Influence of post-deposition annealing on the structural,optical and electrical properties of Li and Mg co-doped ZnO thin films deposited by sol–gel technique

Lithium (Li) and magnesium (Mg) co-doped zinc oxide (ZnO) thin films were deposited by sol–gel method using spin coating technique. The films were deposited on glass substrates and annealed at different temperatures. The effects of annealing temperature on the structural, optical and electrical properties of the deposited films were investigated using X-ray diffraction (XRD), Ultraviolet–Visible absorption spectra (UV–VIS), photoluminescence spectra (PL), X-ray photo electron spectroscopy (XPS) and Hall measurements. XRD patterns indicated that the deposited films had a polycrystalline hexagonal wurtzite structure with preferred (0 0 0 2) orientation. All films were found to exhibit a good transparency in the visible range. Analysis of the absorption edge revealed that the optical band gap energies of the films annealed at different temperatures varies between 3.49 eV and 3.69 eV. Room temperature PL spectra of the deposited films annealed at various temperatures consist of a near band edge emission and visible emission due to the electronic defects, which are related to deep level emissions, such as oxide antisite (O_Zn), interstitial zinc (Zn_i), interstitial oxygen (O_i) and zinc vacancy (V_Zn) which are generated during annealing process. The influence of annealing temperature on the chemical state of the dopants in the film was analysed by XPS spectra. Ion beam analysis (Rutherford back scattering) experiments were performed to evaluate the content of Li and Mg in the films. Hall measurements confirmed the p-type nature of the deposited films.     

非掺杂ZnO薄膜中紫外与绿色发光中心

用直流反应溅射方法在硅衬底上淀积了ZnO薄膜,测量它们的光致发光(PL)光谱,观察到两个发光峰,峰值能量分别为3.18(紫外峰,UV)和2.38eV(绿峰).样品用不同温度分别在氧气、氮气和空气中热处理后,测量了PL光谱中绿峰和紫外峰强度随热处理温度和气氛的变化,同时比较了用FP-LMT方法计算的ZnO中几种本征缺陷的能级位置.根据实验和能级计算的结果,推测出ZnO薄膜中的紫外峰与ZnO带边激子跃迁有关,而绿色发光主要来源于导带底到氧错位缺陷(O_Zn)能级的跃迁,而不是通常认为的氧空 关键词： ZnO薄膜 热处理 光致发光光谱 缺陷能级     

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.     

Single violet luminescence emitted from ZnO films obtained by oxidation of Zn film on quartz glass

The photoluminescence (PL) emission properties of ZnO films obtained on quartz glass substrate by the oxidation of Zn films were studied. The strong single violet emission centering about 413-424 nm was observed in the room temperature PL spectra of the ZnO films. The intensity of violet emission increased and the peak position shift from 424 to 413 nm with increasing oxygen pressures. The violet emission was attributed to the electron transition from the valence band to interstitial zinc (Zn_i) level under low oxygen pressure conditions (50-500 Pa). Under high oxygen pressure conditions (5000-23,000 Pa), both interstitial zinc (Zn_i) and zinc Vacancy (V_Zn) were thought to be responsible for the violet emission.     

Room-Temperature Ferromagnetism in Zn1-xMnxO Thin Films Deposited by Pulsed Laser Deposition

Zn1-xMnxO （x = O.Olq3.1） thin films with a Curie temperature above 300K are deposited on Al2O3 （0001） substrates by pulsed laser deposition. X-ray diffraction （XRD）, ultraviolet （UV）-visible transmission and Raman spectroscopy are employed to characterize the microstructural properties of these films. Room temperature ferromagnetism is observed by superconducting quantum interference device （SQUID）. The results indicate that Mn doping introduces the incorporation of Mn^2＋ ions into the ZnO host matrix and the insertion of Mn^2＋ ions increases the lattice defects, which is correlated with the ferromagnetism of the obtained films. The doping concentration is also proven to be a crucial factor for obtaining highly ferromagnetic Zn1-xMnxO films.     

Effect of Annealing Temperature on Structural and Optical Properties of N-Doped ZnO Films

Nitrogen-doped ZnO （ZnO：N） films are prepared by thermal oxidation of sputtered Zn3N2 layers on A1203 substrates. The correlation between the structural and optical properties of ZnO：N films and annealing temperatures is investigated. X-ray diffraction result demonstrates that the as-sputtered Zn3N2 films are transformed into ZnO：N films after annealing above 600℃. X-ray photoelectron spectroscopy reveals that nitrogen has two chemical states in the ZnO：N films： the No acceptor and the double donor （N2）o. Due to the No acceptor, the hole concentration in the film annealed at 700℃ is predicted to be highest, which is also confirmed by Hall effect measurement. In addition, the temperature dependent photoluminescence spectra allow to calculate the nitrogen acceptor binding energy.     

Epitaxial Properties of Co-Doped ZnO Thin Films Grown by Plasma Assisted Molecular Beam Epitaxy

High quality Co-doped ZnO thin films are grown on single crystalline Al2O3（0001） and ZnO（0001） substrates by oxygen plasma assisted molecular beam epitaxy at a relatively lower substrate temperature of 450℃. The epitaxial conditions are examined with in-situ reflection high energy electron diffraction （RHEED） and ex-situ high resolution x-ray diffraction （HRXRD）. The epitaxial thin films are single crystal at film thickness smaller than 500nm and nominal concentration of Co dopant up to 20%. It is indicated that the Co cation is incorporated into the ZnO matrix as Co^2＋ substituting Zn^2＋ ions. Atomic force microscopy shows smooth surfaces with rms roughness of 1.9 nm. Room-temperature magnetization measurements reveal that the Co-doped ZnO thin films are ferromagnetic with Curie temperatures Tc above room temperature.     

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）.     

Structural and Magnetic Properties of Fe-Doped Anatase TiO2 Films Annealed in Vacuum

Structural and magnetic properties of Fe-doped anatase TiO2 films fabricated by sol-gel spin coating are investigated. X-ray diffraction measurements reveal that Fe^3＋ ions are incorporated into the TiO2 lattice. No ferromagnetism-related secondary phases and magnetic nanopaxticles are observed in the films. The presence of electron paramagnetic resonance signals at 9- 2.0 supports oxygen vacancies and/or defects generated in the films after annealing in vacuum. Magnetic measurements indicate that Fe-doped anatase TiO2 films are ferromagnetic at room temperature. These observations suggest that oxygen vacancies and/or defects axe energetically favorable for the long range Fe^3＋-Fe^3＋ ferromagnetic coupling in Fe-doped anatase TiO2 films.     

Evolution of Structural Defects in SiOx Films Fabricated by Electron Cyclotron Resonance Plasma Chemical Vapour Deposition upon Annealing Treatment

We study the structural defects in the SiO, film prepared by electron cyclotron resonance plasma chemical vapour deposition and annealing recovery evolution. The photoluminescence property is observed in the as-deposited and annealed samples. [-SiO3]^2- defects are the luminescence centres of the ultraviolet photoluminescence （PL） from the Fourier transform infrared spectroscopy and PL measurements. [-SiO3]^2- is observed by positron annihilation spectroscopy, and this defect can make the S parameters increase. After 1000℃ annealing, [-SiO3]^2- defects still exist in the films.     

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.     

p型K:ZnO导电机理的第一性原理研究

基于密度泛函理论,利用局域密度近似的第一性原理平面波赝势方法,对掺K以及含有氢填隙(H_i)、氧空位(V_O)、锌填隙(Zn_i)和锌空位(V_Zn)的K:ZnO电子结构分别进行了研究.结果表明,1) 单独掺K可引入浅受主,但系统总能增高;2) K与H共掺可降低系统总能,提升稳定性;3) V_O在K+H:ZnO中的形成比Zn_i困难得多,二者都是 关键词： 氧化锌 p型 第一性原理 电子结构     

Dominant ultraviolet-blue photoluminescence of ZnO embedded into synthetic opal

The temperature-dependent photoluminescence (PL) characteristics of zinc oxide (ZnO) embedded into the voids of synthetic opal were studied. ZnO was infiltrated into opal from aqueous solution with zinc nitrate precursor followed by thermal annealing. The PL spectra of the ZnO powder exhibit very high and broad emission peaks in the green region due to crystal defects, such as oxygen vacancies and zinc ion interstitials. In contrast to the PL spectra of ZnO powder, nanocrystals of ZnO embedded into the voids of FCC packed opal matrix exhibit dominant ultraviolet (UV)-blue and rapidly decreasing green PL emissions with decreasing temperature. The temperature-dependent PL characteristics show that the green band suppression in the ZnO nanocrystals is due to the influence of photonic crystal. The infiltration of nanoparticles into synthetic opal may be used for the fabrication of polycrystalline ZnO with dominant UV-blue PL. These results indicate that the luminescent materials embedded into photonic crystal may be promising for the fabrication of the RGB pixels in full-color displays.     

Photoluminescence properties of thin nitrogen- and phosphorus-doped ZnO films fabricated using pulsed laser deposition

The production of n- and p-type high-quality film structures is a foreground task in tackling the problem of growing the light-emitting p-n junctions based on zinc oxide. The ZnO:N and ZnO:P thin-film samples are produced from ceramic targets using the pulsed laser deposition. Zn₃N₂, MgO, and Zn₃P₂ are introduced in the ZnO ceramic targets for the fabrication of the p-type ZnO films. Gases O₂ and N₂O are used as buffer gases. The thermal annealing of the ZnO films is employed. The resistance and photoluminescence (PL) spectra of the ZnO films are measured prior to and after annealing. The dependence of the ZnO PL peak amplitude and position prior to and after annealing on the level of doping with nitrogen and phosphorus is established. The PL characteristics of the films are studied at cw optical excitation using a He-Cd laser with a radiation wavelength of 325 nm. The PL spectra in the interval 300–700 nm are recorded by an HR4000 Ocean Optics spectrometer in the temperature range 10–400 K. The effect of the conditions for the film deposition on the PL spectra is analyzed. The effect of the N- and P-doping level of the ZnO films on the PL intensity of the films and the position of the PL bands in the UV region is investigated. The short-wavelength (250–400 nm) transmission spectra of the ZnO:P films are measured. The effect of the P-doping level on the band gap of the ZnO films is studied.     

退火对多晶ZnO薄膜结构与发光特性的影响

用射频反应溅射法在Si（111）衬底上制备了C轴取向的多晶ZnO薄膜，通过不同温度的退火处理，研究了退火对多晶ZnO薄膜结构和发光特性的影响.由x射线衍射得知，随退火温度的升高，晶粒逐渐变大，薄膜中压应力由大变小至出现张应力.光致发光测量发现，样品在430nm附近有一光致发光峰, 峰的强度随退火温度升高而减弱，联合样品电阻率随退火温度升高而逐渐变大的测量及能级图，推测出ZnO薄膜中的蓝光发射主要来源于锌填隙原子缺陷能级与价带顶能级间的跃迁. 关键词： ZnO薄膜 退火 光致发光 射频反应溅射     

Microstructure and optical properties of ZnO/porous silicon nanocomposite films

In this study, porous silicon (PS) templates were formed by electrochemical anodization on p-type (100) silicon wafer and ZnO films were deposited on PS substrates using radio frequency (RF) reactive magnetron sputtering technique. The effects of oxygen partial pressures of growth ZnO films and annealing ambience on the microstructure and photoluminescence (PL) of the ZnO/PS nanocomposite films were systematically investigated by X-ray diffraction and fluorescence spectrophotometry. The results indicated that all ZnO/PS nanocomposite films were polycrystalline in nature with a hexagonal wurtzite structure and the (002) oriented ZnO films had the best crystal quality under O₂:Ar ratio of 10:10 sccm and annealing in vacuum. PL measurements at room temperature revealed that ZnO/PS nanocomposite systems formed a broad PL band including the blue and green emissions from ZnO and red-orange emission from the PS. The mechanism and interpretation of broadband PL of the nanocomposites were discussed in detail using an oxygen-bonding model in PS and a native defects model in ZnO.     

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.     

Room-Temperature Ferromagnetic ZnMnO Thin Films Synthesized by Plasma Enhanced Chemical Vapour Deposition Method

Room-temperature ferromagnetic Mn-doped ZnO films are grown on Si （001） substrates by plasma enhanced chemical vapour deposition （PECVD）. X-ray diffraction measurements reveal that the Znl-xMn.O films have the single-phase wurtzite structure. X-ray photoelectron spectroscopy indicates the existence of Mn^2＋ ions in Mndoped ZnO films. Furthermore, the decreasing additional Raman peak with increasing Mn-doping is considered to relate to the substitution of Mn ions for the Zn ions in ZnO lattice. Superconducting quantum interference device （SQUID） measurements demonstrate that Mn-doped ZnO films have ferromagnetic behaviour at room temperature.     

Transitions of microstructure and photoluminescence properties of the Ge/ZnO multilayer films in certain annealing temperature region

The Ge/ZnO multilayer films have been prepared by rf magnetron sputtering. The effects of annealing on the microstructure and photoluminescence properties of the multilayers have been investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier-transform infrared (FTIR) spectrometry and photoluminescence (PL) spectrometry. The investigation of structural properties indicates that Zn₂GeO₄ has been formed with (2 2 0) texture and Zn deficiency from Ge/ZnO multilayer films in the process of annealing. However, lower Zn/Ge ratio can be improved by annealing. The annealed multilayers show three main emission bands at 532, 700, and 761 nm, which originate from the transition between oxygen vacancy () and Zn vacancies (V_Zn), the radiative recombination of quantum-confined excitons (QCE) in Ge nanocrystals, and the optical transition in the GeO color centers, respectively. Finally, the fabrication of thin film Zn₂GeO₄ from Ge/ZnO multilayer films by annealing at low temperature provides another approach to prepare the green-emitting oxide phosphor film:Zn₂GeO₄:Mn.     

Formation Mechanisms of Electrical Conductivity and Optical Properties of ZnO:N Film Produced by Annealing Treatment

The effects of annealing on the chemical states of N dopant, electrical, and optical properties of N-doped ZnO film grown by molecular beam epitaxy (MBE) are investigated. Both the as-grown ZnO:N film and the film annealed in N₂ are of n-type conductivity, whereas the conductivity converts into p-type conductivity for the film annealed in O₂. We suggest that the transformation of conductivity is ascribed to the change in ratio of the N molecular number on O site (N₂)_O to the N atom number on O site (N_O) in ZnO:N films under the various annealed atmosphere. For the ZnO:N film annealed in N₂, the percentage content of (N₂)_O is larger than that of N_O, i.e.the ratio >1, resulting in the n-type conductivity. However, in the case of the ZnO:N film annealed in O₂, the percentage content of (N₂)_O is fewer than that of N_O, i.e., the ratio <1, giving rise to the p-type conductivity. There is an obvious difference between low-temperature (80K) PL spectra of ZnO:N film annealed in N₂ and that of ZnO:N film annealed in O₂. An emission band located at 3.358eV is observed in the spectra of the ZnO:N film after annealed in N₂, this emission band is due to donor-bound exciton (D⁰X). After annealed in O₂, the PL of the donor-bound exciton disappeared, an emission band located at 3.348eV is observed, this emission band is assigned to acceptor-bound exciton (A⁰X).