Enhancement of surface morphology and optical properties of nanocolumnar ZnO films

Nanocolumnar ZnO films were prepared by electrodeposition (ED) on a glass substrate covered with a conductive layer of thin oxide doped with fluorine (FTO). After deposition the samples were annealed in oxidizing or reducing atmosphere, at temperatures between 100 to 500 C, in order to follow the evolution of optical properties and morphology. The optical properties of these films were studied by means of photoluminescence spectroscopy (PL) and the morphology by scanning electron microscopy (SEM). Films annealed at 300 C exhibit a higher ultraviolet emission peak, originating from exciton transitions. A green band related to deep-level emission centered at 500 nm, shows a drastic increase at 500 C. These results are independent of the annealing atmosphere. An increase of coalescence is also observed after annealing at 500 C. These results are explained taking into account the contribution of different point defects.     

Correlation between the structural and optical properties of Co doped ZnO thin films prepared at different film thickness

Cobalt doped zinc oxide (ZnO:Co) thin films were deposited on glass substrates by ultrasonic spray technique decomposition of Zinc acetate dihydrate and cobalt acetate tetrahydrate in an ethanol solution with film thickness. All films are polycrystalline with a hexagonal wurtzite-type structure with a preferential orientation according to the direction (0 0 2), with the maximum crystallite size was found of 59.42 nm at 569 nm. The average transmittance of all films is about 65–95% measured by UV–vis analyzer. The band gap energy increased from 3.08 to 3.32 eV with increasing the film thickness from 192 to 569 nm. The increase of the electrical conductivity with increases in the film thickness to maximum value of 9.27 (Ω cm)⁻¹ can be explained by the increase in carrier concentration and displacement of the electrons of the films. The correlation between the band gap and crystal structure suggests that the band gap energy of Co doped ZnO is influenced by the crystallite size and the mean strain.     

Structural and optical properties of Mn-doped ZnO nanocrystalline thin films with the different dopant concentrations

The transparent nanocrystalline thin films of undoped zinc oxide and Mn-doped (Zn_1−xMn_xO) have been deposited on glass substrates via the sol–gel technique using zinc acetate dehydrate and manganese chloride as precursor. The as-deposited films with the different manganese compositions in the range of 2.5–20 at% were pre-heated at 100 °C for 1 h and 200 °C for 2 h, respectively, and then crystallized in air at 560 °C for 2 h. The structural properties and morphologies of the undoped and doped ZnO thin films have been investigated. X-ray diffraction (XRD) spectra, scanning electron microscopy (SEM), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS) were used to examine the morphology and microstructure of the thin films. Optical properties of the thin films were determined by photoluminescence (PL) and UV/Vis spectroscopy. The analyzed results indicates that the obtained films are of good crystal quality and have smooth surfaces, which have a pure hexagonal wurtzite ZnO structure without any Mn related phases. Room temperature photoluminescence is observed for the ZnO and Mn-doped ZnO thin films.     

Effect of Ag doping on the photoluminescence properties of ZnO films

ZnO:Ag films were grown on Si (1 0 0) substrates by ultrasonic spray pyrolysis at various substrate temperatures. The effect of deposition temperature on the structural and the room temperature photoluminescence (RT-PL) properties of ZnO:Ag films was studied. With the deposition temperature rising to 550 °C, the intensity of the near-band edge (NBE) emission at 378 nm decreased and a new emission peak at 399 nm was observed. On the basis of the X-ray diffraction pattern (XRD), the X-ray photoelectron (XPS) spectra of ZnO:Ag films, and the effects of annealing on the PL, we suggest that the 399 nm emission should be attributed to the electron transition from the conduction band to Ag_Zn-related complexes defects radiative centers above the valence band.     

Structural and PL properties of Cu-doped ZnO films

Cu-doped ZnO films with hexagonal wurtzite structure were deposited on silicon (1 1 1) substrates by radio frequency (RF) sputtering technique. An ultraviolet (UV) peak at ∼380 nm and a blue band centered at ∼430 nm were observed in the room temperature photoluminescent (PL) spectra. The UV emission peak was from the exciton transition. The blue emission band was assigned to the Zn interstitial (Zn_i) and Zn vacancy (V_Zn) level transition. A strong blue peak (∼435 nm) was observed in the PL spectra when the α_Cu (the area ratio of Cu-chips to the Zn target) was 1.5% at 100 W, and ZnO films had c-axis preferred orientation and smaller lattice mismatch. The influence of α_Cu and the sputtering power on the blue band was investigated.     

Effect of strain on the structural and optical properties of Cu-N co-doped ZnO thin films

Polycrystalline ZnO thin films co-doped with Cu and N have been obtained by chemical bath deposition. Introduction of Cu and N causes the change of strained stress in ZnO films, which subsequently affects the structural and optical properties. The dependence of structural and optical properties of the ZnO films on lattice strained stress is investigated by XRD measurement, SEM, PL spectrum, optical reflection and Raman spectrum. The result of photoluminescence of Cu-N co-doped ZnO films indicates that the UV emission peaks shift slightly towards higher energy side with decrease in tensile strain and vise versa. The blue-shift of the absorption edge and up-shift of E2 (high) mode of the films can be observed in the optical reflection and Raman spectra.     

Influence of films thickness and structure on the photo-response of ZnO films

ZnO thin films were grown using Successive Ionic Layer Adsorption and Reaction (SILAR) method on glass substrates at room temperature. Annealing temperatures and film thickness effect on the structural, morphological, optical and electrical properties of the films were studied. For this as-deposited films were annealed at 200, 300, 400 and 500 °C for 30 min in oxygen atmosphere. The X-ray diffraction (XRD) and scanning electron microscopy (SEM) studies showed that the films are covered well with glass substrates and have good polycrystalline structure and crystalline levels. The film thickness effect on band gap values was investigated and band gap values were found to be within the range of 3.49-3.19 eV. The annealing temperature and light effect on electrical properties of the films were investigated and it was found that the current increased with increasing light intensity. The resistivity values were found as 10⁵ Ω-cm for as-deposited films from electrical measurements. The resistivity decreased decuple with annealing temperature and decreased centuple with light emission for annealed films.     

Al掺杂原子分数及退火温度对ZnO薄膜光学特性的影响

 采用溶胶凝胶法在（0001）Al₂O₃衬底上制备了不同掺杂原子分数的ZnO:Al薄膜,在Ar气氛中进行了600～950 ℃不同温度的退火处理,研究了掺杂原子分数和退火温度对薄膜光致发光、光吸收和透射的影响。结果显示,薄膜的紫外峰强度随掺杂原子分数和退火温度的提高而增强,与缺陷相关的绿光强度却随着掺杂原子分数和退火温度的提高而降低;薄膜光学带隙随掺杂原子分数的提高从3.21 eV增大到3.25 eV;光吸收在可见光区随着退火温度的升高而增大,在紫外区却随着退火温度的升高而减小,透射与吸收的变化规律相反;薄膜吸收边随退火温度的升高出现轻微的红移。     

Influence of excitation light wavelength on the photoluminescence properties for ZnO films prepared by magnetron sputtering

Highly orientated polycrystalline ZnO films were deposited on sapphire, silicon and quartz substrates at room temperature by r.f. magnetron sputtering. Different photoluminescence (PL) spectra were observed when excited with different wavelength light. A UV emission peak (356 nm) and a blue peak (446 nm) were generated for the films on sapphire, silicon and quartz substrates, and only the 446 nm blue emission appeared for the films on glass substrates when the wavelength of the excitation light was 270 nm. With increasing the wavelength of the excitation light up to 300 and 320 nm, the UV emission disappeared for films on various substrates and the wavelength of the PL peaks increased up to 488 and 516 nm, respectively. When the wavelength of the excitation light increased to 398 nm, the PL spectrum becomes a wide band that is consistent with three emission peaks.     

Ni掺杂ZnO薄膜的结构与光学特性研究

使用射频磁控溅射法成功制备了不同掺杂浓度（0—7at.%）的ZnO:Ni薄膜.X射线衍射的θ-2θ和摇摆曲线扫描结果表明,5at.%Ni掺杂ZnO薄膜具有沿c轴方向最佳的择优取向生长特性,（002）衍射峰向大角度方向移动揭示了Ni杂质被掺入ZnO晶格中占据Zn位.ZnO:Ni薄膜具有较好的可见光透明特性,拟合发现薄膜的光学带隙随Ni掺杂量的增加由3.272 eV线性降低到3.253 eV.未掺杂薄膜在550 nm处呈现出一个绿色发光峰,掺入Ni杂质后薄膜主要表现了以430 nm为中心的蓝色发光,分析认为它们分别源于薄膜中O空位和Zn填隙缺陷发光. 关键词： ZnO:Ni薄膜 结构特性 光学带隙 光致发光     

Effect of source temperature on the morphology and photoluminescence properties of ZnO nanostructures

ZnO nanostructures have been synthesized by heating a mixture of ZnO/graphite powders using the thermal evaporation and vapor transport on Si(1 0 0) substrates without any catalyst and at atmospheric argon pressure. The influence of the source temperature on the morphology and luminescence properties of ZnO nanostructures has been investigated. ZnO nanowires, nanoflowres and nanotetrapods have been formed upon the Si(1 0 0) substrates at different source temperatures ranging from 1100 to 1200 °C. Room temperature photoluminescence (PL) spectra showed increase green emission intensity as the source temperature was decreased and ZnO nanowires had the strongest intensity of UV emission compared with other nanostructures. In addition, the growth mechanism of the ZnO nanostructures is discussed based on the reaction conditions.     

Effect of solution concentrations on crystal structure,surface topographies and photoluminescence properties of ZnO thin films

Zinc oxide thin films were deposited on silicon substrates via hydrothermal method. Microstructures, surface topographies and optical properties of ZnO thin films were systematically investigated by X-ray diffraction, atomic force microscopy and fluorescence spectrophotometer. The mean grain size and surface roughness of the thin films decrease first and then increase with increasing the concentration of zinc nitrate hexahydrate. The photoluminescence spectra of ZnO thin films, excited by the 240, 320, 360, 380 and 400 nm excitation wavelength, were investigated in detail. Based on our analysis, it can be noted that mechanisms of the ultraviolet, violet and blue emissions are attributed to the transitions from the localized levels below the conduction band, zinc vacancy, interstitial zinc and extended interstitial zinc levels to the valance band, respectively. Blue–violet emissions of ZnO have great potential in light emitting and biological fluorescence labeling applications.     

Morphology and photoluminescence study of electrodeposited ZnO films

ZnO films on ITO substrates and Au coated ITO substrates were fabricated by using electrodeposition technique. We carried out the experiments by adjusting the concentration of solution, potential, substrate, and temperature. The effect of temperature on the growth of the film has been examined. SEM images have shown that there are several kinds of grown competitions for the deposition of ZnO films, but three kinds of them are dominant. One is the discrete hexagonal column structure, the other is the pentagonal structure, and the third one is of well-oriented hexagonal columns with well-aligned structure. The explanation on the grown competition is discussed. ZnO hexagonal column structures with well-aligned and well-perpendicular to the surface were successfully obtained on Au/ITO substrate in aqueous solvent of electrolyte. Clearly the main columns in the film were obtained by increasing the temperature. Its photoluminescence (PL) study at low temperature exhibited the optical properties as wurtzite ZnO and indicated the existence of macrocrystalline ZnO. A better quality of ZnO columnar structures after annealing was demonstrated from PL analysis and discussion on the existence of 370 nm, 384 nm and 639 nm in the emission bands before and after annealing.     

Effects of annealing on properties of ZnO thin films prepared by electrochemical deposition in chloride medium

The development of cost-effective and low-temperature synthesis techniques for the growth of high-quality zinc oxide thin films is paramount for fabrication of ZnO-based optoelectronic devices, especially ultraviolet (UV)-light-emitting diodes, lasers and detectors. We demonstrate that the properties, especially UV emission, observed at room temperature, of electrodeposited ZnO thin films from chloride medium (at 70 °C) on fluor-doped tin oxide (FTO) substrates is strongly influenced by the post-growth thermal annealing treatments. X-ray diffraction (XRD) measurements show that the films have preferably grown along (0 0 2) direction. Thermal annealing in the temperature range of 150-400 °C in air has been carried out for these ZnO thin films. The as-grown films contain chlorine which is partially removed after annealing at 400 °C. Morphological changes upon annealing are discussed in the light of compositional changes observed in the ZnO crystals that constitute the film. The optical quality of ZnO thin films was improved after post-deposition thermal treatment at 150 °C and 400 °C in our experiments due to the reducing of defects levels and of chlorine content. The transmission and absorption spectra become steeper and the optical bandgap red shifted to the single-crystal value. These findings demonstrate that electrodeposition have potential for the growth of high-quality ZnO thin films with reduced defects for device applications.     

Fabrication and properties of ZnO:Cu and ZnO:Ag thin films

Thin films of ZnS and ZnO:Cu were grown by an original metal–organic chemical vapour deposition (MOCVD) method under atmospheric pressure onto glass substrates. Pulse photo-assisted rapid thermal annealing of ZnO:Cu films in ambient air and at the temperature of 700–800 C was used instead of the common long-duration annealing in a vacuum furnace. ZnO:Ag thin films were prepared by oxidation and Ag doping of ZnS films. At first a closed space sublimation technique was used for Ag doping of ZnO films. The oxidation and Ag doping were carried out by a new non-vacuum method at a temperature >500 C. Crystal quality and optical properties were investigated using X-ray diffraction (XRD), atomic force microscopy (AFM), and photoluminescence (PL). It was found that the doped films have a higher degree of crystallinity than undoped films. The spectra of as-deposited ZnO:Cu films contained the bands typical for copper, i.e. the green band and the yellow band. After pulse annealing at high temperature the 410 and 435 nm photoluminescent peaks were observed. This allows changing of the emission colour from blue to white. Flat-top ZnO:Ag films were obtained with the surface roughness of 7 nm. These samples show a strong ultraviolet (UV) emission at room temperature. The 385 nm photoluminescent peak obtained is assigned to the exciton–exciton emission.     

Effect of annealing on the optical and electrical properties of ZnO:Er films

The effect of dopant concentration and annealing in the oxidizing atmosphere on the structural, optical, and electrical properties of ZnO:Er films deposited on sapphire substrates by the electron-beam evaporation method is investigated. The optical and electrical properties of these films were studied by UV-VIS-IR absorption and reflection spectroscopy, photoluminescence, and resistivity measurements. Experimental results reveal that as-deposited ZnO:Er films have both high transmittance in the visible range and low electrical resistivity and can be used as efficient transparent conducting oxides (TCOs). These films annealed in the oxidizing atmosphere have a visible emission band which can be used to fabricate light-emitting diodes.     

Growth and optical properties of ZnO microwells by chemical vapor deposition method

The well-like ZnO nanostructures were obtained by chemical vapor deposition method. The uniform and dense ZnO slim nano-columns were grown along the circle to form a microwell. The growth mechanisms, such as 1D linear, 2D screw dislocation and step growth are discussed. These observations provide some insight into the growth kinetics in vapor-solid growth process. The fabrication of ZnO microwell morphology provided a direct experimental evidence for explaining the 1D growth mechanism based on the axial screw dislocation. Photoluminescence (PL) microscopy showed the surface-related optical properties. The green light emission enhancement revealed that the ZnO microwells have waveguide properties. The abnormal enhancement of integrated PL intensity of deep-level emission with temperature increase showed abundant surface state existence.     

Effects of rapid thermal annealing on structural, magnetic and optical properties of Ni-doped ZnO thin films

XPS depth profiles were used to investigate the effects of rapid thermal annealing under varying conditions on the structural, magnetic and optical properties of Ni-doped ZnO thin films. Oxidization of metallic Ni from its metallic state to two-valence oxidation state occurred in the film annealed in air at 600 °C, while reduction of Ni²⁺ from its two-valence oxidation state to metallic state occurred in the film annealed in Ar at 600 and 800 °C. In addition, there appeared to be significant diffusion of Ni from the bottom to the top surface of the film during annealing in Ar at 800 °C. Both as-deposited and annealed thin films displayed obvious room temperature ferromagnetism (RTFM) which was from metallic Ni, Ni²⁺ or both with two distinct mechanisms. Furthermore, a significant improvement in saturation magnetization (M_s) in the films was observed after annealing in air (M_s = 0.036 μ_B/Ni) or Ar (M_s = 0.033 μ_B/Ni) at 600 °C compared to that in as-deposited film (M_s = 0.017 μ_B/Ni). An even higher M_s value was observed in the film annealed in Ar at 800 °C (M_s = 0.055 μ_B/Ni) compared to that at 600 °C mainly due to the diffusion of Ni. The ultraviolet emission of the Ni-doped ZnO thin film was restored during annealing in Ar at 800 °C, which was also attributed to the diffusion of Ni.     

The annealing effect on structural and optical properties of ZnO thin films produced by r.f. sputtering

In this work, a study of the structure and optical properties of undoped ZnO thin films produced by r.f. magnetron sputtering technique as a function of the growth parameters is reported. Modification under annealing conditions is also analysed. Raman spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction and optical transmittance have been used. From the position of the (002) X-ray diffraction peak and the E₂ (high) mode detected in Raman spectra, the residual stress both in the as-grown and in the annealed samples has been estimated.     

The structural properties of Al doped ZnO films depending on the thickness and their effect on the electrical properties

In this study, the structural and electrical properties of AZO films with different film thickness deposited by r.f. magnetron sputtering were interpreted in relation with film growth process. The result shows that the grain size increases during film growth, which is accompanied by decrease of compressive stress, indicating the enhancement of crystallinity. The relationship between grain size and compressive stress follows the same tendency for the samples regardless of deposition temperature, which implies the strong dependencies between the grain size and the compressive stress. The XPS analysis shows that the defects such as chemisorbed oxygen and segregated Al₂O₃ cluster at grain boundary are reduced with increase of film thickness or deposition temperature, leading to increase of carrier concentration and mobility. The mobility increase is accompanied by grain size increase and compressive stress reduction, indicating the influences of grain boundary and crystallinity on the mobility.