The fabrication and characterization of ZnO UV detector

ZnO films were deposited on GaAs substrates by radio frequency (rf) magnetron sputtering followed by an ambient-controlled heat treatment process for arsenic doping. In Hall measurements, the As-doped ZnO films showed the characteristics of p-type semiconductor. The ZnO thin film p–n homojuctions were then fabricated to investigate the electrical properties of the films. The p–n homojunctions exhibited the distinct rectifying current–voltage (I–V) characteristics. The turn-on voltage was measured to be 3.0 V under the forward bias. When ultraviolet (UV) light (λ = 325 nm) was irradiated on the p–n homojunction, photocurrent of 2 mA was detected. Based on these results, it is proposed that the p–n homojunction herein is a potential candidate for UV photodetector and optical devices.     

Fine luminescent patterning on ZnO nanowires and films using focused electron-beam irradiation

ZnO thin films and nanowires (NWs) were precisely treated by focused electron-beam (E-beam) irradiation with a line width between 200 nm and 3 μm. For both ZnO films and NWs, an increased green emission was clearly observed for the E-beam-treated parts. Using a high-resolution laser confocal microscope, the photoluminescence intensities for E-beam-treated ZnO structures increased with increasing dose 1.0 × 10¹⁷–1.0 × 10¹⁸ electrons/cm². The resistivity of a single ZnO NW increased from 56 to 1800 Ω cm after the E-beam treatment. From the results for the annealed ZnO thin films, we analyzed that the variations in PL and resistivity were due to the formation of vacancies upon focused E-beam irradiation.     

Violet luminescence from ZnO nanorods grown by room temperature pulsed laser deposition

ZnO thin films were deposited at room temperature by pulsed laser deposition (PLD) varying the oxygen pressure. Morphological analysis using scanning electron microscope (SEM) and atomic force microscopy (AFM) demonstrated the formation of ZnO nanorods at a particular oxygen pressure. Room temperature violet luminescence was observed from these ZnO nanorods and temperature dependence of luminescence was studied. Influence of oxygen pressure on the growth of ZnO thin films by PLD was studied using the X-ray photoelectron spectroscopy of both post ablated targets and deposited films. The ZnO films were crystalline and the formation of crystalline phase is found to follow a pressure–temperature (P–T) scaling with increase of temperature.     

Electroluminescence from ZnO nanowires with a p-ZnO film/n-ZnO nanowire homojunction

ZnO homojunction light-emitting diodes based on ZnO nanowires were fabricated on Si(100) substrates. An N–In codoped p-type ZnO film grown by ultrasonic spray pyrolysis and an unintentionally doped n-type ZnO nanowire quasi-array grown by an easy low-temperature hydrothermal method were employed to form the homojunction diode. Under a forward bias larger than 8 V, electroluminescence, which was composed of an ultraviolet peak centered at 387 nm and a green band around 540 nm, was observed. The electroluminescence emission was contributed by the ZnO nanowires. The results reported here suggest that ZnO-based ultraviolet light-emitting devices could be realized at low cost. PACS 42.72.Bj; 73.40.Lq; 85.60.Jb     

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)     

Structural and optical properties of ZnO thin films on (111) CaF2 substrates grown by magnetron sputtering

ZnO thin films were grown on (111) CaF₂ substrates by magnetron sputtering at room temperature. Structural and optical properties of the ZnO thin films were studied. XRD analysis showed that the ZnO thin films had the (002) preferential orientation. The transmittance of ZnO thin films was over 80% in the visible range. The optical band gap of the ZnO thin films was 3.26 eV. The optical constants (n,k)$(n,k)$ of the ZnO thin films in the wavelength range 300–1000 nm were obtained by infrared spectroscopic ellipsometry measurement. PL spectra of ZnO thin films showed strong UV near-band-edge emission peak at 376.5 nm and weak visible red emission at 643.49 nm using He–Cd laser as the light source, using a synchrotron radiation light source PL spectra showed three emission peak at 320 nm, 410 nm and 542 nm respectively.     

UV-blocking ZnO nanostructure anti-reflective coatings

In this paper, we apply finite difference time domain simulation to determine the absorptance and reflectance of ZnO nanowire and nanohole array structures for an efficient UV-blocking anti-reflective coating. Comparing to ZnO thin films, both nanowires and nanoholes have much improved performance. ZnO nanowires and nanoholes have similar absorptions in the UV range. However, ZnO nanowires have lower absorptance than nanoholes in the visible range. Influences of different parameters including lattice constant a, ZnO filling ratio f and nanowire heights h are analyzed. The optical properties of the nanostructures are less dependent on the incident angle of light, which enables them to be used as wide angle anti-reflective coatings with UV blocking.     

Comparison of ZnO thin films grown on a polycrystalline 3C-SiC buffer layer by RF magnetron sputtering and a sol-gel method

Zinc oxide (ZnO) thin films were deposited on a polycrystalline (poly) 3C-SiC buffer layer using RF magnetron sputtering and a sol-gel method. The post-deposition annealing was performed on ZnO thin films prepared using both methods. The formation of ZnO piezoelectric thin films with less residual stress was due to a close lattice mismatch of the ZnO and SiC layers as obtained by the sputtering method. Nanocrystalline, porous ZnO film prepared using the sol-gel method showed strong ultraviolet UV emission at a wavelength of 380 nm. The 3C-SiC buffer layer improved the optical and piezoelectric properties of the ZnO film produced by the two deposition methods. Moreover, the different structures of the ZnO films on the 3C-SiC intermediate layer caused by the different deposition techniques were also considered and discussed.     

Effect of sputtered films on morphology of vertical aligned ZnO nanowires

Vertical aligned ZnO nanowires were grown by MOCVD technique on silicon substrate using ZnO and AlN thin films as seed layers. The shape of nanostructures was greatly influenced by the under laying surface. Vertical nanopencils were observed on ZnO/Si, whereas the nanowires on both sapphire and AlN/Si substrate have the similar aspect ratio. XRD patterns suggest that the nanostructures have good crystallinity. High-resolution transmission electron microscopy (HRTEM) confirmed the single crystalline growth of the ZnO nanowires along [0 0 1] direction. Room-temperature photoluminescence (PL) spectra of ZnO nanowires on AlN/Si clearly show a band-edge luminescence accompanied with a visible emission. More interestingly, no visible emission for the nanopencils on ZnO/Si substrates, were observed.     

Growth, morphology and optical properties of tris(8-hydroxyquinoline)aluminum/zinc oxide hybrid nanowires

Hybrid tris(8-hydroxyquinoline)aluminum/zinc oxide (Alq₃/ZnO) nanowires were successfully grown from a one-step solution method at very low temperature. The transformation of amorphous Alq₃ into α-phase crystalline nanowires was achieved by incorporating a certain weight fraction of crystalline ZnO nanomaterials. A growth mechanism was proposed to validate the formation of crystalline Alq₃-ZnO hybrid nanowires with the help of nucleation initiated by the ZnO nanomaterials, followed by Alq₃ molecular aggregation. Effects of temperature on the evolution of morphologies of hybrid nanowires were examined by the field-emission scanning electron microscopy (FESEM). The photoluminescence (PL) spectra of hybrid nanowires showed a significant threefold enhancement in PL intensity, along with a slight blue-shift emission, when compared to the pure Alq₃ molecules, which were attributed due to the incorporation of crystalline ZnO nanomaterials and also the shielding effect of ZnO nanomaterials to avoid the excimer formation between the Alq₃ molecules in the excited state.     

I–V characteristics of ZnO/Cu2O thin film n–i–p heterojunction

ZnO/Cu₂O thin film n–i–p heterojunctions were fabricated by magnetron sputtering. The microstructure, optical, and electrical properties of n-type (n‐) ZnO, insulating (i‐) ZnO, and p-type (p‐) Cu₂O films deposited on glass substrates were characterized by X-Ray diffraction (XRD), spectrophotometer, and the van der Pauw method, respectively. XRD results show that the mean grain size of i-ZnO film is much larger than that of n-ZnO film. The optical band gap energies of n-ZnO, i-ZnO, and p-Cu₂O film are 3.27, 3.47, and 2.00 eV, respectively. The carrier concentration of n-ZnO film is two orders of magnitude larger than that of p-Cu₂O film. The current–voltage (I–V) characteristics of ZnO/Cu₂O thin film n–i–p heterojunctions with different i-ZnO film thicknesses were investigated. Results show that ZnO/Cu₂O n–i–p heterojunctions have well-defined rectifying behavior. All ideality factors of these n–i–p heterojunctions are larger than 2.0. The forward bias threshold voltage and ideality factor increase when i-ZnO layer thickness increases from 100 to 200 nm. An energy band diagram was proposed to analyze the I–V characteristics of these n–i–p heterojunctions.     

Synthesis,structural and ellipsometric evaluation of oxygen-deficient and nearly stoichiometric zinc oxide and indium oxide nanowires/nanoparticles

Oxygen-deficient (OD) and nearly stoichiometric (NST) ZnO and In₂O₃ nanowires/nanoparticles were synthesized by chemical vapor deposition on Au-coated silicon substrates. The OD ZnO and OD In₂O₃ nanowires were synthesized at 750 and 950°C, respectively, using Ar flow at ambient pressure. A mixture of flowing Ar and O₂ was used for synthesizing NST ZnO nanowires and NST In₂O₃ nanoparticles. Growth of OD ZnO nanowires and NST In₂O₃ nanoparticles was found to be via a vapor–solid (VS) mechanism and the growth of NST ZnO nanowires was via a vapor–liquid–solid mechanism (VLS). However, it was uncertain whether the growth of OD In₂O₃ nanowires was via a VS or VLS mechanism. The optical constants, thickness and surface roughness of the prepared nanostructured films were determined by spectroscopic ellipsometry measurements. A three-layered model was used to fit the calculated data to the experimental ellipsometric spectra. The refractive index of OD ZnO, NST ZnO nanowires and NST In₂O₃ nanoparticles films displayed normal dispersion behavior. The calculated optical band gap values for OD ZnO, NST ZnO, OD In₂O₃ nanowires and NST In₂O₃ nanoparticles films were 3.03, 3.55, 2.81 and 3.52?eV, respectively.     

Nanoporous structures on ZnO thin films

Porous structures were formed on ZnO thin films which were grown by an electrochemical deposition (ECD) method. The growth processes were carried out in a solution of dimethylsulfoxide (DMSO) zinc perchlorate, Zn(ClO₄)₂, at 120 ^°C on indium tin oxide (ITO) substrates. Optical and structural characterizations of electrochemically grown ZnO thin films have shown that the films possess high (0002) c$c$-axis orientation, high nucleation, high intensity and low FWHM of UV emission at the band edge region and a sharp UV absorption edge. Nanoporous structures were formed via self-assembled monolayers (SAMs) of hexanethiol (C₆SH) and dodecanethiol (C₁₂SH). Scanning electron microscope (SEM) measurements showed that while a nanoporous structure (pore radius 20 nm) is formed on the ZnO thin films by hexanathiol solution, a macroporous structure (pore radius 360 nm) is formed by dodecanethiol solution. No significant variation is observed in X-ray diffraction (XRD) measurements on the ZnO thin films after pore formation. However, photoluminescence (PL) measurements showed that green emission is observed as the dominant emission for the macroporous structures, while no variation is observed for the thin film nanoporous ZnO sample.     

弯曲银/银同质结纳米线的合成及其SERS表征

用液相法合成弯曲的银/银(Ag/Ag)同质结纳米线, 即由Ag/Ag同质结和Ag纳米棒组成。同质结相邻的两个Ag纳米棒以一定的角度形成弯曲的Ag纳米线, 其角度可能是锐角, 也可能是钝角, 而且其长度可达几个微米。研究发现, 反应温度对弯曲Ag/Ag同质结纳米线的形成具有非常重要的作用, 改变反应温度, 得到的是其它形状的纳米粒子; 同时, 表面增强拉曼光谱(SERS)表征发现, 与Ag纳米球和纳米线相比, 弯曲Ag/Ag同质结纳米线具有更好的SERS活性。     

ZnO–SnO2 branch–stem nanowires based on a two-step process: Synthesis and sensing capability

ZnO–SnO₂ branch–stem nanostructures were realized on a basis of a two-step process. In step 1, SnO₂-stem nanowires were synthesized. In step 2, ZnO-branch nanowires were successfully grown on the SnO₂-stem nanowires through a simple evaporation technique. We have pre-deposited thin Au layers on the surface of SnO₂ nanowire stems and subsequently evaporated Zn powders on the nanowires. The ZnO branches, which sprouted from the SnO₂ stems, had diameters in a range of 30–35 nm. As-synthesized branches were of single crystalline hexagonal ZnO structures. Since the branch tips were comprised of Au-containing nanoparticles, the Au-catalyzed vapor–liquid–solid growth mechanism was more likely to control the growth process of the ZnO branches. To test a potential use of ZnO–SnO₂ branch–stem nanostructures in chemical gas sensors, their sensing performances with respect to NO₂ gas were investigated, showing the promising potential in chemical gas sensors.     

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.     

Fabrication and characterization of magnetron sputtered arsenic doped p-type ZnO epitaxial thin films

Arsenic doped p-type ZnO thin films were grown on sapphire substrate by magnetron sputtering. As grown films reveal p-type conduction confirmed by Hall-effect and photoluminescence measurements. The p-type film with a hole concentration of 2.16× 10¹⁷ cm⁻³, mobility of 1.30 cm²/V.s and resistivity of 22.29 Ω-m were obtained at substrate temperature of 700 °C. ZnO homojunction synthesized by in-situ deposition of As doped p-ZnO layer on Al doped n-ZnO layer showed p-n diode like characteristics. X-ray pole figure and Transmission Electron Microscope studies confirm epitaxial nature of the films. Photoluminescence results exhibit the peaks associated with donor acceptor pair emission.     

Characteristics of p-type ZnO:As thin films prepared by the ampoule-tube method and ZnO p–n homojunction

A p-type ZnO thin film was prepared using arsenic diffusion via the ampoule-tube method. This was followed by fabrication of a ZnO p–n homojunction using n-type ZnO and characterization of the device properties. The ZnO thin film exhibited p-type characteristics, with a resistivity of 2.19×10⁻³ Ω cm, a carrier concentration of 1.73×10²⁰/cm³, and a mobility of 26.7 cm²/V s. Secondary ion mass spectrometer analysis confirmed that in- and out-diffusion occurred simultaneously from the external As source and the GaAs substrate. The device exhibited the rectification characteristics of a typical p–n junction; the forward voltage at 20 mA was approximately 5.5 V. The reverse-bias leakage current was very low—0.1 mA for −10 V; the breakdown voltage was −11 V. The ampoule-tube method for fabricating p-type ZnO thin films may be useful in producing ultraviolet ZnO LEDs and other ZnO-based devices.     

Effects of hydrogen flow on properties of hydrogen doped ZnO thin films prepared by RF magnetron sputtering

The hydrogen doped ZnO (ZnO:H) thin films were deposited on quartz glass substrates by radio frequency magnetron sputtering. The doping characteristics of ZnO:H thin films with varied hydrogen flow ratio were investigated. At low hydrogen flow ratio (H₂/(H₂+Ar)≤0.02), the ZnO:H thin films exhibited dominant (002) peaks from X-ray diffraction and the lattice constants became smaller. The particles were mainly a columnar structure. The particles’ size became smaller, and the island-like structure appeared on the thin films surface. In addition, the low resistivity properties of ZnO:H thin films was ascribed to the increase of the carriers concentration and carriers mobility; When the hydrogen flow ratio was more than 0.02 (M≥0.02), two absorption bands at 1400–1800 cm^?1 and 3200–3900 cm^?1 were observed from the FT-IR spectra, which indicated that the ZnO:H thin films had typical Zn–H bonding, O–H bonding (hydroxyl), and Zn–H–O bonding (like-hydroxyl). The scanning electron microscope (SEM) results show that a large number of hydroxyl agglomeration formed an island-like structure on the thin films surface. The absorption peak at about 575 cm^?1 in the Raman spectra indicated that oxygen vacancies (V_O) defects were produced in the process of high hydrogen doping. In this condition, the low resistivity properties of ZnO:H thin films were mainly due to the increasing electron concentration resulted from V_O. Meanwhile, the Raman absorption peaks at approximately 98 cm^?1 and 436 cm^?1 became weaker, and the (002) XRD diffraction peak quenched and the lattice constants increased, which shows that the ZnO:H thin films no longer presented a typical ZnO hexagonal wurtzite structure. With the increasing of hydrogen flow ratio, the optical transmittance of ZnO:H thin films in the ultraviolet band show a clear Burstein–Moss shift effect, which further explained that electron concentration was increased due to the increasing V_O with high hydrogen doping concentration. Moreover, the optical reflectance of the thin films decreased, indicating the higher roughness of the films surface. It was noteworthy that etching effect of H plasma was obvious in the process of heavy hydrogen doping.     

Fabrication of p-ZnO:ZrN thin films by RF magnetron sputtering

An attempt has been made to fabricate p-ZnO thin films from the ZrN mixed ZnO targets by RF magnetron sputtering. The targets of different ZrN concentrations (0, 1, 2, and 4?mol%) have been prepared by solid-state reaction route. The ZrN-codoped ZnO films grown on semi-insulating Si (100) substrates have been characterized by X-ray diffraction (XRD), photoluminescence (PL), Hall effect measurement, time-of-flight secondary ion mass spectrometer (ToF-SIMS), and atomic force microscopy (AFM). XRD studies reveal that all films are oriented along (002) plane. The Hall measurements showed p-conductivity for 1 and 2?mol% ZrN-codoped ZnO films. Further, it has been found that 1?mol% ZrN-codoped film has low resistivity (7.5?×?10^?2?Ω?cm) and considerable hole concentration (8.2?×?10¹⁸?cm^?3) by optimum incorporation of nitrogen due to best codoping. The red shift in near-band-edge emission observed from PL well acknowledged the p-conduction in 1 and 2?mol% ZrN-codoped ZnO film. The incorporation of N and Zr atoms in the ZnO matrix has been confirmed by ToF-SIMS analysis. The increase in peak to valley roughness (R _pv) with increase of doping concentration has been observed from AFM analysis. ZnO homojunction has also been fabricated with the best codoped p-ZnO film and it showed typical rectification behavior of a diode. The junction parameters have also been determined for the fabricated homojunction.