Investigation of Oxygen Vacancy and Interstitial Oxygen Defects in ZnO Films by Photoluminescence and X-Ray Photoelectron Spectroscopy

ZnO films prepared at different temperatures and annealed at 900^o C in oxygen are studied by photoluminescence （PL） and x-ray photoelectron spectroscopy （XPS）. It is observed that in the PL of the as-grown films the green luminescence （GL） and the yellow luminescence （YL） are related, and after annealing the GL is restrained and the YL is enhanced. The 0 ls XPS results also show the coexistence of oxygen vacancy （Vo） and interstitial oxygen （Oi） before annealing and the quenching of the Vo after annealing. By combining the two results it is deduced that the GL and YL are related to the Vo and Oi defects, respectively.     

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.     

Effect of Different Substrate Temperature on Phosphorus-Doped ZnO Thin Films Prepared by PLD on Sapphire Substrates

Phosphorus-doped ZnO （ZnO：P） thin films are deposited on a c-plane sapphire in oxygen at 350℃, 450℃, 550℃ and 650℃, respectively, by pulsed laser deposition （PLD）, then all the ZnO：P samples are annealed at 650℃ in oxygen with a pressure of 1 × 10^5 Pa. X-ray diffraction measurements indicate that the crystalline quality of the ZnO：P thin films is improved with the increasing substrate temperature from 350℃ to 550℃. With a further increase of the deposition temperature, the crystalline quality of the ZnO：P sample is degraded. The measurements of low-temperature photoluminescence spectra demonstrate that the samples deposited at the substrate temperatures of 350℃ and 450℃ show a strong acceptor-bound exciton （A^0X） emission. The electrical properties of ZnO：P films strongly depend on the deposition temperature. The ZnO：P samples deposited at 350℃ and 450℃ exhibit p-type conductivity. The p-type ZnO：P film deposited at 450℃ shows a resistivity of 1.846Ω·cm and a relatively high hole concentration of 5.100 × 10^17 cm^-3 at room temperature.     

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.     

Influence of annealing atmosphere on ZnO thin films grown by MOCVD

ZnO films were deposited on c-plane sapphire substrates by metal-organic chemical vapor deposition (MOCVD). Annealing treatments for as-deposited samples were performed in different atmosphere under various pressures in the same chamber just after growth. The effect of annealing atmosphere on the electrical, structural, and optical properties of the deposited films has been investigated by means of X-ray diffraction (XRD), atomic force microscope (AFM), Hall effect, and optical absorption measurements. The results indicated that the electrical and structural properties of the films were highly influenced by annealing atmosphere, which was more pronounced for the films annealed in oxygen ambient. The most significant improvements for structural and electrical properties were obtained for the film annealed in oxygen under the pressure of 60 Pa. Under the optimum annealing condition, the lowest resistivity of 0.28 Ω cm and the highest mobility of 19.6 cm² v⁻¹ s⁻¹ were obtained. Meanwhile, the absorbance spectra turned steeper and the optical band gap red shifted back to the single-crystal value.     

Properties of ZnO thin films grown on Si substrates by photo-assisted MOCVD

ZnO thin films were grown on (1 0 0) p-Si substrates by Photo-assisted Metal Organic Chemical Vapor Deposition (PA-MOCVD) using diethylzinc (DEZn) and O₂ as source materials and tungsten-halogen lamp as a light source. The effects of tungsten-halogen lamp irradiation on the surface morphology, structural and optical properties of the deposited ZnO films have been investigated by means of atomic force microscope (AFM), X-ray diffraction and photoluminescence (PL) spectra measurements. Compared with the samples without irradiation, the several characteristics of ZnO films with irradiation are improved, including an improvement in the crystallinity of c-axis orientation, an increase in the grain size and an improvement in optical quality of ZnO films. These results indicated that light irradiation played an important role in the growth of ZnO films by PA-MOCVD.     

Synchrotron radiation assistant MOCVD deposition of ZnO films on Si substrate

The growth of ZnO film on Si(1 0 0) substrate has been studied with synchrotron radiation (SR) assisted MOCVD method. The diethylzinc (DEZn) and CO₂ are used as source materials, while Nitrogen is employed as a carrier gas for DEZn. With the assistance of SR the ZnO film can be deposited even at room temperature. XRD, SEM and photoluminescence (PL) studies show that the crystal quality of ZnO films grown with the assistance of SR is higher than that of those without SR assistance. The growth mechanism of ZnO film with the SR assistant MOCVD system is primarily discussed.     

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.     

Comparative studies on structural and optical properties of ZnO films grown on c-plane sapphire and GaAs (001) by MOCVD

ZnO thin films were grown on c-plane sapphire and GaAs (001) substrates by metalorganic chemical vapor deposition. Atomic force microscopy and double-crystal X-ray diffractometry were utilized to investigate the structural properties of the ZnO films. The optical properties of ZnO films were also investigated in terms of time integrated and resolved photoluminescence (TIPL and TRPL). Large hexagonal crystallites and better crystalline quality were observed from the ZnO film on sapphire. Also, both the TIPL and TRPL showed a significant difference as the substrate changed. In particular, a detected sharp contrast in the result of TRPL measurement is due to the different defect structure and the lattice strain and stress of ZnO films on different substrates.     

Room temperature electroluminescence from ZnO/Si heterojunction devices grown by metal-organic chemical vapor deposition

Heterojunction light-emitting diodes with ZnO/Si structure were fabricated on both high-resistivity (p) and low-resistivity (p⁺) Si substrates by metal-organic chemical vapor deposition technology. Fairly good rectifications were observed from the current-voltage curves of both heterojunctions. Ultraviolet (UV) and blue-white electroluminescence (EL) from ZnO layer were observed only from ZnO/p⁺-Si heterojunction under forward bias at room temperature (RT), while strong infrared (IR) EL emissions from Si substrates were detected from both ZnO/p-Si and ZnO/p⁺-Si heterojunctions. The UV and IR EL mechanisms have been explained by energy band structures. The realization of RT EL in UV-visible and IR region on Si substrate has great applicable potential for Si-based optoelectronic integrated circuits.     

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)     

Photoluminescence properties of nitrogen-doped ZnO films deposited on ZnO single crystal substrates by the plasma-assisted reactive evaporation method

Photoluminescence (PL) spectra of nitrogen-doped ZnO films (ZnO:N films) grown epitaxially on n-type ZnO single crystal substrates by using the plasma-assisted reactive evaporation method were measured at 5 K. In PL spectra, free exciton emission at about 3.375 eV was very strong and emissions at 3.334 and 3.31 eV were observed. These two emissions are discussed in this paper. The nitrogen concentration in ZnO:N films measured by secondary ion mass spectroscopy was 10^19-20 cm⁻³. Current-voltage characteristics of the junction consisting of an n-type ZnO single crystal substrate and ZnO:N film showed good rectification. Also, ultraviolet radiation and visible light were emitted from this junction under a forward bias at room temperature. It is therefore thought that ZnO:N films have good crystallinity and that doped nitrogen atoms play a role as acceptors in ZnO:N films to form a good pn junction. From these phenomena and the excitation intensity dependency of PL spectra, emissions at 3.334 and 3.31 eV were assigned to neutral acceptor-bound exciton (A⁰X) emission and a donor-acceptor pair (DAP) emission due to doped nitrogen, respectively.     

Photoluminescence properties of bare and ZnO infilled artificial opal

Photoluminescence of bare and ZnO infilled artificial opals was investigated. A presence of a photonic band gap results in distortion of the photoluminescence spectra of both the bare and ZnO infilled opal nanocomposite. Filling of the opal with ZnO resulted in a shift of the Bragg diffraction peak from 430 to 460 nm. The emission from ZnO infilled opal contains no UV photoluminescence from ZnO nanocrystals, while the ZnO nanocrystals deposited on substrate by the same method exhibit strong excitonic UV emission. Although a high temperature treatment in ambient air results in an increase in the photoluminescence intensity of the ZnO nanocrystals, the quenched behavior of the excitonic emission from ZnO nanocrystals embedded in the opal matrix remains. A domination of the artificial opal matrix intrinsic emission in the photoluminescence spectra from the untreated as well as heat treated ZnO filled opal nanocomposites is observed.     

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]     

A Simple Route of Morphology Control and Structural and Optical Properties of ZnO Grown by Metal-Organic Chemical Vapour Deposition

Employing the metal-organic chemical vapour deposition （MOCVD） technique, we prepare ZnO samples with different morphologies from the film to nanorods through conveniently changing the bubbled diethylzinc flux （BDF） and the carrier gas flux of oxygen （OCGF）. The scanning electron microscope images indicate that small BDF and OCGF induce two-dimensional growth while the large ones avail quasi-one-dimensional growth. X-ray diffraction （XRD） and Raman scattering analyses show that all of the morphology-dependent ZnO samples are of high crystal quality with a c-axis orientation. From the precise shifts of the 20 locations of ZnQ （002） face in the XRD patterns and the E2 （high） locations in the Raman spectra, we deduce that the compressive stress forms in the ZnO samples and is strengthened with the increasing BDF and OCGF. Photoluminescence spectroscopy results show all the samples have a sharp ultraviolet luminescent band without any defects-related emission. Upon the experiments a possible growth mechanism is proposed.     

Photoluminescence and absorption in sol-gel-derived ZnO films

Highly c-axis-oriented ZnO films were obtained on corning glass substrate by sol-gel technique. The characteristics of photoluminescence (PL) of ZnO, as well as the exciton absorption in the absorption (UV) spectra are closely related to the post-annealing treatment. The difference between PL peak position and the absorption edge, designated as Stokes shift, is found to decrease with the increase of annealing temperature. The minimum Stokes shift is about 150 meV. The decrease of Stokes shift is attributed to the decrease in carrier concentration in ZnO film with annealing. X-ray diffraction, surface morphology and refractive index results indicate an improvement in crystalline quality with annealing. Annealed films also exhibit a green emission centered at ∼520 nm with activation energy of 0.89 eV. The green emission is attributed to the electron transition from the bottom of the conduction band to the antisite oxygen O_Zn defect levels.     

Photoluminescence properties of Co-doped ZnO nanocrystals

We performed photoluminescence experiments on colloidal, Co²⁺-doped ZnO nanocrystals in order to study the electronic properties of Co²⁺ in a ZnO host. Room temperature measurements showed, next to the ZnO exciton and trap emission, an additional emission related to the Co²⁺ dopant. The spectral position and width of this emission does not depend on particle size or Co²⁺ concentration. At 8 K, a series of ZnO bulk phonon replicas appear on the Co²⁺-emission band. We conclude that Co²⁺ ions are strongly localized in the ZnO host, making the formation of a Co²⁺d-band unlikely. Magnetic measurements revealed a paramagnetic behaviour.     

Photoluminescence and Raman scattering of Cu-doped ZnO films prepared by magnetron sputtering

The Cu-doped ZnO films were prepared by direct current reactive magnetron sputtering using a zinc target with various Cu-chips attached. The influences of Cu-doping on the microstructure, photoluminescence, and Raman scattering of ZnO films were systematically investigated. The results indicate that ZnO films doped with moderate Cu dopant (2.0-4.4 at.%) can obtain wurtzite structure with strong c-axis orientation. The near band edge (NBE) emission of ZnO film can be enhanced by Cu dopant with a concentration of 2.0 at.% and quench quickly with further increase of doping concentration. Two additional modes at about 230 and 575 cm⁻¹, which could be induced by Cu dopant, can be observed in Raman spectra of the Cu-doped ZnO films.     

Optical and Magnetic Properties of Fe-Doped GaN Diluted Magnetic Semiconductors Prepared by MOCVD Method

Fe-doped GaN thin films are grown on c-sapphires by metal organic chemical vapour deposition method （MOCVD） Crystalline quality and phase purity are characterized by x-ray diffraction and Raman scattering measurements. There are no detectable second phases formed during growth and no significant degradation in crystalline quality as Fe ions are doped. Fe-related optical transitions are observed in photoluminescence spectra. Magnetic measurements reveal that the films show room-temperature ferromagnetic behaviour. The ferromagnetism may originate from carrier-mediated Fe-doped GaN diluted magnetic semiconductors or nanoscale iron clusters and FeN compounds which we have not detected.     

Chemical characterization of gallium droplets grown by LP-MOCVD

This study is concerned with the chemical characterization of metallic gallium droplets, obtained on silicon (1 0 0) substrates with a single growth step, by the LP-MOCVD technique with TMGa like precursor. These structures are characterized by SIMS, XPS and TEM. The analyses results lead to a structure proposition for the droplets. The core is composed of metastable metallic gallium with a non-negligible carbon quantity probably coming from incomplete precursor decomposition. The outer part, composed of gallium oxide maintains the structure stability. Covering of the substrate by a thin gallium layer of gallium compounds is observed.