Fabrication of Co-doped ZnO nanowires and their temperature-dependent ultraviolet emission properties

Co-doped ZnO nanowires have been fabricated through a high temperature vapor–solid deposition process. The temperature-dependent ultraviolet emission properties of Co-doped ZnO nanowires under 10–300 K were reported. The results show that there are multipeak emissions situated at the ultraviolet region. The investigation of the excitonic transition in Co-doped ZnO nanowires shows that there is an intensive ultraviolet periodic emission of Co-doped ZnO nanowires under low temperature. The oscillatory structure has an energy periodicity about 70 meV. The oscillatory structure is mainly attributed to the longitudinal optical phonon replicas of the free exciton. The ultraviolet emission shows an obvious redshift with the increasing temperature.     

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.     

Effects of annealing temperature on the structure, photoluminescence and ferromagnetism properties of Cr-implanted ZnO nanowires

Room temperature ferromagnetism was observed in Cr-implanted ZnO nanowires annealed at 500, 600, and 700 °C. The implantation dose for Cr ions was 1×10¹⁶ cm^?2, while the implantation energies were 100 keV. Except for ZnO (100), (002), and (200) orientations, no extra diffraction peaks from Cr-related secondary phase or impurities were observed. With the increasing of annealing temperatures, the intensity of the peaks increased while the FWHM values decreased. The Cr 2p_1/2 and 2p_3/2 peaks, with a binding energy difference of 10.6 eV, appear at 586.3 and 575.7 eV, can be attributed to Cr³⁺ in ZnO nanowires. For the Cr-implanted ZnO nanowires without annealing, the band energy emission disappears and the defect related emission with wavelength of 500–700 nm dominates, which can be attributed to defects introduced by implantation. Cr-implanted ZnO nanowires annealed at 500 °C show a saturation magnetization value of over 11.4×10^?5 emu and a positive coercive field of 67 Oe. The origin of ferromagnetism behavior can be explained on the basis of electrons and defects that form bound magnetic polarons, which overlap to create a spin-split impurity band.     

A rapid synthesis/growth process producing massive ZnO nanowires for humidity and gas sensing

We report a rapid and simple process to massively synthesize/grow ZnO nanowires capable of manufacturing massive humidity/gas sensors. The process utilizing a chemical solution deposition with an annealing process (heating in vacuum without gas) is capable of producing ZnO nanowires within an hour. Through depositing the ZnO nanowires on the top of a Pt-interdigitated-electrode/SiO₂/Si-Wafer, a humidity/gas-hybrid sensor is fabricated. The humidity sensitivity (i.e., ratio of the electrical resistance of the sensor at 11–95 % relative humidity level) is approximately 10⁴. The response and recovery time with the humidity changing from 11 to 95 % directly and reversely is 6 and 10 s, respectively. The gas sensitivity (i.e., ratio of electrical resistance of the sensor under the air to vaporized ethanol) is increased from 2 to 56 when the concentration of the ethanol is increased from 40 to 600 ppm. Both the response and recovery times are less than 15 s for the gas sensor. These results show the sensor utilizing the nanowires exhibits excellent humidity and gas sensing.     

Synthesis,characterization, and effect of concentration variation on metal oxide nanostructures

Zinc oxide (ZnO) has been successfully synthesized by an anodization method, and it has been fabricated through anodization method with different concentration of zinc nitrate. The element composition, surface inspection, structural, and morphological features of the products are depend on the concentration of zinc nitrate. At lower concentration (0.01M), SEM image shows ZnO nanowires with average width of about 30 and 50 nm. With increase in the concentration of zinc nitrate from 0.01 to 0.05 M, the nanowires change into the nanosheets with average width of about 0.5 and 1.5 μm. For samples (0.1 M) exhibits nanodots, morphology was composed of hundreds of nanosheets with thickness is about 90 nm on average. When the concentration increases to 0.2 M, the nanodots trench became bigger with diameter about 1.2–2.0 μm. When the concentration of zinc nitrate is 0.3 M, the average diameter of nanodots is about 2–2.5 μm. The trench of nanosheets becomes thinner and shorter, but the number of nanosheets increases with diameter 20–50 nm. The formation of nanowires, nanodots, and nanosheets nanostructures is also believed to result from actions on concentration of zinc nitrate as an aquas medium. The EDX result shows the atomic percentage (at.%) of the oxygen increased when the concentration of zinc nitrate increased. The pattern of EDX indicates that the ZnO nanostructures are composed of Zn, O, and Al. They represent Al composition in the sample because the anode using the aluminum rod during experiment.     

Synthesis of ordered ZnO nanowire arrays from aqueous solution using AAO template

In this paper we report a simple method that enables the easy fabrication of ordered ZnO nanowire arrays using Anodic Aluminium Oxide (AAO) template. We have used a vacuum injection technique to fill solution into the pores of an AAO template. The AAO template has been fabricated by a two-step anodization process using 0.3 M oxalic acid (H₂C₂O₄) solution under a constant voltage of 40 V. The AAO template formed through this process has been detached from Al substrate via an anodic voltage pulse using perchloric acid (HClO₄) solution (70%). The nanowires of ZnO have been synthesized by injecting the saturated Zn(NO₃)₂ solution into the pores of the detached AAO template using a vacuum pump. The ZnO nanowires synthesized by this technique have been found dense & continuous with uniform diameter throughout the length of the wire. The structural characteristics of AAO template and ZnO nanowires have been studied by Field Emission Scanning Electron Microscope (FESEM), Atomic force microscope (AFM) and Transmission Electron Microscope (TEM).     

Influence of Sb on a controlled-growth of aligned ZnO nanowires in nanoparticle-assisted pulsed-laser deposition

Single-crystalline ZnO nanowires on a sapphire substrate have been synthesized by a nanoparticle-assisted pulsed-laser deposition (NAPLD) using a pure and Sb₂O₃ doped ZnO target. Low density and vertically well-aligned ZnO nanowires were grown on hexagonal cone-shape ZnO cores by introduction of a ZnO buffer layer. More than 90% of the ZnO cores of the Sb-induced ZnO nanowires are formed in the same size of 400 nm. The ZnO nanowires consist of single-crystalline wurtzite ZnO crystal and grow along [0001] direction. The room-temperature photoluminescence spectrum exhibited a strong ultraviolet emission at around 380 nm and a relatively low broad band emission in the visible region, indicating a low concentration of structural defect in the nanowires. Sb can be used as one of the effective additives to control the morphology and alignment of ZnO nanowires synthesized by NAPLD.     

Novel epoxy-silicone thermolytic transparent packaging adhesives chemical modified by ZnO nanowires for HB LEDs

A novel high transparent thermolytic epoxy-silicone for high-brightness light-emitting diode (HB-LED) is introduced, which was synthesized by polymerization using silicone matrix via diglycidyl ether bisphenol-A epoxy resin (DGEBA) as reinforcing agent, and filling ZnO nanowires to modify thermal conductivity and control refractive index of the hybrid material. The interactions of ZnO nanowires with polymers are mediated by the ligands attached to the nanoparticles. Thus, the ligands markedly influence the properties of ZnO nanowires/epoxy-silicone composites. The refractive indices of the prepared hybrid adhesives can be tuned by the ZnO nanowires from 1.4711 to 1.5605. Light transmittance can be increased by 20% from 80 to 95%. The thermal conductivity of the transparent packaging adhesives is 0.89–0.90 W/mK.     

Controllable synthesis and characterization of tube brush-like ZnO nanowires produced via a simple chemical vapor deposition method

Tube brush-like ZnO nanostructures were synthesized by a simple chemical vapor deposition method with Zn and ZnO as precursors. These special ZnO nanostructures were characterized by Scanning Electron Microscope, Energy Dispersive X-ray Spectroscopy, High Resolution Transmission Electron Microscope and Cathodoluminescence (CL) techniques. Empty backbones or comb ribbons backbones were found inside the tube brush-like ZnO structures and fuzzy ZnO nanowires outside. Outside ZnO nanowires grow along the c axis and show green CL emission. The growth mechanism of the hierarchical ZnO nanostructures was investigated by a series of experiments at different growth temperatures and different duration times, and a secondary growth mechanism has been proposed and discussed.     

Interfacial engineering of CuO nanorod/ZnO nanowire hybrid nanostructure photoanode in dye-sensitized solar cell

Developing efficient and cost-effective photoanode plays a vital role determining the photocurrent and photovoltage in dye-sensitized solar cells (DSSCs). Here, we demonstrate DSSCs that achieve relatively high power conversion efficiencies (PCEs) by using one-dimensional (1D) zinc oxide (ZnO) nanowires and copper (II) oxide (CuO) nanorods hybrid nanostructures. CuO nanorod-based thin films were prepared by hydrothermal method and used as a blocking layer on top of the ZnO nanowires’ layer. The use of 1D ZnO nanowire/CuO nanorod hybrid nanostructures led to an exceptionally high photovoltaic performance of DSSCs with a remarkably high open-circuit voltage (0.764 V), short current density (14.76 mA/cm² under AM1.5G conditions), and relatively high solar to power conversion efficiency (6.18%) . The enhancement of the solar to power conversion efficiency can be explained in terms of the lag effect of the interfacial recombination dynamics of CuO nanorod-blocking layer on ZnO nanowires. This work shows more economically feasible method to bring down the cost of the nano-hybrid cells and promises for the growth of other important materials to further enhance the solar to power conversion efficiency.     

Synthesis and field emission properties of ZnO nanoneedle arrays grown at low temperatures via a thermal evaporation method

We have developed a straightforward and simple strategy for large-scale growth of well-aligned ZnO nanoneedles via a thermal evaporation method. XRD and SAED patterns of nanoneedles can be indexed to hexagonal ZnO with wurtzite structure. Room temperature photoluminescence analysis showed a strong ultra violet emission at 365 nm and a broad deep level visible emission at 472 nm. The growth mechanism of the nanoneedles has been investigated by SEM and the lower pressure of both evaporated zinc and oxygen flux would favor the nucleation of the finer nanowires from those previously formed high coverage spots. The field emission current density of ZnO nanoneedles sharply reached ~0.048 mA/cm² at a field of 3.1 V/m.     

Growth,structure, and cathodoluminescence of Dy-doped ZnO nanowires

Dy-doped ZnO nanowires have been prepared using high-temperature and high-pressure pulsed-laser deposition. The morphology, structure, and composition of the as-prepared nanostructures are characterized by field emission scanning electron microscopy, X-ray diffraction, Raman scattering spectrometry, X-ray photoelectron spectrometry, transmission electron microscopy, and energy dispersive X-ray spectroscopy. The alloying droplets are located at the top of the as-prepared Dy-doped ZnO nanowires, which means that the growth of the Dy-doped ZnO nanowires is a typical vapor-liquid-solid process. The luminescence properties of Dy-doped ZnO nanowires are characterized by cathodoluminescence spectra and photoluminescence spectra at low temperature (8 K). Two peaks at 481 and 583 nm, respectively, are identified to be from the doped Dy³⁺ ions in the CL spectra of Dy-doped ZnO nanowires.     

Flexible electrically pumped random lasing from ZnO nanowires based on metal–insulator–semiconductor structure

Flexible electrically pumped random laser(RL) based on ZnO nanowires is demonstrated for the first time to our knowledge. The ZnO nanowires each with a length of 5 μm and an average diameter of 180 nm are synthesized on flexible substrate(ITO/PET) by a simple hydrothermal method. No obvious visible defect-related-emission band is observed in the photoluminescence(PL) spectrum, indicating that the ZnO nanowires grown on the flexible ITO/PET substrate have few defects. In order to achieve electrically pumped random lasing with a lower threshold, the metal–insulator–semiconductor(MIS) structure of Au/SiO_2/ZnO on ITO/PET substrate is fabricated by low temperature process. With sufficient forward bias, the as-fabricated flexible device exhibits random lasing, and a low threshold current of ～ 11.5 m A and high luminous intensity are obtained from the ZnO-based random laser. It is believed that this work offers a case study for developing the flexible electrically pumped random lasing from ZnO nanowires.     

Hydrothermal synthesis and gas sensing properties of?single-crystalline ultralong ZnO nanowires

Ultralong ZnO nanowires were successfully synthesized by a simple hydrothermal reaction of Zn foil and aqueous Na₂C₂O₄ solution at 140°C. The as-synthesized ZnO nanowires are single crystalline with the wurtzite structure and grow in the [0001] direction. The role of Na₂C₂O₄ in the formation of ultralong ZnO nanowires was investigated, and a possible mechanism was also proposed to account for the formation of the ultralong ZnO nanowires. The gas sensor fabricated on the basis of the ultralong ZnO nanowires showed excellent response characteristics towards NH₃ and N(C₂H₅)₃ vapors with low concentration, and its detection limits for NH₃ and N(C₂H₅)₃ are about 0.2 and 0.15 ppm at the working temperature of 180°C, respectively. This result suggests potential applications of the ultralong ZnO nanowires in monitoring flammable, toxic and corrosive gases.     

Na mole concentration dependence on optical p-type behaviors of Na-doped ZnO nanowires

We report the structural and optical features of Na-doped ZnO nanowires as a function of Na mole concentration to demonstrate the p-type conduction of Na-doped ZnO nanowires. The samples are prepared on RF-sputtered ZnO seed layers by using a simple hydrothermal method with sodium nitrate, zinc nitrate, and hexamethylenetetramine (HMTA) in an aqueous solution at low temperature (<90 °C). At first, the crystal structure of the c-axis orientation was analyzed using X-ray diffraction patterns. These exhibited a slight shift to lower values of the diffraction angle with decreasing Na mole concentration. To further verify the p-type behaviors of Na-doped ZnO nanowires, cryo-photoluminescence was employed at temperatures ranging from 10 to 300 K, corresponding to the clear appearance of excitons bound to a deeper acceptor (A_D⁰X) and its LO phonon replicas.     

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     

Influence of metallic coatings on the photoluminescence properties of ZnO nanowires

We report on low‐temperature photoluminescence studies of ZnO nanowires coated with thin metallic films. For all analyzed metals (Al, In, Au, Ni, Cu), we find an increased relative intensity of the green deep‐level emission. This is accompanied by a significant reduction of the relative intensity of the surface exciton band. The observed effects are most likely related to the formation of metal induced gap states in the surface region of the ZnO nanowires. A model for the band structure in the surface region of the metal‐coated nanowires is proposed that successfully explains the changes in the photoluminescence spectra after the coating process. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Optimization of pulsed laser deposited ZnO thin-film growth parameters for thin-film transistors (TFT) application

In this work we present the optimization of zinc oxide (ZnO) film properties for a thin-film transistor (TFT) application. Thin films, 50±10 nm, of ZnO were deposited by Pulsed Laser Deposition (PLD) under a variety of growth conditions. The oxygen pressure, laser fluence, substrate temperature and annealing conditions were varied as a part of this study. Mobility and carrier concentration were the focus of the optimization. While room-temperature ZnO growths followed by air and oxygen annealing showed improvement in the (002) phase formation with a carrier concentration in the order of 10¹⁷–10¹⁸/cm³ with low mobility in the range of 0.01–0.1 cm²/V?s, a Hall mobility of 8 cm²/V?s and a carrier concentration of 5×10¹⁴/cm³ have been achieved on a relatively low temperature growth (250 °C) of ZnO. The low carrier concentration indicates that the number of defects have been reduced by a magnitude of nearly a 1000 as compared to the room-temperature annealed growths. Also, it was very clearly seen that for the (002) oriented films of ZnO a high mobility film is achieved.     

ZnO three-dimensional hedgehog-like nanostructure: synthesis,growth mechanism and optical enhancement

The 3D hedgehog-like ZnO nanostructures were synthesized on Si substrate through chemical vapor deposition process. The morphology and structure of the products were characterized by X-ray diffraction, Raman spectroscopy, scanning electron microscopy, as well as transmission electron microscopy. The ZnO 3D hedgehog-like architectures were found to consist of a central nucleus and multiple side-growing nanowires with diameter of 100–250 nm and length up to 10 µm. The growth mechanism of the hedgehog-like ZnO nanostructures was studied. It revealed a three-step process during the entire growth. Finally, room temperature photoluminescence spectra of ZnO 3D nanostructures showed that the center excitation would render much stronger PL emission intensity. Furthermore, simulation results indicated that the enhanced emission came from light-trapping-induced excitation light field enhancement.     

Microbead dynamics in optical trap assisted nanopatterning

An optically pumped ZnO nanowire laser with a 10-period SiO₂/SiN _x distributed Bragg reflector (DBR) was demonstrated. Stimulated emissions with equally distributed Fabry–Pérot lasing modes were observed at pumping powers larger than 121 kW/cm². This result, when compared to nanowires of the same length and without a DBR structure, shows that a lower threshold of pumping power, higher quality factor, and larger cavity finesse can be achieved due to the high reflectivity of the DBR in the designed wavelength range. A coexistence of stimulated and spontaneous emissions was also observed above threshold and was attributed to partially confined waveguide modes in nanowires with diameters smaller than 100 nm.