Growth mechanism studies of ZnO nanowire arrays via hydrothermal method

Well-controlled ZnO nanowire arrays have been synthesized using the hydrothermal method, a low temperature and low cost synthesis method. The process consists of two steps: the ZnO buffer layer deposition on the substrate by spin-coating and the growth of the ZnO nanowire array on the seed layer. We demonstrated that the microstructure and the morphology of the ZnO nanowire arrays can be significantly influenced by the main parameters of the hydrothermal method, such as pH value of the aqueous solution, growth time, and solution temperature during the ZnO nanowire growth. Scanning electron microscopy observations showed that the well oriented and homogeneous ZnO nanowire arrays can be obtained with the optimized synthesis parameters. Both x-ray diffraction spectra and high-resolution transmission electron microscopy (HRTEM) observations revealed a preferred orientation of ZnO nanowires toward the c-axis of the hexagonal Wurtzite structure, and HRTEM images also showed an excellent monocrystallinity of the as-grown ZnO nanowires. For a deposition temperature of 90 °C, two growth stages have been identified during the growth process with the rates of 10 and 3 nm/min, respectively, at the beginning and the end of the nanowire growth. The ZnO nanowires obtained with the optimized growth parameters owning a high aspect ratio about 20. We noticed that the starting temperature of seed layer can seriously influence the nanowire growth morphology; two possible growth mechanisms have been proposed for the seed layer dipped in the solution at room temperature and at a high temperature, respectively.     

Growth of vertically aligned one-dimensional ZnO nanowire arrays on sol–gel derived ZnO thin films

Vertically aligned one-dimensional ZnO nanowire arrays have been synthesized by a hydrothermal method on sol–gel derived ZnO films. Sol–gel derived ZnO films and corresponding ZnO nanowire arrays have been characterized by X-ray diffraction and field-emission scanning electron microscopy. The effect of sol–gel derived ZnO film surface on the morphology of ZnO nanowire arrays has been investigated. The authors suggest from our investigation that sol–gel derived ZnO films affect the growth of one-dimensional ZnO nanostructures. Not only crystalline ZnO films but also amorphous ones can act as a scaffold for ZnO nucleus. Tilted ZnO micro-rods are grown on ZnO gel films, whereas vertically aligned ZnO nanowire arrays are grown on nanometer-sized ZnO grains. The average diameter of ZnO nanowire arrays are correlated strongly with the grain size of sol–gel derived ZnO films.     

Aligned growth of ZnO nanowires by NAPLD and their optical characterizations

Not only vertically aligned ZnO nanowires but also horizontally aligned ZnO nanowires have been successfully grown on the annealed (0 0 0 1) c-cut and (1 1 2 0) a-cut sapphire substrates, respectively using catalyst-free nanoparticle-assisted pulsed-laser ablation deposition (NAPLD). The as-synthesized ZnO nanowires exhibit an ultraviolet emission at around 390 nm and the absent green emission under room temperature. The single ZnO nanowire was collected in the electrode gap by dielectrophoresis (DEP). Under the optical pumping, the single ZnO nanowire exhibited UV emission at around 390 nm with several sharp peaks whose energy spacings are almost constant, which greatly differs from the broad UV emission of the film with many nanowires, suggesting ZnO nanowires as candidates for laser media. The single ZnO nanowire showed polarized photoluminescence (PL). The as-synthesized ZnO nanowires could find many interesting applications in short-wavelength light-emitting diode (LED), laser diode and gas sensor.     

Synthesis and piezoelectric properties of?well-aligned ZnO?nanowire arrays via a?simple solution-phase approach

An effective, low cost and catalyst-free solution-phase approach was demonstrated for achieving a tailored length and controlled surface-to-volume ratio of aligned ZnO nanowire (NW) arrays. By a slight variation of the solution concentration and growth time, significant changes in length and surface-to-volume ratio of the obtained ZnO NW arrays have been controlled, respectively. The morphology and microstructure of the synthesized products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Also the growth mechanism was discussed. For the study of the piezoelectric property of aligned ZnO NW arrays, some measuring models of nanogenerators (NGs) were fabricated with two pieces of grown ZnO NW array structures stacking together and penetrating into each other. One of the pieces was coated with Au film as the conductive nanotip (NTP) array. The NG was driven by an ultrasonic wave. The piezoelectric output current was gained and characteristic curves have been illustrated for different measuring results. The curves show that increasing the length and surface-to-volume ratios of ZnO NW arrays can enhance the output power of the NGs, respectively. It can be seen that the NGs fabricated with size-controlled ZnO NW arrays provide a feasible technology for building high-power output or power-controlled NGs for applications where a smaller size or appointed power output NGs are required. However, no relationship was found between the piezoelectric current output and the driving frequency of ultrasonic waves from 10 to 50 kHz.     

Growth and characterization of type-II ZnO/ZnTe core-shell nanowire arrays for solar cell applications

Large area, well-aligned type-II ZnO/ZnTe core-shell nanowire arrays have been fabricated on an a-plane sapphire substrate. The ZnO nanowires were grown in a furnace by chemical vapor deposition with gold as catalyst and then were coated with a ZnTe shell on the ZnO nanowires surface by a metal-organic chemical deposition chamber. The morphology and size distribution of the ZnO/ZnTe core-shell nanowire arrays were studied by scanning electron microscopy (SEM) and the crystal structure was examined by x-ray diffraction (XRD). Transmission measurement was used to study the optical properties of the core-shell nanowires. The results indicated that the ZnO/ZnTe core-shell nanowire arrays have good crystalline quality. In addition, it was found that the nanowire arrays have good light absorption characteristics and these properties make it suitable for making photovoltaic devices.     

Aligned growth of ZnO nanowires and lasing in single ZnO nanowire optical cavities

Ordered ZnO nanowire arrays have been fabricated in N₂ background gas by catalyst-free nanoparticle-assisted pulsed-laser deposition. A single ZnO nanowire was collected in an electrode gap by dielectrophoresis. Under the optical pumping above an exciting laser (λ= 355 nm) threshold of ∼ 334 kW/cm², ultraviolet lasing action in a single ZnO nanowire was observed at room temperature, indicating that the as-synthesized nanowires in pure N₂ background gas are of high quality. The crystalline facets of both ends of the nanowire acted to form an optical cavity. Therefore, the mode spacings corresponding to cavity lengths of the respective nanowires were observed in photoluminescence spectra. PACS 78.66.Hf; 81.07.Bc; 78.67.-n; 81.16.Mk     

Synthesis of ZnO compound nanostructures via a chemical route for photovoltaic applications

A facile, low-temperature, and low-cost chemical route has been developed to prepare ZnO nanowire and nanosphere compound structures. The morphology, structure, and composition of the yielded products have been examined by field-emission scanning electron microscopy, transmission electron microscopy, and X-ray diffraction measurements. We have systematically investigated the optical properties of the ZnO nanostructures by micro-Raman, photoluminescence, and transmission spectroscopy. The results demonstrate that the yielded ZnO nanostructures possess good optical quality with high light absorption. We have further successfully employed the obtained ZnO compound nanostructures in dye-sensitized solar cells. The light-to-electricity conversion results show that the compound nanostructure exhibits a significant enhancement of short-circuit current density due to the increased surface area and light scattering in the compound nanostructures. The present chemical route provides a simple way to synthesize various compound nanostructures with high surface area for nanodevice applications.     

Investigation of the effects of tensile strain on optical properties of ZnO nanowire

In this paper, the effects of mechanical tensile strain on optical properties of ZnO nanowire before and after embedding ZnS nanowire were investigated by simulation. Finite element modeling (FEM) software package ABAQUS and three-dimensional (3D) finite-difference time-domain (FDTD) methods were furnished to analyze the problems numerically, including the nonlinear mechanical behavior and optical properties of the sample, respectively. The physical deformation model was imported into the FDTD to investigate optical properties of ZnO nanowire under mechanical tensile strain. Besides, the stress-strain curve via tensile experimental was compared with stress-strain curve that was obtained from finite element modeling. The results disclosed that the mechanical strain was demonstrated to play an important role in determining the optical properties of ZnO nanowire such as absorption coefficient and optical density.     

Synthesis and characterization of highly-ordered ZnO/PbS core/shell heterostructures

The strategy to manipulate nanoscale building blocks into well-organized heterostructures is very important to both material synthesis and nanodevice applications. In this work, highly-ordered ZnO/PbS core/shell nanowire arrays were fabricated by a facile and low temperature chemical route. Large area and well-aligned ZnO nanowire arrays were firstly fabricated on conductive glass substrates, and then the synthesis of ZnO/ZnS and ZnO/PbS core/shell nanowire arrays were realized by a chemical conversion method. The morphology, structure, and composition of the obtained nanostructures were confirmed by field-emission scanning electron microscopy, energy-dispersive X-ray analysis, and X-ray diffraction measurements. The optical properties of the synthesized nanostructures were investigated by micro-Raman and photoluminescence spectroscopy. In the synthesized ZnO/PbS core/shell nanowire arrays, the ZnO cores can provide direct conduction pathways for electron transport and PbS shells possess superior photoelectric performance. Therefore, the obtained ZnO/PbS core/shell nanostructures may have potential application in photovoltaic devices.     

Fabrication and characterization of Cu–CdSe–Cu nanowire heterojunctions

The Cu–CdSe–Cu nanowire heterojunctions were fabricated by sequential electrochemical deposition of layers of Cu metal and CdSe semiconductor within the nano-pores of anodic alumina membrane templates. X-ray diffraction reveals the cubic phase for Cu and hexagonal phase for CdSe in the electrodeposited Cu–CdSe–Cu nanowire heterojunctions. The composition of the nanowire heterojunction segments is characterized by energy dispersive X-ray spectroscopy. The morphological study of nanowire heterojunctions has been made using scanning electron microscope and high resolution transmission microscopy. The nanowire heterojunctions grown in 100 and 300 nm nano-pore size templates have been found to have optical band gaps of 1.92 and 1.75 eV, respectively. The absorption spectra of 100 nm nanowire heterojunctions show a blue shift of 0.18 eV. The collective nonlinear current–voltage (I–V) characteristics of the 300 and 100 nm nanowire heterojunctions show their rectifying and asymmetric behaviour, respectively.     

Strong Coulomb correlation effects in ZnO

The electronic structure, band parameters, and optical spectra of wurtzite-type ZnO were studied by first-principles calculations within different approximations of the density functional theory. The local-density approximation underestimates the band gap, the energy levels of the Zn-3d states, the band dispersion, the crystal-field splitting, the spin-orbit interaction, and location of peaks in the optical spectra. The generalized-gradient approximation slightly corrects the discrepancies with the experimental findings and it shows good agreement for the optical spectra with experimental data at energies 10-20 eV for E⊥c. Studies within the local-density approximation with the multiorbital mean-field Hubbard potential show that strong Coulomb correlations are in operation. From effective mass calculations it is found that holes are much heavier and more anisotropic than the conduction-band electrons in ZnO.     

Optical properties of ZnO and ZnO:Ce layers grown by spray pyrolysis

In this paper, zinc oxide (ZnO) and cerium-doped zinc oxide (ZnO:Ce) films were deposited by reactive chemical pulverization spray pyrolysis technique using zinc and cerium chlorides as precursors. The effects of Ce concentration on the structural and optical properties of ZnO thin films were investigated in detail. These films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and photoluminescence (PL) measurements. All deposited ZnO layers at the temperature 450 °C are polycrystalline and indicate highly c-axis oriented structure. The dimension of crystallites depends on incorporation of Ce atoms into the ZnO films. The photoluminescence spectra of the films have been studied as a function of the deposition parameters such as doping concentrations and post grows annealing. Photoluminescence spectra were measured at the temperature range from 13 K to 320 K.     

Fabrication of ZnO/Al2O3 core-shell nanostructures and crystalline Al2O3 nanotube

We have demonstrated the crystalline ZnO-Al₂O₃ core-shell nanowire structure by atomic layer deposition (ALD) at a temperature 100 °C. The core-shell structure could have potential applications in the fabrication of ZnO field effect transistor. After dissolving the ZnO core, shape defined, rigid and robust crystalline Al₂O₃ shelled nanostructures have been fabricated. Nanowire ZnO nanostructures have been replicated by alumina shell. This is one of the most effective techniques for producing core-shell or shell/hollowed nanostructures of any desired objects. The Al₂O₃ shelled nanostructures could have potential applications as space confined nanoreactors, drug delivery, nanofluidic channels and optical transmitting.     

Effect of zinc nitrate concentration on the structural and the optical properties of ZnO nanostructures

ZnO nanorods and nanodisks were formed on indium-tin-oxide-coated glass substrates by using an electrochemical deposition method. Scanning electron microscopy images showed that the ZnO nanorods were transformed into nanodisks with increasing Zn(NO₃)₂ concentration. X-ray diffraction patterns showed that the ZnO nanostructures had wurzite structures. The full widths at half maxima of the near band-edge emission peak of photoluminescence spectra at 300 K for ZnO nanorods were small, indicative of the high quality of the nanorods. These results indicate that the structural and the optical properties of ZnO nanostructures vary by changing Zn(NO₃)₂ concentration.     

树形结构Si/ZnO纳米线阵列的制备及光学性能

用一种低成本的方法制备出了树形结构Si/ZnO纳米线阵列。首先在室温条件下用金属辅助化学腐蚀法在Si(100)衬底上制备了Si纳米线阵列,Si纳米线的直径尺寸及分布都很均匀,通过改变腐蚀时间,能够得到高度不同的Si纳米线阵列。利用磁控溅射在Si纳米线表面制备一层ZnO薄膜,然后利用水热法在Si纳米线阵列上生长了ZnO纳米线。通过扫描电子显微镜(SEM)、能谱分析仪(EDS)和光致发光(PL)测试对样品进行了表征。通过这种方法制备的Si/ZnO复合结构在太阳能电池、光催化等领域有潜在应用价值。     

Wetting characteristics of ZnO smooth film and nanowire structure with and without OTS coating

ZnO is an important material that is used in a variety of technologies including optical devices, sensors, and other microsystems. In many of these technologies, wettability is of great concern because of its implications in numerous surface related interactions. In this work, the effects of surface morphology and surface energy on the wetting characteristics of ZnO were investigated. ZnO specimens were prepared in both smooth film and nanowire structure in order to investigate the effects of surface morphology. Also, a hydrophobic octadecyltrichlorosilane (OTS) coating was used to chemically modify the surface energy of the ZnO surface. Wettability of the surfaces was assessed by measuring the water contact angle. The results showed that the water contact angle varied significantly with surface morphology as well as surface energy. OTS coated ZnO nanowire specimen had the highest contact angle of 150°, which corresponded to a superhydrophobic surface. This was a drastic difference from the contact angle of 87° obtained for the smooth ZnO film specimen. In addition to the initial contact angle, the evolution of the water droplet with respect to time was investigated. The wetting state of water droplet was analyzed with both Wenzel and Cassie-Baxter models. Spontaneous and gradual spreading, together with evaporation phenomenon contributed to the changing shape, and hence the varying contact angle, of the water droplet over time.     

Structural, optical and electrical properties of Al-N codoped ZnO films by RF-assisted MOCVD method

N-doped ZnO films were produced using N₂ as N source by metal-organic chemical vapor deposition (MOCVD) system which has been improved with radio-frequency (RF)-assisted equipments. The data of secondary ion mass spectroscopy (SIMS) indicate that the concentration of N in N-doped ZnO films is around 5 × 10²⁰ cm⁻³, implying that sufficient incorporation of N into ZnO can be obtained by RF-assisted equipment. On this basis, the structural, optical and electrical properties of Al-N codoped ZnO films were studied. Then, the effect of RF power on crystal quality, surface morphologies, optical properties was analyzed using X-ray diffraction, atomic force microscopy and photo-luminescence methods. The results illustrate that the RF plasma is the key factor for the improvement of crystal quality. Then the observation of A⁰X recombination associated with N_O acceptor in low-temperature PL spectrum proved that some N atoms have occupied the positions of O atoms in ZnO films. Hall measurements shown that p-type ZnO film deposited on quartz glasses was obtained when RF power was 150 W for the Al-N codoped ZnO films, while the resistivity of N-doped ZnO films was rather high. Compared with the Al-doped ZnO film, the obviously increased resistivity of codoped films indicates that the formation of N_O acceptors compensate some donors in ZnO films effectively.     

Pulsed-laser deposition and characterization of ZnO nanowires with regular lateral arrangement

We report on the high-pressure pulsed-laser deposition growth of periodic arrays of free-standing single zinc oxide nanowires with uniform hexagonal arrangement and cross-section with thickness of less than 100 nm. In order to achieve the wire alignment, we prepared an ordered array of catalytic gold seed particles by a nanosphere lithography mask transfer technique using monodisperse spherical polystyrol nanoparticles. These templates were investigated by scanning electron microscopy and atomic force microscopy prior to nanowire growth. X-ray diffraction revealed the epitaxial relationships between the nanostructures and the a-plane sapphire substrate and excellent crystal quality. The optical properties of the ZnO nanowire arrays were measured by cathodoluminescence. PACS 61.82.Rx; 81.05.-t; 81.05.Dz; 81.10.-h     

Highly flexible,transparent, conductive and antibacterial films made of spin-coated silver nanowires and a protective ZnO layer

We prepared highly flexible, transparent, conductive and antibacterial film by spin coating a silver nanowire suspension on a poly (ethylene terephthalate) (PET) substrate. The ZnO layer covered the conductive silver nanowire (AgNW) network to protect the metal nanowires from oxidization and enhance both wire-to-wire adhesion and wire-to-substrate adhesion. It is found that the number of AgNW coatings correlates with both the sheet resistance (R_s) and the transmittance of the AgNW/ZnO composite films. An excellent 92% optical transmittance in the visible range and a surface sheet resistance of only 9 Ω sq⁻¹ has been achieved, respectively. Even after bending 1000 times (5 mm bending radius), we found no significant change in the sheet resistance or optical transmittance. The real-time sheet resistance measured as a function of bending radius also remains stable even at the smallest measured bending radius (1 mm). The AgNW/ZnO composite films also show antibacterial effects which could be useful for the fabrication of wearable electronic devices.     

Photoluminescent zinc oxide polymer nanocomposites fabricated using picosecond laser ablation in an organic solvent

Nanocomposites made of ZnO nanoparticles dispersed in thermoplastic polyurethane were synthesized using picosecond laser ablation of zinc in a polymer-doped solution of tetrahydrofuran. The pre-added polymer stabilizes the ZnO nanoparticles in situ during laser ablation by forming a polymer shell around the nanoparticles. This close-contact polymer shell has a layer thickness up to 30 nm. Analysis of ZnO polyurethane nanocomposites using optical spectroscopy, high resolution transmission electron microscopy and X-ray diffraction revealed that oxidized and crystalline ZnO nanoparticles were produced. Those nanocomposites showed a green photoluminescence emission centred at 538 nm after excitation at 350 nm, which should be attributed to oxygen defects generated during the laser formation mechanism of the monocrystalline nanoparticles. Further, the influence of pulse energy and polymer concentration on the production rate, laser fluence and energy-specific mass productivity was investigated.