Structural and electrical properties of VO2/ZnO nanostructures

We examined the structural and electrical properties of uniformly-oriented VO₂/ZnO nanostructures. VO₂ was deposited on ZnO templates by using a direct current-sputtering deposition. Scanning electron microscope and transmission electron microscope measurements indicated that b-oriented VO₂ were uniformly crystallized on ZnO templates with different lengths. VO₂/ZnO formed nanorods on ZnO nanorods with length longer than 250 nm. X-ray absorption fine structure at the V K edge of VO₂/ZnO showed M₁ and R phases of VO₂ at 30 and 100 °C, respectively, suggesting structural-phase transition occurring between the two temperatures. Temperature-dependent resistance measurements of VO₂/ZnO nanostructures revealed metal-to-insulator transition at 65 °C and 55 °C during a heating and a cooling, respectively, regardless of ZnO length. Asymmetry behavior of resistance curves from VO₂/ZnO nanostructure during a heating and a cooling was attributed from a strong bond of VO₂ and ZnO.     

Synthesis and field-emission properties of roselike ZnO nanostructures

Self-assembled roselike ZnO nanostructures were synthesized via thermal evaporation of zinc powders without catalytic assistance at the relatively low temperature of 550 °C. The roselike structures consist of a large number of ZnO nanorods that uniformly arrange into hexagonal multilayers. The spontaneous nanoindentation effects under geometric constraints can be used to explain the structures. The cathodoluminescence spectra show a wide visible emission band related to Zn interstitials and oxygen vacancies. Field emission measurements demonstrate that the roselike ZnO nanostructures possess good electron emission characteristics with a turn-on field of 4.3 V/μm. PACS 68.70.+w; 78.55.Cr; 81.05.Cy     

Morphology transition of ZnO films with DMZn flow rate in MOCVD process

We used a metal-organic chemical vapor deposition (MOCVD) method to grow ZnO films on MgAl₂O₄ (1 1 1) substrate, and succeeded in preparing films with microstructures from well-aligned ZnO nanorods to continuous and dense films by adjusting the ratio of the input rates of oxygen and zinc sources (VI/II). At the growth temperature of 350 °C, the ZnO nanorods were formed under a low flow rate of a zinc precursor. On the other hand, continuous and dense ZnO films were formed under a high flow rate of the zinc precursor. There is a transition zone at medium zinc precursor flow rate, where nanorods transform to dense films. We proved that the height of ZnO nanorods and the thickness of ZnO dense films both increase with zinc flow rate, and are consistent with the mass-transport mechanism for ZnO growth. The XRD spectra of the sample in the transition zone show both (0 0 2) and (1 0 1) peaks, where (1 0 1) peaks are formed only in the transition zone. We consider that there are (0 0 2) and (1 0 1) ZnO grains in the early growth stage of dense ZnO films.     

Utilization of surface plasmon resonance of Au/Pt nanoparticles for highly photosensitive ZnO nanorods network based plasmon field effect transistor

Hydrothermally processed highly photosensitive ZnO nanorods based plasmon field effect transistors (PFETs) have been demonstrated utilizing the surface plasmon resonance coupling of Au and Pt nanoparticles at Au/Pt and ZnO interface. A significantly enhanced photocurrent was observed due to the plasmonic effect of the metal nanoparticles (NPs). The Pt coated PFETs showed I_on/I_off ratio more than 3 × 10⁴ under the dark condition, with field-effect mobility of 26 cm² V⁻¹ s⁻¹ and threshold voltage of −2.7 V. Moreover, under the illumination of UV light (λ = 350 nm) the PFET revealed photocurrent gain of 10⁵ under off-state (−5 V) of operation. Additionally, the electrical performance of PFETs was investigated in detail on the basis of charge transfer at metal/ZnO interface. The ZnO nanorods growth temperature was preserved at 110 °C which allowed a low temperature, economical and simple method to develop highly photosensitive ZnO nanorods network based PFETs for large scale production.     

水热法合成ZnO纳米棒图案及其场增强效应

利用水热合成方法在图案化的Au岛上合成了ZnO纳米棒图案,采用的溶液体系为六次甲基四胺和硝酸锌溶液,ZnO纳米棒的基底是ITO导电玻璃上的有序Au岛. 由于ZnO的异相成核速度在Au和ITO基底上具有不同的成核速度,因此ZnO优先生长在成核速度快的Au岛上,同时由于受到了溶液中前驱物种扩散的限制,纳米棒继续生长也被受到了约束. 通过调控六次甲基四胺和硝酸锌的浓度,可以调整不同的图案. 此外,利用X射线衍射、光致发光谱和场发射特性性能对水热合成的ZnO纳米棒图案进行了研究. ZnO纳米棒表现出良好的场增强性     

The growth mechanism of ZnO single-crystal nanorods synthesized by polymer complexing with zinc salts

The growth mechanism of single-crystal ZnO nanorods synthesized by the method of polymer complexing with zinc salts is investigated. The annealing temperature is controlled at about the decomposition temperature of dihydrate zinc acetate (Zn(O₂CCH₃)₂·2H₂O) of 573 K. By changing the annealing time, the ZnO nanostructures can be modified from nanoparticles to nanorods. As a result, the formation of single-crystal ZnO nanorods can be observed. Through investigating the Fourier transform infrared spectra of (a) polyvinyl pyrrolidone (PVP), (b) Zn(O₂CCH₃)₂·2H₂O and (c) the mixture of PVP and Zn(O₂CCH₃)₂(H₂O)₂, the interaction between PVP and Zn(O₂CCH₃)₂·2H₂O can be observed. PVP plays an important role in the growth of the single-crystal ZnO nanorods. We analyze the growth process of ZnO nanorods by observing their TEM images at different moments. Consequently, our results indicate that the single-crystal ZnO nanorods were formed by self-assembling the ZnO nanoparticles. PACS 61.46.Hk; 61.46.Df; 78.30.-j; 81.07.-b; 81.16.Be     

Strong temperature and substrate effect on ZnO nanorod flower structures in modified chemical vapor condensation growth

We have reported low temperature growth (300 °C) of ZnO nanorod flower structures by depositing zinc acetate vapor on Ge (100) substrate in the form of a jet using chemical vapor condensation technique. The flowers were comprised of hierarchical arrangement of highly crystalline ZnO nanorods oriented isotropically around a common nucleus. The temperature window for stability of these structures was found to be very narrow and the formation of the flowers was highly depended on the type of the substrates used. The flower morphology changed to a different hemispherical shape when the growth temperature was increased by only 50 °C while decreasing the growth temperature of the same degrees resulted in an amorphous deposition of ZnO. The temperature and substrate effect has been explained on the basis of adatom kinetics during growth. X-ray diffraction and TEM study revealed wurtzite ZnO nanorods with lattice constants a and c of 3.2 and 5.19 Å, respectively. The flower structures showed strong room temperature photoluminescence having pure excitonic transition at around 3.298 eV.     

Enormous enhancement of ZnO nanorod photoluminescence

ZnO nanorod arrays were grown on quartz slices in the aqueous solution of zinc acetate and hexamethylenetetramine at 90 °C. Then ZnO:Mg shells were epitaxially grown on the nanorods to form core/shell structures in the aqueous solution of zinc acetate, magnesium acetate and hexamethylenetetramine at the same temperature. Effects of the shells and UV laser beam irradiation on the crystal structure and photoluminescence properties of ZnO nanorods were studied. ZnO:Mg shells suppress the green emission and enhance the UV emission intensity of the nanorods by 38 times. Enhancement of the UV emission depends on the Mg content in the shells. Short time UV laser beam irradiation could improve ZnO nanorod emission efficiently. The UV emission intensity of ZnO nanorods is enhanced by 71 times by capping and subsequent UV laser beam irradiation.     

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.     

Intrinsic defects, impurities and doping in ZnO nanorods grown at low temperature

We report on the defect properties of single-crystalline ZnO nanorods grown from solutions at temperatures below 90 °C. The nanorods can easily be doped by providing impurity precursors during growth. In the as-grown state the nanorods exhibit considerable lattice strain and distortions which compromise their electrical and optical properties. Upon annealing at moderate temperatures of <400 °C the lattice strain is converted into dislocation-type defects, and the dopant impurities become optically active. In the annealed state the near-bandgap photoluminescence quantum efficiency is improved more than 5 times and reaches ～16 % at room temperature. Thus with moderate annealing, interesting device applications become feasible for nanorods grown at T<90 ^°C.     

A simple growth route towards ZnO thin films and nanorods

Highly orientated ZnO thin films and the self-organized ZnO nanorods can be easily prepared by a simple chemical vapor deposition method using zinc acetate as a source material at the growth temperature of 180 and 320 °C, respectively. The ZnO thin films deposited on Si (100) substrate have good crystallite quality with the thickness of 490 nm after annealing in oxygen at 800 °C. The ZnO nanorods grown along the [0001] direction have average diameter of 40 nm with length up to 700 nm. The growth mechanism for ZnO nanorods can be explained by a vapor-solid (VS) mechanism. Photoluminescence (PL) properties of ZnO thin films and self-organized nanorods were investigated. The luminescence mechanism for green band emission was attributed to oxygen vacancies and the surface states related to oxygen vacancy played a significant role in PL spectra of ZnO nanorods.     

Nitrogen incorporation in homoepitaxial ZnO CVD epilayers

ZnO:N thin films have been deposited on oxygen and zinc terminated polar surfaces of ZnO. The nitrogen incorporation in the epilayers, using NH₃ as doping source, was investigated as a function of the growth temperature in the range between 380 °C and 580 °C. We used Raman spectroscopy and low temperature photoluminescence to investigate the doping properties. It turned out that the nitrogen incorporation strongly depends on both, the surface polarity of the epitaxial films and the applied growth temperatures. In our CVD process low growth temperatures and Zn‐terminated substrate surfaces clearly favour the nitrogen incorporation in the ZnO thin films. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of the polymer emission on the electroluminescence characteristics of n-ZnO nanorods/p-polymer hybrid light emitting diode

Hybrid light emitting diodes (LEDs) based on zinc oxide (ZnO) nanorods and polymers (single and blended) were fabricated and characterized. The ZnO nanorods were grown by the chemical bath deposition method at 50°C. Three different LEDs, with blue emitting, orange-red emitting or their blended polymer together with ZnO nanorods, were fabricated and studied. The current–voltage characteristics show good diode behavior with an ideality factor in the range of 2.1 to 2.27 for all three devices. The electroluminescence spectrum (EL) of the blended device has an emission range from 450 nm to 750 nm, due to the intermixing of the blue emission generated by poly(9,9-dioctylfluorene) denoted as PFO with orange-red emission produced by poly(2-methoxy-5(20-ethyl-hexyloxy)-1,4-phenylenevinylene) 1,4-phenylenevinylene) symbolized as MEH PPV combined with the deep-band emission (DBE) of the ZnO nanorods, i.e. it covers the whole visible region and is manifested as white light. The CIE color coordinates showed bluish, orange-red and white emission from the PFO, MEH PPV and blended LEDs with ZnO nanorods, respectively. These results indicate that the choice of the polymer with proper concentration is critical to the emitted color in ZnO nanorods/p-organic polymer LEDs and careful design should be considered to obtain intrinsic white light sources.     

Thermo-electrochemical selective growth of ZnO nanorods on any noble metal electrodes

Selective growth of ZnO nanorods has been successfully performed on the patterned Au/Ti metal electrode regions on a glass substrate by using a seeded thermo-electrochemical method in an acidic growth solution. The selective growth mechanism of the thermo-electrochemical method was proposed by using a series of chemical reactions for the first time. The thermo-electrochemical selective ZnO growth was performed on the cathode electrode at a temperature below 90 °C. A ZnO seed layer was precoated and selectively etched away from the non-metal regions in order to create the patterned selective nucleation sites on which the precursors are transferred and crystallized into ZnO nanorods. Both the dimensions and the placements of the ZnO nanorods have been simultaneously controlled. Energy dispersive X-ray spectrometry showed that the selectively grown ZnO nanorods consist of only Zn and O, indicating that the selectively grown ZnO nanorods are pure and contamination free. XRD and electron diffraction patterns revealed that the obtained ZnO nanorods have a wurtzite single-crystal structure.     

Characterization and ammonia sensing properties of pure and?modified ZnO films

Zinc oxide (ZnO) films have been prepared by thermal oxidation of pre-deposited zinc films on the glass substrate kept at room temperature. These films were surface modified by dipping them into an aqueous solution (0.1 M) of lithium chloride (LiCl) and aluminium chloride (AlCl₃) followed by firing at 500°C. Based on X-ray diffraction results it is observed that modification of pure ZnO by lithium and aluminium precursor results a change in the lattice parameters. Li and Al ions appear to enhance the a-axis orientation and c-axis orientation of pure ZnO films, respectively. Field emission scanning electron micrographs of lithium-modified ZnO film indicate the presence of nanoneedles, while nanorods are observed in case of aluminium-modified ZnO film. The electrical resistance measurements of modified ZnO films also show variation in resistance as compared to pure ZnO film. Pure and Al-modified films of ZnO are sensitive to ammonia at room temperature, while Al-modified ZnO film is found to be more sensitive with 99% of response at 250 ppm.     

Nanostructure size evolution during Au-catalysed growth by carbo-thermal evaporation of well-aligned ZnO nanowires on (100)Si

We report the structural and morphological properties of well-aligned ZnO nanowires grown at 750 °C on Au-deposited and annealed (100)Si substrates using carbo-thermal evaporation. As-grown nanowires are made of wurtzite ZnO, have cylindrical shape and carry droplet-like nanoparticles (NPs) at their tips, as expected for vapour–liquid–solid (VLS) growth. Grazing incidence X-ray diffraction measurements demonstrate that the NPs are made of pure fcc Au. No secondary Au/Zn alloy phases were detected. Bragg diffraction patterns confirmed that the nanowires were grown with their crystal c-axes parallel to the [100] direction of Si (i.e. normal to the substrate surface), while Au NPs are mostly (111)-oriented. The diameter distribution of ZnO nanowires mimics that of the Au NPs at their tips. A quantitative study of the nanostructure size distribution after sequential annealing and growth steps evidences the occurrence of three nanoscale processes: (i) Ostwald ripening and/or coalescence of Au NPs before nanowire nucleation, (ii) Au-catalysed VLS nucleation and axial growth of ZnO nanowires and (iii) radial growth of nanowires by a vapour–solid process. These processes originate the NP and nanowire size evolution during the experiments. The present findings are interpreted in terms of Zn vapour pressure changes during carbo-thermal evaporation. PACS 61.46.+w; 68.65.-k; 81.16.Dn     

Photoelectric properties of ZnO: In nanorods/SiO2/Si heterostructure assembled in aqueous solution

In-doped zinc oxide (ZnO:In) nanorods were grown onto SiO₂/n-Si substrate without catalyst in aqueous solution. The ZnO:In nanorods/SiO₂/n-Si heterostructure photovoltaic device was prepared. The structural and photoelectric properties of the as-grown ZnO:In nanorods were analyzed. ZnO:In nanorods had a strong and broad UV surface photovoltage response in the range of 300–400 nm, and the bands were identified. The photoelectric conversion properties of ZnO:In nanorods/SiO₂/n-Si heterostructure were investigated. ZnO:In/SiO₂/n-Si heterostructure showed a wide range photocurrent spectral response with high intensity in the UV and visible region. The rectifying behavior of this heterostructure was observed. Moreover, the device had a low turn-on voltage and a high breakdown voltage. Current–voltage characteristic was studied for the heterostructure, and the open-circuit voltage and short-circuit current were obtained. PACS 73.40.Lq; 85.35.Be; 81.16.Dn     

Effect of annealing temperature on optical and electrochemical properties of chitosan–ZnO nanostructure

Chitosan–ZnO nanostructures were prepared by chemical precipitation method using different concentration of zinc chloride and sodium hydroxide solutions. Nanorod-shaped grains with hexagonal structure for samples annealed at 300 °C and porous structure with amorphous morphology for samples annealed at 600 °C were revealed in SEM analysis. X-ray diffraction patterns confirmed the hexagonal phase ZnO with crystallite size found to be in the range of ~24.15–34.83 nm. Blue shift of UV–Vis absorption shows formation of nanocrystals/nanorods of ZnO with marginal increase in band gap. Photoluminescence spectra show that blue–green emission band at 380–580 nm. The chitosan–ZnO nanostructures used on surface of a glassy carbon electrode gives the oxidation peak potential at ~0.6 V. The electrical conductivity of chitosan–ZnO composites were observed at 2.1?×?10^?5 to 2.85?×?10^?5?S/m. The nanorods with high surface area and nontoxicity nature of chitosan–ZnO nanostructures observed in samples annealed at 300 °C were suitable as a potential material for biosensing.     

Synthesis,structural, optical and magnetic properties of Cu-doped ZnO nanorods prepared by a simple direct thermal decomposition route

Cu-doped ZnO nanorods (i.e. Cu = 1.75, 3.55, 5.17 and 6.39 at.%) have been successfully synthesized by simple, direct, thermal decomposition of zinc and copper acetates in air at 300 °C for 6 h. The prepared samples were characterized by X-ray diffraction (XRD) and transmission electron microscopy. The XRD results indicate that the 1.75 at.% Cu-doped ZnO sample has a pure phase with the ZnO wurtzite structure, while the impurity phases are detected with increasing Cu concentrations. It was found that the doping of Cu results in a reduction of the preparation temperature. The optical properties of the samples were also investigated by UV–visible spectroscopy and photoluminescence measurements. The results show that the Cu doping causes the change in energy-band structures and effectively adjusts the intensity of the luminescence properties of ZnO nanorods. X-ray photoelectron spectroscopy analysis implies that there are some oxygen vacancies in the samples and also indicates that all the doped samples are associated with the mixture of Cu ion states (Cu²⁺ and Cu¹⁺/Cu⁰). Magnetic measurements by vibrating sample magnetometry indicate that undoped ZnO is diamagnetic, whereas all of the Cu-doped ZnO samples exhibit room temperature ferromagnetic behavior. We suggest that Cu substitution and density of oxygen vacancies (V _o) may play a major role in the room temperature magnetism of the Cu-doped ZnO samples.     

Direct comparison of the electrical,optical, and structural phase transitions of VO2 on ZnO nanostructures

We examined the temperature-dependent electrical, optical, and structural properties of VO₂ on ZnO nanorods with different lengths in the temperature range from 30 to 100 °C. ZnO nanorods with a uniform length were grown on Al₂O₃ substrates using a metal organic chemical vapor deposition, and subsequently, VO₂ was ex-situ deposited on ZnO nanorods/Al₂O₃ templates using a sputtering deposition. The optical properties of the VO₂/ZnO nanorods were measured simultaneously with direct current (DC) resistance using the reflectivity of an infrared (IR) laser beam with a wavelength of 790 nm. The local structural properties around V atoms of VO₂/ZnO nanorods were simultaneously measured with the DC resistance using x-ray absorption fine structure at the V K edge. Direct comparison of the temperature-dependent resistance, IR reflectivity, and local structure reveals that an optical phase transition first occurs, a structural phase transition follows, and an insulator-to-metal transition finally appears during heating.