS and CdSe colloidal quantum dots are assembled onto ZnO nanorods array using water-soluble nanocrystals capped as-synthesized with a short-chain bifuncional linker thioglycolic acid. The solar cells co-sensitized with both CdS and CdSe quantum dots demonstrate superior efficiency compared with the cells using only one type of quantum dots. A thin Al2O3 layer deposited prior to quantum dot anchoring successfully acts as a barrier inhibiting electron recombination at the Zn/ZnO/electrolyte interface, resulting in power conversion efficiency of approximately 1% with an improved fill factor of 0.55. The in situ growth of ZnO nanorod arrays in a solution containing CdSe quantum dots provides better contact between two materials resulting in enhanced open circuit voltage.     

Growth and optical properties of ZnO nanorod arrays on Al-doped ZnO transparent conductive film

ZnO nanorod arrays (NRAs) on transparent conductive oxide (TCO) films have been grown by a solution-free, catalyst-free, vapor-phase synthesis method at 600°C. TCO films, Al-doped ZnO films, were deposited on quartz substrates by magnetron sputtering. In order to study the effect of the growth duration on the morphological and optical properties of NRAs, the growth duration was changed from 3 to 12 min. The results show that the electrical performance of the TCO films does not degrade after the growth of NRAs and the nanorods are highly crystalline. As the growth duration increases from 3 to 8 min, the diffuse transmittance of the samples decreases, while the total transmittance and UV emission enhance. Two possible nanorod self-attraction models were proposed to interpret the phenomena in the sample with 9-min growth duration. The sample with 8-min growth duration has the highest total transmittance of 87.0%, proper density about 75 μm⁻², diameter about 26 nm, and length about 500 nm, indicating that it can be used in hybrid solar cells.     

Catalytic growth of ZnO nanostructures by r.f. magnetron sputtering

The catalytic effect of gold seed particles deposited on a substrate prior to zinc oxide (ZnO) thin film growth by magnetron sputtering was investigated. For this purpose, selected ultra thin gold layers, with thicknesses close to the percolation threshold, are deposited by thermal evaporation in ultra high vacuum (UHV) conditions and subsequently annealed to form gold nanodroplets. The ZnO structures are subsequently deposited by r.f. magnetron sputtering in a UHV chamber, and possible morphological differences between the ZnO grown on top of the substrate and on the gold are investigated. The results indicate a moderate catalytic effect for a deposited gold underlayer of 4 nm, quite close to the gold thin film percolation thickness.     

Effect of substrate temperature on the structural,electrical, and optical properties of GZO/ZnO films deposited by radio frequency magnetron sputtering

Ga-doped ZnO (GZO)/ZnO bi-layered films were deposited on glass substrates by radio frequency magnetron sputtering at different substrate temperatures of 100, 200 and 300 °C to investigate the effects of substrate temperature on the structural, electrical, and optical properties of the films. Thicknesses of the GZO and ZnO buffer layer were kept constant at 85 and 15 nm by controlling the deposition times.     

水热合成法制备ZnO纳米棒有序阵列薄膜

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10．0nm和3．3μm。     

Room-temperature nonequilibrium growth of controllable ZnO nanorod arrays

In this study, controllable ZnO nanorod arrays were successfully synthesized on Si substrate at room temperature (approx. 25°C). The formation of controllable ZnO nanorod arrays has been investigated using growth media with different concentrations and molar ratios of Zn(NO₃)₂ to NaOH. Under such a nonequilibrium growth condition, the density and dimension of ZnO nanorod arrays were successfully adjusted through controlling the supersaturation degree, i.e., volume of growth medium. It was found that the wettability and electrowetting behaviors of ZnO nanorod arrays could be tuned through variations of nanorods density and length. Moreover, its field emission property was also optimized by changing the nanorods density and dimension.     

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.     

Enhanced wettability and photocatalytic activity of seed layer assisted one dimensional ZnO nanorods synthesized by hydrothermal method

The wettability and photocatalytic activity of ZnO nanostructures synthesized by hydrothermal method are reported. XRD, FESEM, XPS, TEM, AFM, Contact angle, UV/Vis and photoluminescence spectroscopy are used to characterize the samples. It is observed that ZnO seeded layer results in the formation of nanorods whereas the absence of seed gives rise to flake like morphology. The XRD indicates that ZnO nanorods have preferred orientation along (002) direction. The formation of ZnO nanorods along (002) direction is due to the existence of nucleation sites resulting from the lattice matching of ZnO seed. Wettability studies show that the ZnO nanorods grown on seeded substrate approaches superhydrophobic state with water contact angle (WCA) of 137.0°. The high contact angle is due to the large surface roughness and low surface energy. The enhanced catalytic performance of ZnO nanorods is attributed to the 1D structure, enhanced roughness, crystallinity and a large number of reactive oxidizing species.     

Highly Uniform Epitaxial ZnO Nanorod Arrays for Nanopiezotronics

Highly uniform and c-axis-aligned ZnO nanorod arrays were fabricated in predefined patterns by a low temperature homoepitaxial aqueous chemical method. The nucleation seed patterns were realized in polymer and in metal thin films, resulting in, all-ZnO and bottom-contacted structures, respectively. Both of them show excellent geometrical uniformity: the cross-sectional uniformity according to the scanning electron micrographs across the array is lower than 2%. The diameter of the hexagonal prism-shaped nanorods can be set in the range of 90–170 nm while their typical length achievable is 0.5–2.3 μm. The effect of the surface polarity was also examined, however, no significant difference was found between the arrays grown on Zn-terminated and on O-terminated face of the ZnO single crystal. The transmission electron microscopy observation revealed the single crystalline nature of the nanorods. The current–voltage characteristics taken on an individual nanorod contacted by a Au-coated atomic force microscope tip reflected Schottky-type behavior. The geometrical uniformity, the designable pattern, and the electrical properties make the presented nanorod arrays ideal candidates to be used in ZnO-based DC nanogenerator and in next-generation integrated piezoelectric nano-electromechanical systems (NEMS).     

Growth of ZnO Nanorods by the Chemical Solution Method with Assisted Electrical Field

Zinc oxide (ZnO) nanorod arrays on the ZnO-coated seed substrates were prepared by the solution chemical method from Zn(NO₃)₂/NaOH under an assisted electrical field. The influence of the electrical field on ZnO nanorod growth was primarily explored, and the positive effects of the electrical field were demonstrated by adding polyethylene glycol in growth solution. It has been proved that the electrical field enhances ion adsorption to the substrate and lowers the nucleation energy barrier by increasing charge intensity; meanwhile, it produces H⁺ through oxidation of OH⁻ and increases properly the degree of solution supersaturation near the substrate surface. XRD results show that the nanorods grown under the electrical field primarily have a zincite structure. With increasing precursor concentration, the average diameter and length of ZnO nanorods increase. The maximum rod growth rate at a given concentration of Zn²⁺ ion occurs at a specific temperature.     

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 patterning of ZnO nanorods on silicon substrates using nanoimprint lithography

In this research, nanoimprint lithography (NIL) was used for patterning crystalline zinc oxide (ZnO) nanorods on the silicon substrate. To fabricate nano-patterned ZnO nanorods, patterning of an n-octadecyltrichlorosilane (OTS) self-assembled monolayers (SAMs) on SiO₂ substrate was prepared by the polymer mask using NI. The ZnO seed layer was selectively coated only on the hydrophilic SiO₂ surface, not on the hydrophobic OTS SAMs surface. The substrate patterned with the ZnO seed layer was treated with the oxygen plasma to oxidize the silicon surface. It was found that the nucleation and initial growth of the crystalline ZnO were proceeded only on the ZnO seed layer, not on the silicon oxide surface. ZnO photoluminescence spectra showed that ZnO nanorods grown from the seed layer treated with plasma showed lower intensity than those untreated with plasma at 378 nm, but higher intensity at 605 nm. It is indicated that the seed layer treated with plasma produced ZnO nanorods that had a more oxygen vacancy than those grown from seed layer untreated with plasma. Since the oxygen vacancies on ZnO nanorods serve as strong binding sites for absorption of various organic and inorganic molecules. Consequently, a nano-patterning of the crystalline ZnO nanorods grown from the seed layer treated with plasma may give the versatile applications for the electronics devices.