Enhanced p-Type ZnO Films through Nitrogen and Argentum Codoping Grown by Ultrasonic Spray Pyrolysis

The N-Ag codoped ZnO films are deposited on quartz glass substrates by ultrasonic spray pyrolysis technology. The results indicate that the p-type conductivity in ZnO films is greatly enhanced by the double acceptor codoping of N and Ag compared with that of Ag- and N-monodoped ZnO films, and the NAg codoped low-resistivity p-type ZnO films with the resistivity of 1.05 Ω·cm, relatively high carrier concentration of 5.43×10^17 cm^-3, and Hall mobility of 10.09 cm^2 V^-1s^-1 are obtained under optimized conditions. This achievement confirms that p- type ZnO with acceptable properties for optoelectronic applications could be realized by simultaneous codoping with two potential acceptors.     

Photoluminescence and X-Ray Photoelectron Spectroscopy of p-Type Phosphorus-Doped ZnO Films Prepared by MOCVD

Reproducible p-type phosphorus-doped ZnO （p-ZnO：P） films are prepared on semi-insulating InP substrates by metal-organic chemical vapour deposition technology. The electrical properties of these films show a hole concentration of 9.02 × 10^17 cm ^-3, a mobifity of 1.05 cm^2 /Vs, and a resistivity of 6.6 Ω.cm. Obvious acceptorbound-exciton-related emission and P-induced zinc vacancy （Vzn） emission are observed by low-temperature photoluminescence spectra of the films, and the acceptor binding energy is estimated to be about 125meV. The local chemical bonding environments of the phosphorus atoms in the ZnO are also identified by x-ray photoelectron spectra. Our results show direct experimental evidence that Pzn-2Vzn shallow acceptor complex most likely contributes to the p-type conductivity of ZnO：P films.     

Effect of Different Substrate Temperature on Sb-Doped ZnO Thin Films Prepared by Pulsed Laser Deposition on Sapphire Substrates

Sb-doped ZnO thin films are deposited on c-plane sapphire substrates by pulsed laser deposition. Hall results indicate that the conductivity of the Sb-doped ZnO thin films is strongly dependent on the substrate temperature. The sample deposited at the temperature of 550°C exhibits p-type conductivity. It gives a resistivity of 15.25Ω＆#12539;cm, with a Hall mobility of 1.79cm2V-1s-1 and a carrier concentration of 2.290×1017cm-3 at room temperature. The x-ray diffraction indicates that the Sb-doped ZnO thin films deposited in the range of 450-650°C are high c-axis oriented. Low-temperature photoluminescence spectra indicate that the sample deposited at 550°C shows the strong acceptor-bound exciton （A0X） emission.     

Realization of controllable etching for ZnO film by NH4Cl aqueous solution and its influence on optical and electrical properties

ZnO films were deposited on c-plane Al₂O₃ substrates by pulsed laser deposition. The etching treatments for as-grown ZnO films were performed in NH₄Cl aqueous solution as a function of NH₄Cl concentration and etching time. It was found that NH₄Cl solution is an appropriate candidate for ZnO wet etching because of its controllable and moderate etching rate. The influence of etching treatment on the morphology, optical and electrical properties of the ZnO films has been investigated systematically by means of X-ray diffraction, atomic force microscope, photoluminescence and Hall effect. The results indicated that the surface morphology and optical properties of the films were highly influenced by etching treatment.     

Photosensitivity of nanocrystalline ZnO films grown by PLD

We have studied the properties of ZnO thin films grown by laser ablation of ZnO targets on (0 0 0 1) sapphire (Al₂O₃), under substrate temperatures around 400 °C. The films were characterized by different methods including X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and atomic force microscopy (AFM). XPS analysis revealed that the films are oxygen deficient, and XRD analysis with θ-2θ scans and rocking curves indicate that the ZnO thin films are highly c-axis oriented. All the films are ultraviolet (UV) sensitive. Sensitivity is maximum for the films deposited at lower temperature. The films deposited at higher temperatures show crystallite sizes of typically 500 nm, a high dark current and minimum photoresponse. In all films we observe persistent photoconductivity decay. More densely packed crystallites and a faster decay in photocurrent is observed for films deposited at lower temperature.     

ZnO thin films on Si(1 1 1) grown by pulsed laser deposition from metallic Zn target

ZnO thin films with highly c-axis orientation have been fabricated on p-type Si(1 1 1) substrates at 400 °C by pulsed laser deposition (PLD) from a metallic Zn target with oxygen pressures between 0.1 and 0.7 mbar. Experimental results indicate that the films deposited at 0.3 and 0.5 mbar have better crystalline and optical quality and flatter surfaces than the films prepared at other pressures. The full width at half maximum (FWHM) of (0 0 0 2) diffraction peak decreases remarkably from 0.46 to 0.19° with increasing annealing temperature for the film prepared at 0.3 mbar. In photoluminescence (PL) spectra at room temperature, the annealed film at 700 °C exhibits a smaller ultraviolet (UV) peak FWHM of 108 meV than the as-grown film (119 meV). However, an enhanced deep-level emission is observed. Possible origins to above results are discussed.     

Growth and Characterization of InN Thin Films on Sapphire by MOCVD

Indium nitride thin films are grown on sapphire substrates by metal-organic chemical vapour deposition （MOCVD） By employing three-step layer buffers, the mirror-like layers on two-inch sapphire wafers have been obtained. The structural, optical and electrical characteristics of InN are investigated by x-ray diffraction, scanning electron microscopy, atomic force microscopy, photoluminescence and infrared optical absorption. The photoluminescence and the absorption studies of the materials reveal a marked energy bandgap structure around 0.70eV at room temperature. The room-temperature Hall mobility and carrier concentration of the film are typically 939 cm^2 /Vs, and 3.9 × 1018cm^-3, respectively.     

Donor-acceptor pair luminescence in nitrogen-doped ZnO films grown on lattice-matched ScAlMgO4 (0001) substrates

We have grown nitrogen-doped ZnO (ZnO:N) films by laser molecular-beam epitaxy. The use of lattice-matched ScAlMgO₄ substrates prevented the degradation of crystallinity induced by the nitrogen incorporation to the films. Despite this improvement, we have not obtained ZnO:N films which showed p-type conductivity. We studied the optical properties of these ZnO:N films. Donor-acceptor pair (DAP) luminescence was observed. The results indicate the formation of an acceptor state. The energy position of the DAP luminescence is lower than that reported by Look et al. [Appl. Phys. Lett. 81 (2002) 1830]. The DAP luminescence band shifts to lower energy with increasing nitrogen concentration. A photoluminescence recombination possibly due to the free-electron-to-acceptor (FA) transition was observed at temperatures higher than 40 K. The acceptor ionization energy was estimated from the energy position of the FA luminescence to be 266 meV.     

不同衬底温度下PLD法制备的氧化锌薄膜的特性

利用GCR-170型脉冲激光器Nd:YAG的三次谐波(355nm),以蓝宝石Al2O3(0001)为衬底,在不同温度下采用脉冲激光沉积法制备了ZnO薄膜.通过原子力显微镜、Raman谱、光致发光谱、红外透射谱、霍尔效应和表面粗糙度分析仪对制备的ZnO薄膜进行了测试.分析了在不同衬底温度下薄膜的表面形貌、光学特性,同时进行了薄膜结构和厚度的测试.研究表明:衬底温度对ZnO薄膜的表面形貌、光学特性、结构特性都是重要的工艺参量,尤其在500℃时沉积的ZnO薄膜致密均匀,并表现出较强的紫外发射峰.     

Photoluminescence of ZnO and Mn-Doped ZnO Polycrystalline Films Prepared by Plasma Enhanced Chemical Vapour Deposition

ZnO and Mn-doped ZnO polycrystalline films are prepared by plasma enhanced chemical vapour deposition at low temperature （220℃）, and room-temperature photoluminescence of the films is systematically investigated. Analysis from x-ray diffraction reveals that a11 the prepared films exhibit the wurtzite structure of ZnO, and Mndoping does not induce the second phase in the films. X-ray photoelectron spectroscopy confirms the existence of Mn^2＋ ions in the films rather than metalic Mn or Mn^4＋ ions. The emission efficiency of the ZnO film is found to be dependent strongly on the post-treatment and to degrade with increasing temperature either in air or in nitrogen ambient. However, the enhancement of near band edge （NBE） emission is observed after hydrogenation in ammonia plasma, companied with more defect-related emission. Furthermore, the position of NBE shifts towards to high-energy legion with increasing Mn-doped concentration due to Mn incorporation into ZnO lattice.     

Laser–MBE growth of high-quality ZnO thin films on Al2O3(0001) and SiO2/Si(100) using the third harmonics of a Nd:YAG laser

High-quality ZnO thin films were grown on single-crystalline Al₂O₃(0001) and amorphous SiO₂/Si(100) substrates at 400–640 °C using laser molecular beam epitaxy. For film growth, the third harmonics of a pulsed Nd:YAG laser were illuminated on a ZnO target. The ZnO films were epitaxially grown on Al₂O₃(0001) with the narrow X-ray diffraction full width at half maximum (FWHM) of 0.04° and the films on SiO₂/Si(100) exhibited a preferred c-axis orientation. Furthermore, the films exhibited excellent optical properties in photoluminescence (PL) measurements with very sharp excitonic and weak deep-level emission peaks. At 15 K, PL FWHM values of the films grown on Al₂O₃(0001) and SiO₂/Si(100) were 3 and 18 meV, respectively. Received: 8 May 2001 / Accepted: 18 September 2001 / Published online: 20 December 2001     

Effects of Substrate Temperature and Nitrogen Pressure on Growth of AIN Films by Pulsed Laser Deposition

Highly oriented aluminium nitride （AIN） films are grown on p-Si （100） substrates by pulsed laser deposition, and their characteristics of structure and composition are studied by x-ray diffraction, Fourier transform infrared spectroscopy and scanning electron microscopy. The results show that the deposited films exhibit good crystalline properties with a sharp x-ray diffraction peak at 2θ= 33.15 ° corresponding to AIN h （100） crystalline orientation. The influences of substrate temperature and ambient nitrogen （N2） pressure on the crystallinity of A1N films are remarkable. At room temperature, when the ambient N2 pressure arises from 5 × 10^-6 Pa to 5 Pa, the crystallinity of the film becomes better. When the substrate temperature is 600℃, the film has the best crystallinity at 0.05 Pa. Furthermore, the effects of substrate temperature and ambient N2 pressure on the combination of A1-N bonds and surface morphology of AIN films are also studied.     

Identification of Acceptor States in Li-N Dual-Doped p-Type ZnO Thin Films

Li-N dual-doped p-type ZnO （ZnO：（Li, N）） thin films are prepared by pulsed laser deposition. The optical properties are studied using temperature-dependent photoluminescence. The Lizn-No complex acceptor with an energy 1evel of 138 me V is identified from the free-to-neutral-acceptor （e, A0 ） emission. The Haynes factor is about 0.087 for the Lizn-No complex acceptor, with the acceptor bound-exciton binding energy of 12meV. Another deeper acceptor state located at 248 meV, also identified from the （e, A0） emission, is attributed to zinc vacancy acceptor. The two acceptor states might both contribute to the observed p-type conductivity in ZnO：（Li,N）.     

Particulate assisted growth of ZnO nanorods and microrods by pulsed laser deposition

Zinc oxide (ZnO) thin films were deposited on the gallium nitride (GaN) and sapphire (Al₂O₃) substrates by pulsed laser deposition (PLD) without using any metal catalyst. The experiment was carried out at three different laser wavelengths of Nd:YAG laser (λ = 1064 nm, λ = 532 nm) and KrF excimer laser (λ = 248 nm). The ZnO films grown at λ = 532 nm revealed the presence of ZnO nanorods and microrods. The diameter of the rods varies from 250 nm to 2 μm and the length varies between 9 and 22 μm. The scanning electron microscopy (SEM) images of the rods revealed the absence of frozen balls at the tip of the ZnO rods. The growth of ZnO rods has been explained by vapor-solid (V-S) mechanism. The origin of growth of ZnO rods has been attributed to the ejection of micrometric and sub-micrometric sized particulates from the ZnO target. The ZnO films grown at λ = 1064 nm and λ = 248 nm do not show the rod like morphology. X-ray photoelectron spectroscopy (XPS) has not shown the presence of any impurity except zinc and oxygen.     

ZnO Nanostructures Grown on A1N/Sapphire Substrates by MOCVD

ZnO nanorods and nanotubes are successful synthesized on A1N/sapphire substrates by metal-organic chemical vapour deposition （MOGVD）. The different morphology and structure properties of ZnO nanorods and nanotubes are found to be affected by the A1N under-layer. The photoluminescence spectra show the optical properties of the ZnO nanorods and nanotubes, in which a blueshift of UV emission is observed and is attributed to the surface effect.[第一段]     

ZnO nanowall networks grown on DiMPLA pre‐patterned thin gold films

ZnO nanowall networks grown by a high pressure pulsed laser deposition (PLD) technique on a pre‐patterned thin gold film are presented. The thin gold film on a c ‐plane oriented sapphire substrate was structured with diffraction mask projection laser ablation (DiMPLA). It is shown that only areas processed with the laser patterning technique reveal homogeneous growth of ZnO nanowall networks. Photoluminescence measurements prove the higher material quality of the pre‐patterned regions compared to the untreated ones. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Homoepitaxy of ZnO by pulsed‐laser deposition

ZnO thin films were grown homoepitaxially on O‐face ZnO single crystals by pulsed‐laser deposition. The ZnO substrates grown by the hydrothermal method were heat‐treated in oxygen ambient at 1000 °C for 2 h prior to deposition. After the thermal treatment the substrates show bilayer steps between 200–400 nm wide terraces and a considerably improved crystalline structure. Thin film surfaces exhibit closed loop spirals and show steps of c /2 or c. The FWHM of the (0002) rocking curve of the best sample is 29″. Similar to the substrates used, Al is contained in the thin films (<10¹⁴ cm^–3) as photoluminescence (PL) and thermal admittance spectroscopy suggest. However, deep levels between 200 and 400 meV below the conduction band are the dominant donors at room temperature. Low temperature PL is dominated by (Al⁰,X) (I6, FWHM: 200 µeV) and extremely homogeneous (σ ≈ 1%).

     

Influence of CH3COO on the room temperature photoluminescence of ZnO films prepared by CVD

ZnO films with strong c-axis-preferred orientation have been prepared by a single source chemical vapor deposition technique using zinc acetate as source material at the growth temperature of 230 °C. The strong UV and blue emissions were observed in the photoluminescence spectra of as-grown films. A small quantity of residual zinc acetate was reserved on the surface of as-grown ZnO films and the emission mechanism of blue luminescence was nearly related to the CH₃COO^- of unidentate type. The blue emission disappeared and the green emission appeared after annealing treatment. The green emission is related to the singly ionized oxygen vacancies.     

Analytic Solution of Charge Density of Single Wall Carbon Nanotube under Conditions of Field Electron Emission

We derive the analytic solution of induced electrostatic potential along single wall carbon nanotubes. Under the hypothesis of constant density of states in the charge-neutral level, we are able to obtain the linear density of excess charge in an external field parallel to the tube axis.     

Band-edge photoluminescence in nanocrystalline ZnO:In films prepared by electrostatic spray deposition

ZnO:In films are successfully prepared by using the electrostatic spray deposition technique. X-ray diffraction indicates that the ZnO:In films have a polycrystalline hexagonal wurtzite structure with lattice parameters a=3.267 Å and c=5.209 Å. Photoluminescence properties of the films are investigated in the temperature range of 11.6-300 K, showing strong luminescence in the whole range of temperature. The temperature dependence of the photoluminescence are carried out with full profile fitting of spectra, which clearly shows that the ultraviolet (UV) emission in In-doped ZnO films at low temperature are attributed to emission of a neutral donor-bound exciton (D^°X) and recombination of donor-acceptor pairs (DAP), while the UV emission at room temperature originates from radiative transition of an electron bound on a donor to the valence band.