Photoluminescence of ZnO nanostructures grown by the aqueous chemical growth technique

Zinc oxide nanostructured films were grown by the aqueous chemical growth technique using equimolar aqueous solutions of zinc nitrate and hexamethylenetetramine as precursors. Silicon(100) and glass substrates were placed in Pyrex glass bottles with polypropylene autoclavable screw caps containing the precursors described above, and heated at 95 C for several hours. X-ray diffraction 2θ/θ scans showed that the only crystallographic phase present was the hexagonal wurtzite structure. Scanning electron microscopy showed the formation of flowerlike ZnO nanostructures, consisting of hexagonal nanorods with a diameter of a few hundred nanometers. The photoluminescence spectra of the ZnO nanostructures were recorded at 18–295 K using a cw He–Cd laser (325 nm) and a pulsed laser (266 nm). The ZnO nanostructures exhibit an ultraviolet emission band centered at 3.192 eV in the vicinity of the band edge, which is attributed to the well-known excitonic transition in ZnO.     

Morphological control of ZnO nanostructures on silicon substrates

ZnO nanostructures are grown on Au-catalyzed Si substrates by vapour phase transport between 800 and 1150 C. Nanostructures grown at 800 C are mainly rod-like in structure with diameters of <200 nm. Increasing growth temperature yields combination growth modes with 2D structures (nanowalls/nanosheets) connecting 1D nanorods at intermediate temperatures and a 3D growth mode of foam-like appearance at the highest temperatures. The present work indicates that it may be possible to systematically control the morphology of ZnO nanostructures by varying the growth temperature.     

A novel deposition method to grow ZnO nanorods: Spray pyrolysis

ZnO layers were deposited by chemical spray pyrolysis (CSP) using zinc chloride aqueous solutions onto indium tin oxide (ITO) glass substrates at growth temperatures in the region of 400–580 C. The layers were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and low-temperature () photoluminescence (PL) measurements. The flat film of ZnO obtained at 400 C evolves to a structured layer by raising the temperature up to 500 C. Deposition around 550 C and above results in a layer comprising well-shaped hexagonal ZnO nanorods with diameter of 100–150 nm and length of up to 1 micron. XRD shows strong c-axis orientation of ZnO being in accordance with the SEM study. Deposition of nanorods was successful using ITO with grain size around 100 nm, whereas on fine-grained ITO (grain size < 50 nm) with smooth surface fat crystals with diameter up to 400 nm and length of about 300 nm were formed. Sharp near band edge (NBE) emission peaks centered at 3.360 and 3.356 eV dominated the PL spectra of ZnO at , originating from the exciton transition bound to neutral donors. PL and XRD results suggest that ZnO rods prepared by spray pyrolysis are of high optical and crystalline quality.     

Effects of annealing temperature on morphologies and optical properties of ZnO nanostructures

The effects of annealing temperature on the morphologies and optical properties of ZnO nanostructures synthesized by sol–gel method were investigated in detail. The SEM results showed that uniform ZnO nanorods formed at 900 C. The PL results showed an ultraviolet emission peak and a relatively broad visible light emission peak for all ZnO nanostructures sintered at different temperature. The increase of the crystal size and decrease of tensile stress resulted in the UV emission peak shifted from 386 to 389 nm when annealing temperature rose from 850 to 1000 C. The growth mechanism of the ZnO nanorods is discussed.     

Vapour phase transport growth of ZnO layers and nanostructures

We have developed a novel advanced VPT set-up. ZnO layers and nanorods were grown employing a specially designed horizontal vapour transport system with elemental sources at relatively low temperatures without catalysis. We employed 6N elemental Zn carried by nitrogen and 99.995% oxygen as reactants. Sapphire, SiC, bulk ZnO and ZnO epitaxial layers were implemented as substrates for ZnO growth. Growth temperatures ranged from 500 to 900 C. Reactor pressures were from 5 mbar to atmospheric pressure. We employed x-ray diffractometry, optical microscopy, scanning electron microscopy and atomic force microscopy to investigate the obtained ZnO samples and the influence of different growth parameters on the ZnO homo- and heteroepitaxial growth and to optimise the set of growth parameters either for both epitaxial layers and nanostructures. We also show that the quality of the VPT grown ZnO epitaxial layers on sapphire can be even higher (evaluated from FWHM of the XRD rocking curves) than the MBE grown ones used as epiwafers for VPT growth. High quality ZnO layers with extremely narrow FWHM of the (0002) rocking curve of 38″ are fabricated employing our VPT approach.     

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.     

Effect of heat and time-period on the growth of ZnO nanorods by sol–gel technique

Sol–gel routes to metal oxide nanoparticles in organic solvents under exclusion of water have become a versatile alternative to aqueous methods. We focus on the preparation of well-aligned ZnO nanorod arrays using non-aqueous sol–gel synthesis route, where ZnO nanorods arrays have been grown on glass substrates. This work provides a systematic study of controlled morphology and crystallinity of ZnO nanorod arrays. The investigation demonstrates that the synthesis process conditions of ZnO thin film have strong influences on the morphology and crystallinity of the ZnO nanorod arrays grown thereon, where non-aqueous process offers the possibility of better understanding and controlling the reaction pathways on the molecular level, enabling the synthesis of nanomaterials with high crystallinity and well-defined, uniform particle morphologies. Here the annealing temperature plays an important role on the growth of nanostructures of the ZnO grains and nanorod arrays. The scanning electron microscopy (SEM) image shows that the growth of ZnO nanorod arrays are high-quality single crystals growing along the c-axis perpendicular to the substrates. A detailed analysis of the growth characteristics of ZnO nanostructures as functions of growth time is also reported.     

Study of Zinc Oxide nano/micro rods grown on ITO and glass substrates

Highly oriented multilinked ZnO nano and micro rods were deposited using aqueous solution growth technique on ITO and glass substrates. Their study provides a basic understanding of effect of the base material on the growth of nanorods. An equimolar aqueous solution of Zinc nitrate and hexamine (HMT) was used for the preparation of ZnO nanorods arrays. ZnO was deposited on ITO and glass substrates after establishing the optimal pH and concentration, which yield the best substrate coverage for precursor solution. To achieve uniform growth and high density of ZnO nanorods, the prepared solution was heated at certain constant temperature. The experimental results have been obtained by using Scanning Electron Microscope (SEM), X-ray diffractometer (XRD) and Fluorescence Spectroscope which shows highly oriented nanorods perpendicular to the surface of substrates and a comparative study of ITO and glass grown nanorod arrays shows that the structural chemistry of the substrate clearly affects the growth nanostructures. The high variation in optical properties can be attributed by the heating temperatures and limited presence of reactants available for the controlled growth on substrates. It is also observed confined and decreased particle size with enhanced nucleation on ITO substrate as compared to glass. Due to the physical limitations in the growth, this kinetically controlled nucleation would be responsible for producing the highly uniform, dense and perpendicularly oriented nanorods.     

Synthesis and field emission of patterned ZnO nanorods

A simple and self-catalytic method has been developed for synthesizing finely patterned ZnO nanorods on ITO-glass substrates under a low temperature of 500 °C. The patterned ZnO nanorod arrays, a unit area is of 400 × 100 μm², are synthesized via vapor phase transport method. The surface morphology and composition of the as-synthesized ZnO nanorods are characterized by means of scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX). The mechanism of formation of ZnO nanorods is also discussed. The measurement of field emission (FE) reveals that the as-synthesized ZnO nanorods arrays have a turn-on field of 3.3 V/μm at the current density of 0.1 μA/cm² and a low threshold field of 6.2 V/μm at the current density of 1 mA/cm². So this approach must have a potential application of fabricating micropatterned oxide thin films used in FE-based flat panel displays.     

Photoluminescence behavior of ZnO nanorods produced by eclipse PLD from a Zn metal target

In this work, arrays of one-dimensional ZnO nanostructures were deposited on c-axis sapphire by standard and eclipse pulsed laser deposition (EPLD) using a metallic Zn target. One reference sample was grown by standard PLD and nine were grown by EPLD using a 16 by 16 mm² square shadow mask. Three shadow mask positions were used, with three depositions at varying oxygen pressures for each mask position. The oxygen partial pressure was between 100 and 200 mTorr for all growth procedures with a substrate temperature of 600 C.SEM reveals that arrays of nanorods are formed when growing by standard PLD. When grown by EPLD the rods tend to clump together with ordering on the micron scale. Low temperature photoluminescence was carried out as a function of position over several of the samples with 1 or 2 mm spacing. In general, it was found that the luminescence intensity is maximum in the center of the samples and falls off toward the edges while the shape stays roughly the same. Free exciton emission was resolved in most samples along with several other emission peaks from donor-bound excitons. The integrated PL intensity for all the EPLD samples is an order of magnitude higher than for the standard PLD sample. Linewidths are significantly reduced as well. Hence, the EPLD grown samples have superior optical quality and this growth technique shows promise for growth of high quality ZnO nanostructures.     

Control of diameter of ZnO nanorods grown by chemical vapor deposition with laser ablation of ZnO

We made a study of controlling diameters of well-aligned ZnO nanorods grown by low-pressure thermal chemical vapor deposition combined with laser ablation of a sintered ZnO target, which was developed by us. Until now, it has been impossible to control diameters of ZnO nanorods, while the growth orientation was maintained well-aligned. In this study we developed a multi-step growth method to fabricate well-aligned nanorods whose diameters could be controlled. Metal Zn vapor and O₂ are used as precursors to grow ZnO nanorods. N₂ is used as a carrier gas for the precursors. A substrate is an n-Si (111) wafer. A sintered ZnO target is placed near the substrate and ablated by a Nd–YAG pulsed laser during ZnO nanorod growth. The growth temperature is 530 C and the pressure is 66.5 Pa. A vertical growth orientation of ZnO nanorods to the substrate is realized in the first-step growth although the diameter cannot be controlled in this step. When an O₂ flow rate is 1.5 sccm, well-aligned nanorods with 100 nm diameter are grown. Next, the second-step nanorods are grown on only the flat tip of the first-step nanorods. The diameters of the second-step nanorods can be controlled by adjusting the O₂ flow rate, and the growth direction is kept the same as that of the first-step nanorods. When the O₂ flow rate in second-step growth is smaller than 0.6 sccm, the diameter of the second-step nanorods is 30–50 nm. When the O₂ flow rate is between 0.75 and 3.0 sccm, the diameter is almost same as that of the first-step nanorods. When the O₂ flow rate is larger than 4.5 sccm, the diameter is increased with increasing O₂ flow rate. Further, the third-step ZnO nanorods with gradually increased diameters can be grown on the second-step nanorods with 1.5 sccm O₂ flow rate and without laser ablation.     

Fabrication of needle-like ZnO nanorods arrays by a low-temperature seed-layer growth approach in solution

Uniform, large-scale, and well-aligned needle-like ZnO nanorods with good photoluminescence and photocatalysis properties on Zn substrates, have been successfully fabricated using a simple low-temperature seed-layer growth approach in solution (50 °C). The formation of ZnO seed-layer by the anodic oxidation technique (AOT) plays an important role in the subsequent growth of highly oriented ZnO nanorods arrays. Temperature also proved to be a significant factor in the growth of ZnO nanorods and had a great effect on their optical properties. X-ray diffraction (XRD) analysis, selected-area electron diffraction (SAED) pattern and high-resolution TEM (HRTEM) indicated that the needle-like ZnO nanorods were single crystal in nature and that they had grown up preferentially along the [0001] direction. The well-aligned ZnO nanorods arrays on Zn substrates exhibited strong UV emission at around 380 nm at room temperature. To investigate their potential as photocatalysts, degradation of pentachlorophenol (PCP) in aqueous solution was carried out using photocatalytic processes, with comparison to direct photolysis. After 1 h, the degradation efficiencies of PCP by direct photolysis and photocatalytic processes achieved 57% and 76% under given experimental conditions, respectively. This improved degradation efficiency of PCP illustrates that ZnO nanorods arrays on Zn substrates have good photocatalytic activity. This simple low-temperature seed-layer growth approach in solution resulted in the development of an effective and low-cost fabrication process for high-quality ZnO nanorods arrays with good optical and photocatalytic properties that can be applicable in many fields such as photocatalysis, photovoltaic cells, luminescent sensors, and photoconductive sensors. PACS 81.07.Bc; 81.10.Dn; 81.15.Pq; 82.50.Hp; 85.60.Jb     

X-ray analysis of ZnO nanorods grown by microwave irradiation heating on ZnO films

Utilizing microwave irradiation heating, 100-nm-diameter ZnO nanorods were grown from aqueous solution on sputtered ZnO films on glass substrates. Its out-of-plane X-ray diffraction (XRD) measurement indicated that the ZnO nanorods were grown with c-axis orientation, similar with the underlying ZnO films. In the in-plane XRD measurement, intensity of the () diffraction was comparable with that of the () one, suggesting their intensity ratio would contain useful information on nanorods density.     

Study of structural, optical and electrical properties of ZnO and SnO2 thin films

The investigation of structure, optical and electrical properties of tin and zinc oxide films on glass substrates by using magnetron sputtering are carried out. X-ray data show the formation of textured tin oxides film during deposition and its transformation to SnO₂ polycrystalline film at low temperature (200 C) if the concentration of oxygen in the chamber is high (O₂ — 100%, Ar — 0%). Optimal conditions of SnO₂ polycrystalline film deposition (pressure of Ar–O₂ mixture in chamber — 2.7 Pa, concentration of O₂ — 10%) are determined. Low resistivity of as-deposited ZnO film and increasing ZnO crystallite sizes and phase volume at temperatures higher than the melting point of Zn (419.5 C) are explained by formation of conductive Zn and ZnO particle chains and their destruction, respectively.     

Study of the MOCVD growth of ZnO on GaAs substrates: Influence of the molar ratio of the precursors on structural and morphological properties

ZnO thin films were grown by metal-organic chemical vapour deposition (MOCVD) on GaAs(100) and GaAs(111)A substrates. The growth experiments were performed at temperatures ranging from 290 to 500 C and atmospheric pressure. Diethylzinc (DEZn) and tertiary butanol (tBuOH) were used as Zn and O precursors, respectively. The crystallinity of the grown films was studied by X-Ray Diffraction (XRD) and the thickness and morphology were investigated by Scanning Electron Microscopy (SEM). The influence of substrate orientation and molar ratio of the precursors on the crystalline orientation and morphology of the ZnO grown films was analysed.     

Fabrication and properties of ZnO:Cu and ZnO:Ag thin films

Thin films of ZnS and ZnO:Cu were grown by an original metal–organic chemical vapour deposition (MOCVD) method under atmospheric pressure onto glass substrates. Pulse photo-assisted rapid thermal annealing of ZnO:Cu films in ambient air and at the temperature of 700–800 C was used instead of the common long-duration annealing in a vacuum furnace. ZnO:Ag thin films were prepared by oxidation and Ag doping of ZnS films. At first a closed space sublimation technique was used for Ag doping of ZnO films. The oxidation and Ag doping were carried out by a new non-vacuum method at a temperature >500 C. Crystal quality and optical properties were investigated using X-ray diffraction (XRD), atomic force microscopy (AFM), and photoluminescence (PL). It was found that the doped films have a higher degree of crystallinity than undoped films. The spectra of as-deposited ZnO:Cu films contained the bands typical for copper, i.e. the green band and the yellow band. After pulse annealing at high temperature the 410 and 435 nm photoluminescent peaks were observed. This allows changing of the emission colour from blue to white. Flat-top ZnO:Ag films were obtained with the surface roughness of 7 nm. These samples show a strong ultraviolet (UV) emission at room temperature. The 385 nm photoluminescent peak obtained is assigned to the exciton–exciton emission.     

Electrodeposition of aligned arrays of ZnO nanorods in aqueous solution

We report electrodeposition of ZnO nanorods from aqueous solution at low temperature (～80 ^°C). The substrates used were thin films of silver grown on glass by thermal evaporation. Nanorods were grown by electrodeposition from aqueous solution of Zinc Nitrate and Hexamethylenetetramine (HMT). The growth process lasts for up to 4 h and the optimum potential for growth of nanorods was ?0.8 V. The nanorods have a well-defined hexagonal morphology and have a Wurtzite structure. The nanorods were characterized by different techniques and have a band gap of 3.08 eV. The width of nanorods has a bimodal distribution.     

The role of a ZnO buffer layer in the growth of ZnO thin film on Al2O3 substrate

A ZnO buffer layer and ZnO thin film have been deposited by the pulsed laser deposition technique at the temperatures of 200 C and 400 C, respectively. Structural, electrical and optical properties of ZnO thin films grown on sapphire (Al₂O₃) substrate with 1, 5, and 9 nm thick ZnO buffer layers were investigated. A minute shift of the (101) peak was observed which indicates that the lattice parameter was changed by varying the thickness of the buffer layer. High resolution transmission electron microscopy (TEM) was used to investigate the thickness of the ZnO buffer layer and the interface involving a thin ZnO buffer between the film and substrate. Selected area electron diffraction (SAED) patterns show high quality hexagonal ZnO thin film with 30 in-plane rotation with respect to the sapphire substrate. The use of the buffer can reduce the lattice mismatch between the ZnO thin film and sapphire substrate; therefore, the lattice constant of ZnO thin film grown on sapphire substrate became similar to that of bulk ZnO with increasing thickness of the buffer layer.     

A template-free sol-gel technique for controlled growth of ZnO nanorod arrays

The growth of ZnO nanorod arrays via a template-free sol-gel process was investigated. The nanorod is single-crystalline wurtzite structure with [0 0 0 1] growth direction determined by the transmission electron microscope. The aligned ZnO arrays were obtained directly on the glass substrates by adjusting the temperatures and the withdrawal speeds, without seed-layer or template assistant. A thicker oriented ZnO nanorod arrays was obtained at proper experimental conditions by adding dip-coating layers. Room temperature photoluminescence spectrum exhibits an intensive UV emission with a weak broad green emission as well as a blue double-peak emission located at 451 and 468 nm, respectively. Further investigation results show that the difference in the alignment of nanorods ascribes to the different orientations of the nanoparticles-packed film formed prior to nanorods on the substrate. Well ordered ZnO nanorods are formed from this film with good c-axis orientation. Our study is expected to pave a way for direct growth of oriented nanorods by low-cost solution approaches.     

Light-induced reversible hydrophilicity of ZnO structures grown by aqueous chemical growth

ZnO wurtzite microrods and flowerlike structures were deposited on glass and ITO substrates by the aqueous chemical growth (ACG) technique at mild temperature (95 °C). Wettability studies revealed that the as-deposited structures are hydrophilic and super-hydrophilic for short and long growth times, respectively. The hydrophilic ZnO surfaces could be reversibly switched to super-hydrophilic by alternation of UV illumination and dark storage. Our results demonstrate that ACG at low temperatures can be efficiently employed to deposit transparent photosensitive ZnO structures exhibiting reversible wettability changes.