Charge influence and growth mechanism of ZnO nanorods

We demonstrate the influence of charges near the substrate surface on vertically aligned ZnO nanorod growth. ZnO nanorods were fabricated on n-type GaN with and without H+ treatments by catalyst-free metal-organic chemical vapor deposition. The ZnO nanorods grown on n-GaN films were vertically well-aligned and had a well-ordered wurtzite structure. However, the ZnO did not form into nanorods and the crystal quality was very degraded as they were deposited on the H+ treated n-GaN films. The charge influence was also observed in the ZnO nanorod growth on sapphire substrates. These results implied that the charges near the substrate surface dominantly affected on the crystalization and formation of ZnO nanorods.     

Charge influence and growth mechanism of ZnO nanorods

We demonstrate the influence of charges near the substrate surface on vertically aligned ZnO nanorod growth. ZnO nanorods were fabricated on n-type GaN with and without H+ treatments by catalyst-free metal-organic chemical vapor deposition. The ZnO nanorods grown on n-GaN films were vertically well-aligned and had a well-ordered wurtzite structure. However, the ZnO did not form into nanorods and the crystal quality was very degraded as they were deposited on the H+ treated n-GaN films. The charge influence was also observed in the ZnO nanorod growth on sapphire substrates. These results implied that the charges near the substrate surface dominantly affected on the crystallization and formation of ZnO nanorods.     

Synthesis and Luminescent Properties of Planar-tip and Tapered-tip ZnO Nanorod Arrays

Vertically aligned ZnO nanorods were synthesized on a-plane sapphire via a metal catalyzed vapor phase transport and condensation process in a two-zone vacuum furnace. Planar-tip and tapered-tip ZnO nanorods were successfully synthesized by utilizing different source materials under the same growth conditions. The growth mechanisms were proposed to be vapor-liquid-solid （VLS） process for planar-tip ZnO nanorods and a combination of VLS and self-catalyzed processes for tapered-tip ZnO nanorods, From cathodoluminescence （CL） measurements, tapered-tip ZnO nanorods have more intense green emission than planar-tip ZnO nanorods, and therefore possess higher oxygen vacancy concentration than planar-tip ZnO nanorods. From CL characteristics, well-aligned planar-tip ZnO nanorods shall serve effectively as laser source, while well-aligned tapered-tip ZnO nanorods are suitable for direction-related optical applications.     

Control of epitaxial growth orientation in ZnO nanorods on c-plane sapphire substrates

This paper presents a study on low temperature hydrothermal growth of ZnO nanorods (NRs) on pre-seeded (0001) sapphire substrates. Prior to hydrothermal growth of ZnO NRs, epitaxial ZnO seeds were grown by metal-organic chemical vapour deposition under various process conditions. Findings show that the majority of ZnO NRs inclined at a specific angle of about 38° to the direction perpendicular to the substrate surface and exhibited a preferential in-plane alignment, besides other NRs growing vertically from the sapphire surface. X-ray diffraction φ-scan measurements reveal that the ZnO nanorods displayed two distinct epitaxial relationships with sapphire which were (0001)_ZnO//(0001)_sapphire and (0001)_ZnO//(101?4)_sapphire, respectively. Reduced lattice mismatch between ZnO and sapphire is responsible for the inclined ZnO NRs growth. The growth direction of ZnO NRs is remarkably dependent on the growth conditions of ZnO seeds and sapphire substrate pre-treatment. The epitaxial orientations of ZnO seeds grown on the sapphire substrate dominate the subsequent ZnO NRs growth and can be controlled through adjusting growth conditions.     

Analysis of SAW properties of epitaxial ZnO films grown on R-Al2O3 substrates

ZnO thin films with a high piezoelectric coupling coefficient are widely used for high frequency and low loss surface acoustic wave (SAW) devices when the film is deposited on top of a high acoustic velocity substrate, such as diamond or sapphire. The performance of these devices is critically dependent on the quality of the ZnO films as well as of the interface between ZnO and the substrate. In this paper, we report the studies on piezoelectric properties of epitaxial (112¯0) ZnO thin films grown on R-plane sapphire substrates using metal organic chemical vapor deposition (MOCVD) technique. The c-axis of the ZnO film is in-plane. The ZnO/R-Al₂O₃ interface is atomically sharp. SAW delay lines, aligned parallel to the c-axis, were used to characterize the surface wave velocity, coupling coefficient, and temperature coefficient of frequency as functions of film thickness to wavelength ratio (h/λ). The acoustic wave properties of the material system were calculated using Adler's matrix method, and the devices were simulated using the quasi-static approximation based on Green's function analysis     

ZnO nanorod arrays grown on glass substrates below glass transition temperature by metalorganic chemical vapor deposition

High density, well-aligned ZnO nanorods with uniform distributions in their diameters and lengths are successfully prepared on amorphous substrates by metalorganic chemical vapor deposition. The X-ray diffraction measurements indicate that the ZnO nanorods are of wurtzite crystal structure, and are grown preferentially on glass substrates along the [0001]_ZnO direction. The degree of the preferred orientation of the ZnO nanorods is enhanced by increasing the growth temperature, as confirmed by the X-ray diffraction and selected area electron diffraction patterns. Photoluminescence investigations revealed the enhancement of the band edge emission with increasing growth temperature, suggesting the improvement in the optical quality of the ZnO nanorods with increasing temperature.     

Realization of nonpolar a-plane ZnO films on r-plane sapphire substrates using a simple single-source chemical vapor deposition

Nonpolar (112?0) ZnO thin films (a-plane ZnO) have been grown on (11?02) sapphire substrates (r-plane sapphire) by a simple atmospheric pressure single-source chemical vapor deposition (SSCVD) approach. The crystallinity, surface morphology and optical property of the films were investigated using high-resolution X-ray diffraction (HRXRD), scanning electron microscope (SEM) and transmission spectrum, respectively. XRD results revealed that the ZnO films were grown on the substrates epitaxially along (112?0) orientation, and the epitaxial relationship between the ZnO films and the substrates was determined to be (112?0)ZnO∥(11?02) Al2O3, and [1?101]ZnO∥[022?1]Al₂O₃. The SEM image exhibited that the a-plane ZnO films showed a high density of well-aligned ZnO sheets with rectangular structure. The transmission spectrum showed that the ZnO films were highly transparent in the visible region.     

ZnO纳米棒阵列和薄膜的同步外延生长及其光电化学性能

使用化学气相沉积法在a面蓝宝石衬底上同步外延生长氧化锌(ZnO)竖直纳米棒阵列和薄膜,研究了阵列和薄膜的光电化学性能。结果表明,纳米结构中的竖直单晶纳米棒有六棱柱形和圆柱形,其底部ZnO薄膜使竖直纳米棒互相联通。与ZnO纳米薄膜的比较表明,这种纳米结构具有优异的光电化学性能,其入射光电流效率是ZnO纳米薄膜的2.4倍;光能转化效率是ZnO纳米薄膜的5倍。这种纳米结构优异的光电化学性能,可归因于其高表面积-体积比以及其底部薄膜提供的载流子传输通道。本文分析了这种纳米结构的生长过程,提出了协同生长机理：Au液化吸收气氛中的Zn原子生成合金,合金液滴过饱和后ZnO开始成核,随后在衬底表面生成了ZnO薄膜。同时,还发生了Zn自催化的气-固(VS)生长和Au催化的气-液-固(VLS)生长,分别生成六棱柱纳米棒和圆柱形纳米棒,制备出底部由薄膜连接的竖直纳米棒阵列。     

Sputter deposition of ZnO nanorods/thin-film structures on Si

Using a recently developed sputter deposition technique, ZnO deposits were grown at the room temperature on silicon wafers with various kinds of copper surface layers. The copper layers were prepared using sputter deposition, thermal evaporation, or electroless plating technique. It was found that the surface copper prepared using both sputter deposition and thermal evaporation technique grew only ZnO thin films, while the surface copper prepared using sputter deposition technique grew ZnO nanorods/thin-film deposits. The relation between the copper characteristics and the growth of ZnO nanorods/thin-film deposits was investigated. The growth kinetics of the ZnO nanorods/thin film structure is also discussed.     

Efficient dye-sensitized solar cells based on the combination of ZnO nanorods and microflowers

Well-aligned ZnO nanorod films were grown onto transparent conducting substrates by using an aqueous solution route. The presence of some reflections in the X-ray diffraction pattern of the ZnO films indicates the vertical alignment of the nanorods along the c axis of the wurtzite hexagonal structure. Well-aligned ZnO nanorods were observed by scanning electron microscopy. The presence of top ZnO microflower layers over the ZnO nanorod film was observed for all growth times studied. The ZnO nanorods with ZnO microflower top layers were applied as photoelectrodes in dye-sensitized solar cells. Higher photocurrent densities and photovoltages were observed with longer nanorod growth times. The high performance of the dye-sensitized solar cells might be associated to the combination of ZnO nanorods and microflowers in the same photoelectrode.     

Catalytic effects of ZnO nanorods grown by sonochemical decomposition of zinc acetate dihydrate

In this study, we prepared ZnO nanorods by a sonochemical method using a zinc acetate dihydrate as a new precursor. Well-aligned high-quality ZnO nanorods were synthesized on FTO glass by the sonochemical decomposition of zinc acetate dihydrate using a ZnO thin-film as the catalytic layer. The ZnO thin-films were deposited on the FTO glass by a sputtering method. To investigate their catalytic effects on the ZnO nanorods, catalytic ZnO thin-films of 20 nm, 40 nm, and 60 nm thickness were prepared by adjusting the sputtering time. The ZnO nanorods grown on catalytic layers with different thicknesses were characterized by SEM, XRD, and PL. The ZnO nanorods grown on the catalytic layer of 40 nm thickness show the best crystal and spatial orientation and as a result display the best optical properties. It was found that a catalytic ZnO thin-film of 40 nm in thickness yields well-aligned high-quality ZnO nanorods, due to its small surface roughness and structural strain.     

Investigations on structural, optical and electrical properties of p-type ZnO nanorods using hydrothermal method

Undoped and doped ZnO nanorods were grown from an aqueous solution at low temperature (90 °C) on sapphire (100) substrates coated with ZnO thin film annealed in air at 550 °C for 1 h. X-ray diffraction results show that these nanorods have wurtzite type structure, and they are oriented in the c-axis direction. The optical properties are examined by room temperature micro photoluminescence and Raman scattering analysis which confirm that the nanorods exhibit good optical and electrical properties. A strong enhancement of multiple-phonon Raman scattering process with longitudinal optical phonon overtone up to fifth order was observed. It is found that the thin film coating of ZnO plays an important role in the c-axis oriented growth of undoped and doped ZnO nanorods due to good lattice match between the thin film and nanorods.     

Optical investigations of multi-dimensional ZnO hybrid structures

The authors report on the optical properties of multi-dimensional ZnO hybrid structures, consisting of film (2D)/nanorods (1D)/sapphire substrate (2D), grown by metalorganic chemical vapor deposition (MOCVD). Photoluminescence investigations reveal that the sample with top layer grown at a decreased growth temperature of 240 °C and increased reactor pressure of 5 Torr exhibits superior emission properties. The presence of strong E₂^high optical phonon mode at 438.5 cm^− 1 in the visible micro-Raman spectra demonstrates the wurtzite nature of ZnO. Although the ultraviolet Raman scattering measurements of the hybrid structures reveal the presence of in-plane tensile stress in the top ZnO layer, the sample with the improved emission performance shows the release of tensile stress.     

Effects of temperature on ZnO hybrids grown by metal-organic chemical vapor deposition

The growth of three-dimensional ZnO hybrid structures by metal-organic chemical vapor deposition was controlled through their growth pressure and temperature. Vertically aligned ZnO nanorods were grown on c-plane of sapphire substrate at 600 °C and 400 Torr. ZnO film was then formed in situ on the ZnO nanorods at 100, 600, and 700 °C and 10 Torr. High-resolution X-ray diffraction measurements showed that the ZnO film on the nanorods/sapphire grew epitaxially, and that the ZnO film/nanorods hybrid structures had well-ordered wurtzite structures. The hybrid ZnO structure was shown to be about 3–5 μm by field-emission scanning electron microscopy. The hybrid formed at 600 °C showed better crystalline quality those formed at 100 °C or 700 °C. These structures have potential applicability as nanobuilding blocks in nanodevices.     

Selective growth of ZnO nanorods on SiO2/Si substrates using a graphene buffer layer

A promising strategy for the selective growth of ZnO nanorods on SiO₂/Si substrates using a graphene buffer layer in a low temperature solution process is described. High densities of ZnO nanorods were grown over a large area and most ZnO nanorods were vertically well-aligned on graphene. Furthermore, selective growth of ZnO nanorods on graphene was realized by applying a simple mechanical treatment, since ZnO nanorods formed on graphene are mechanically stable on an atomic level. These results were confirmed by first principles calculations which showed that the ZnO-graphene binding has a low destabilization energy. In addition, it was found that ZnO nanorods grown on SiO₂/Si with a graphene buffer layer have better optical properties than ZnO nanorods grown on bare SiO₂/Si. The nanostructured ZnO-graphene materials have promising applications in future flexible electronic and optical devices.     

Low temperature epitaxial growth of ZnO layer by plasma-assisted epitaxy

Plasma-assisted epitaxial growth of ZnO layers were achieved on C- and R-plane sapphire substrates in oxygen plasma excited by radio frequency power at 13.56 MHz with evaporation of pure elemental Zn. The ZnO layers were grown at 300–400°C with high growth rate around 1.7 μm/h. Surface cleaning of sapphire substrates using Ar-plasma was crucial for good quality ZnO growth. Photoluminescence spectra at 10 K were dominated by band-edge emission due to bound excitons without deep level emission in green-light region. The intensity of band-edge emission was strongly dependent on applied radio frequency power to excite Ar- and O₂-plasma for sapphire surface cleaning and ZnO growth, respectively, and was about 50 times larger on the layer grown in oxygen plasma than that grown in non-excited oxygen gas. The ZnO layer grown on R-plane sapphire was epitaxially grown above 300°C in oxygen plasma, however, on C-plane sapphire the ZnO layer was easily polycrystallized for thick films even at 400°C. Growth mode and surface morphology of ZnO layers were drastically changed with the substrate orientation.     

Tailoring the morphology of electrodeposited ZnO and its photoluminescence properties

High density ZnO columnar films with well-aligned and well-perpendicular to the surface of film were electrodeposited on ITO substrates by using an electrolyte consisting of a mix of water and organic solvent namely dimethylsulfoxide (DMSO). The effect of mixing ratio of water and DMSO on the growth of film has been examined critically. SEM images have shown that well-oriented ZnO quasi-nano columns were formed perpendicular to the substrate. At the same time we found there are three kinds of competitions for growth of ZnO crystalmorphology i.e. column, rod and needle like. The needle like morphology has high density with well-aligned structure. The reasons for the growth of films of different morphology and their photoluminescence (PL) properties have been presented and discussed. It has been found that the three-dimensional (3D) ordered ZnO structure exhibits high intensity PL band which may shift their position and intensity with the varying conditions of depositions.     

Effect of precursor on epitaxially grown of ZnO thin film on p-GaN/sapphire (0 0 0 1) substrate by hydrothermal technique

Single crystalline ZnO thin film on p-GaN/sapphire (0 0 0 1) substrate, using two different precursors by hydrothermal route at a temperature of 90 °C were successfully grown. The effect of starting precursor on crystalline nature, surface morphology and optical emission of the films were studied. ZnO thin films were grown in aqueous solution of zinc acetate and zinc nitrate. X-ray diffraction analysis revealed that all the thin films were single crystalline in nature and exhibited wurtzite symmetry and c-axis orientation. The thin films obtained with zinc nitrate had a more pitted rough surface morphology compared to the film grown in zinc acetate. However the thickness of the films remained unaffected by the nature of the starting precursor. Sharp luminescence peaks were observed from the thin films almost at identical energies but deep level emission was slightly prominent for the thin film grown in zinc nitrate.     

ZnO thin films epitaxially grown by electrochemical deposition method with constant current

The electrochemical deposition (ECD) method is well suited to the preparation of large area devices and has several advantages, although the deposited films have a crystallinity problem. A constant current deposition method was employed for preparation of ZnO thin films in this study, because it was expected that the growth rate of the films could be controlled by means of the current density. The intensity of X-ray diffraction (XRD) peaks, and the size and shape of grains of ZnO films grown on polycrystalline Au substrates were observed to depend on the cathodic current density. On the basis of those results, deposition of ZnO on a Pt layer epitaxially grown on c-sapphire was carried out. The results of ?-scan XRD measurements showed in-plane orientation in agreement with the in-plane direction of the Pt substrate layer, which suggests that the ZnO thin film was epitaxially grown by the ECD method.     

ZnO/GO纳米材料基热稳定钙钛矿太阳能电池

为了使钙钛矿太阳能电池在高温退火后能够保持稳定, 本研究通过电化学方法制备出氧化锌/氧化石墨烯纳米粒子, 并将其运用到钙钛矿太阳能电池中作为电子传输层使用。通过原位掠入射X射线衍射(GIXRD)、X射线衍射(XRD)、扫描电子显微镜(SEM)和紫外-可见吸收光谱(UV-Vis)等方法对沉积在氧化锌和氧化锌/氧化石墨烯纳米材料上面的甲胺铅碘的结构、形貌以及电池性能变化进行分析测试。结果表明: 氧化锌/氧化石墨烯对于甲胺铅碘有保护作用, 沉积在氧化锌/氧化石墨烯上面的甲胺铅碘薄膜稳定性更高, 电池性能更加稳定, 为将来大面积应用提供了一定的指导。