Structural and optical properties of ZnO films grown on the AAO templates

Structural and optical properties of ZnO films grown on Al substrate and anodic alumina oxide (AAO) templates by rf magnetron reactive sputtering deposition were investigated using X-ray diffraction (XRD), atomic-force microscope (AFM) and photoluminescence (PL). We found that ZnO thin films on Al substrate show good C-axis orientation, while the orientation of ZnO film on AAO templates is disordered, this due to the fact that the crystalline of ZnO is greatly influenced by surface morphology of substrates. PL measurements show a blue band in the wavelength range of 400–500 nm caused by the interstitial Zn in the ZnO films. The intensity of emission peak of ZnO films deposited on AAO templates increases compared with that on the Al substrate. Combining electrical resistivity and carrier concentration measurements, we found that that the blue emission intensity is consistent with the concentration for the interstitial zinc in the ZnO films.     

Ni2+掺杂ZnO薄膜及粉体的结构和发光性能研究

采用激光脉冲沉积法,用XeCl准分子激光器在Si (100)基片、真空和5Pa氧气气氛下制备了Ni2+(0.8％(原子分数))掺杂的呈六角纤锌矿结构的ZnO薄膜.氧气气氛下制备的薄膜沿(002)取向生长,表面比较平整,平均颗粒尺寸为80nm.真空条件下制备的薄膜出现Zn2SiO4杂相,平均颗粒尺寸为150nm.和真空条件下制备的薄膜相比,氧气气氛下制备的薄膜具有较强的ZnO本征发光,在425nm附近出现由于填隙Zn缺陷引起的较宽的蓝光发光带,并且在482nm处出现了由于氧空位和氧间隙间的转换引起的较强的蓝光发光峰,同时由于氧缺陷引起的449nm附近的蓝光发光峰强度明显降低.     

氧分压对磁控溅射ZnO薄膜生长行为和光学特性的影响

采用反应射频磁控溅射方法, 在Si(001)基片上制备了具有高$c$轴择优取向的ZnO薄膜. 利用原子力显微镜、X射线衍射、透射光谱和室温光致荧光光谱等分析技术, 研究了氧分压对薄膜的表面形貌和光学特性的影响. 研究结果显示: 0.04～0.23Pa的氧分压范围内, ZnO薄膜存在三个不同的生长模式, 薄膜生长模式转变的临界氧分压分别位于0.04～0.08Pa和0.16～0.19Pa之间; 在0.16Pa以下时, ZnO薄膜的表面岛呈+c取向的竹笋状生长; 当氧分压>0.19Pa时, 薄膜的表面岛以-c取向生长为主; ZnO薄膜的折射率、光学带隙宽度以及PL光谱强度均随着氧分压的增大而增大, 氧分压为0.19Pa时, 薄膜的发光峰最窄, 其半峰宽为88meV.     

Synthetics of ZnO nanostructures by thermal oxidation in water vapor containing environments

Metallic Zn films deposited on glass were wet or dry oxidized at 390 °C in pure N₂ or O₂ to understand the effects of water vapor in different oxygen partial pressure on growth of ZnO nanostructure during thermal oxidation. As-prepared ZnO oxides were characterized by a scanning electron microscope (SEM), an X-ray diffractometer (XRD), and a transmission electron microscope (TEM). Optical and electric properties of these ZnO films were characterized by photoluminescence (PL) and resistance measurements, respectively. It was found that the oxygen partial pressure and water vapor of environment significantly affect the morphologies of ZnO nanostructures. Decreasing oxygen partial pressure in dry oxidation can enhance a green light peak at 500 nm on PL spectra arising from defect-related emission and reduce the resistivity of the oxide films. High H₂O^(g)/O₂ ratio in wet oxidation will significantly increase the intensity of a green light peak and reduce the resistivity of the oxide films. The effect of oxygen partial pressure and H₂O^(g)/O₂ ratio on the PL spectra and resistivity of ZnO films are explained by the theory of defects equilibrium during oxidation.     

Effects of oxygen pressure on the structure and photoluminescence of ZnO thin films

A series of ZnO thin films were deposited on silicon (100) substrate at 473 K by using facing target RF magnetron sputtering system at different oxygen pressure in this paper. The structure, surface morphology and photoluminescence of the ZnO thin films were characterized by X-ray diffraction, atomic force microscopy (AFM), and photoluminescence spectra (PL), respectively. The results showed that only a (002) peak of hexagonal wurtzite appeared in all ZnO thin films, indicating that ZnO films exhibited strong texture. With increasing the oxygen pressure, the results indicated that the ZnO film deposited at 1.2 Pa Ar pressure and 0.6 Pa oxygen pressure had the best preferential C-axis orientation and the weakest compressive stress. Meanwhile, AFM observation showed that ZnO film deposited at pure Ar had the highest surface roughness. With the increment of oxygen pressure, the surface roughness decreased gradually. In addition, PL measurement showed that the ZnO film deposited at 1.2 Pa Ar pressure and 0.6 Pa oxygen pressure had the strongest ultraviolet emission and the weakest blue emission.     

Effect of growth temperature on structural, electrical and optical properties of dual ion beam sputtered ZnO thin films

ZnO epitaxial thin films were grown on p-type Si(100) substrates by dual ion beam sputtering deposition system. The crystalline quality, surface morphology, optical and electrical properties of as-deposited ZnO thin films at different growth temperatures were studied. Substrate temperature was varied from 100 to 600 °C at constant oxygen percentage O₂/(O₂ + Ar) % of 66.67 % in a mixed gas of Ar and O₂ with constant chamber pressure of 2.75 × 10^?4 mBar. X-Ray diffraction analyses revealed that all the films had (002) preferred orientation. The minimum value of stress was reported to be ?0.32 × 10¹⁰ dyne/cm² from ZnO film grown at 200 °C. Photoluminescence measurements demonstrated sharp near-band-edge emission (NBE) was observed at ~375 nm along with deep level emission (DLE) in the visible spectral range at room temperature. The DLE Peak was found to have decrement as ZnO growth temperature was increased from 200 to 600 °C. The minimum FWHM of the NBE peak of 16.76 nm was achieved at 600 °C growth temperature. X-Ray photoelectron spectroscopy study revealed presence of oxygen interstitials and vacancies point defects in ZnO film grown at 400 °C. The ZnO thin film was found to be highly resistive when grown at 100 °C. The ZnO films were found to be n-type conducting with decreasing resistivity on increasing substrate temperature from 200 to 500 °C and again increased for film grown at 600 °C. Based on these studies a correlation between native point defects, optical and electrical properties has been established.     

Effects of buffer layer thickness on properties of ZnO thin films grown on porous silicon by plasma-assisted molecular beam epitaxy

ZnO thin films with different buffer layer thicknesses were grown on Si and porous silicon (PS) by plasma-assisted molecular beam epitaxy (PA-MBE). The effects of PS and buffer layer thickness on the structural and optical properties of ZnO thin films were investigated by atomic force microscopy (AFM), scanning electron microscopy (SEM), X-ray diffraction (XRD), and photoluminescence (PL). The ZnO buffer layers, the intensity of the (002) diffraction peak for the ZnO thin films and its full width at half maximum (FWHM) decreased with an increase in the thickness of the ZnO buffer layers, indicating an improvement in the crystal quality of the films. On introducing PS as a substrate, the grain sizes of the ZnO thin films became larger and their residual stress could be relaxed compared with the ZnO thin films grown on Si. The intensity ratio of the ultraviolet (UV) to visible emission peak in the PL spectra of the ZnO thin films increased with an increase in buffer layer thickness. Stronger and narrower UV emission peaks were observed for ZnO thin films grown on PS. Their structural and optical properties were enhanced by increasing the buffer layer thickness. In addition, introduction of PS as a substrate enhanced the structural and optical properties of the ZnO thin films and also suppressed Fabry-Perot interference.     

Exciting Dilute Magnetic Semiconductor: Copper-Doped ZnO

The present study is focused on the copper-doped ZnO system. Bulk copper-doped ZnO pellets were synthesized by a solid-state reaction technique and used as target material in pulsed laser deposition. Thin films were grown for different Cu doped pellets on sapphire substrates in vacuum (5×10^?5 mbar). Thin films having (002) plane of ZnO showed different oxidation states of dopants. M–H curves exhibited weak ferromagnetic signal for 1–3 % Cu doping but for 5 % Cu doped thin film sample showed the diamagnetic behavior. For deeper information, thin films were grown for 5 % Cu doped ZnO bulk pellet in different oxygen ambient pressures and analyzed. PL measurement at low temperature showed the emission peak in thin films samples due to acceptor-related transitions. XPS results show that copper exists in Cu²⁺ and Cu⁺¹ valence states in thin films and with increasing O₂ ambient pressure the valence-band maximum in films shifts towards higher binding energy. Furthermore, in lower oxygen ambient pressure (1×10^?2 mbar) thin films showed magnetic behavior but this vanished for the film grown at higher ambient pressures of oxygen (6×10^?2 mbar), which hints towards the decrease in donor defects.     

Structural, Morphological and Optical Properties of ZnO Thin Films Grown on γ-LiAlO2 Substrate by Pulsed Laser Deposition

ZnO thin films were deposited on the substrates of (100) γ-LiAlO2 at 400, 550 and 700℃ using pulsed laser deposition (PLD) with the fixed oxygen pressure of 20 Pa, respectively. When the substrate temperature is 400℃, the grain size of the film is less than 1 μm observed by Leitz microscope and measured by X-ray diffraction (XRD). As the substrate temperature increases to 550℃, highly-preferred c-orientation and high-quality ZnO film can be attained.While the substrate temperature rises to 700℃, more defects appears on the surface of film and the ZnO films become polycrystalline again possibly because more Li of the substrate diffused into the ZnO film at high substrate temperature. The photoluminescence (PL) spectra of ZnO films at room temperature show the blue emission peaks centered at 430 nm. We suggest that the blue emission corresponds to the electron transition from the level of interstitial Zn to the valence band. Meanwhile, the films grown on γ-LiAlO2 (LAO) exhibit green emission centered at 540 nm, which seemed to be ascribed to excess zinc and/or oxygen vacancy in the ZnO films caused by diffusion of Li from the substrates into the films during the deposition.     

Abnormal photoluminescence of ZnO thin film on ITO glass

The photoluminescence (PL) properties of ZnO thin films on ITO glass substrate deposited by rf magnetron sputtering with different oxygen partial pressures were studied. It was found that the exciton related emission of ZnO thin films depends on oxygen partial pressure, and that the visible emission related to intrinsic defects has no obvious change with various oxygen partial pressures. Abnormal UV-PL characteristics were observed, and its intensity was obviously enhanced. The emission position has a strong red-shift with increasing excitation intensity, and the emission intensity increases notably with increasing excitation cycle.     

The effect of annealing temperature on the properties of ZnO films with preferential nonpolar plane orientation by SSCVD

The effect of annealing temperature on the structural morphology and optical properties of preferential nonpolar plane orientated ZnO thin films on Si (100) substrates by single source chemical vapor deposition (SSCVD) was investigated. The structural and morphological properties of the films were characterized by X-ray diffraction (XRD) and atomic force microscope (AFM) measurements respectively. All the ZnO films annealed at the selected temperatures (500–800 °C) exhibiting a–b axis orientation, but with preferential nonpolar (100) plane orientation. It is found that the intensity of the (100) peak depends strongly on the annealing temperature, while that of (101) peak shows a variation in a very small scale. The surface morphology demonstrates that the film is of the uniform grains except for that annealed at 800 °C, for the aggregation of the ZnO particles occurred. The film shows a superior smooth surface annealed at 600 and 700 °C in comparison with other thermal annealed. It is also found from the photoluminescence(PL) measurements that the film annealed at 700 °C exhibits the lowest deep-level emission(DLE). However, the intensity of the near band edge emissions (NBE) and DLE show a wavelike variation, which are consistent to the variation of the intensity of (100) peak in the XRD results.     

Influence of oxygen partial pressure on the structure and photoluminescence of direct current reactive magnetron sputtering ZnO thin films

The effects of oxygen partial pressure on the structure and photoluminescence (PL) of ZnO films were studied. The films were prepared by direct current (DC) reactive magnetron sputtering with various oxygen concentrations at room temperature. With increasing oxygen ratio, the structure of films changes from zinc and zinc oxide phases, single-phase ZnO, to the (002) orientation, and the mechanical stresses exhibit from tensile stress to compressive stress. Films deposited at higher oxygen pressure show weaker emission intensities, which may result from the decrease of the oxygen vacancies and zinc interstitials in the film. This indicates that the emission in ZnO film originates from the oxygen vacancy and zinc interstitial-related defects. From optical transmittance spectra of ZnO films, the plasma edge shifts towards the shorter wavelength with the improvement of film stoichiometry.     

Dependency of oxygen partial pressure on the characteristics of ZnO films grown by radio frequency magnetron sputtering

The effects of oxygen and argon gas contents on the structural and optical properties of epitaxially grown ZnO thin films on sapphire substrates by radio frequency magnetron sputtering were investigated. The growth rate of ZnO thin film decreases with increase in oxygen gas contents in the gas mixture. The high-resolution x-ray diffraction $ {\left( {10\overline{1} 2} \right)} $ rocking curve and plane-view transmission electron microscopy investigations reveal the presence of a reduced dislocation density in the ZnO thin films with decrease in oxygen/argon flow ratio. However, large density of defects were observed in the boundaries and inside of the micro-hillocks formed on the surface of ZnO thin film grown with pure argon. The increase in oxygen gas ratio resulted in the improvement of optical properties with suppression and red-shift of the deep level emission.     

PLD法生长高质量 ZnO薄膜及其光电导特性研究

采用脉冲激光沉积（PLD）法在单晶Si（100）衬底上生长ZnO薄膜，以X射线衍射（XRD）和场发射扫描电镜（SEM）等手段分析了所得ZnO薄膜的晶体结构和微观形貌．结果表明，随着衬底温度和薄膜生长时氧分压的增加，ZnO薄膜的晶体结构和化学计量比得到显著改善．优化工艺（700℃，20Pa）下生长的ZnO薄膜呈c轴高度择优取向，柱状晶垂直衬底表面生长，结构致密均匀．以不同暗电阻的ZnO薄膜为材料，利用剥离（1ift-off）技术制备了MSM结构ZnO光电导型紫外探测器．紫外光照射前后的I-V特性测试表明ZnO薄膜产生非常明显的光电导现象，分析了其光电响应机理．     

Structure and physical properties of undoped ZnO and vanadium doped ZnO films deposited by pulsed laser deposition

Undoped ZnO films were deposited using pulsed laser deposition technique on Si and glass substrates in different O2 partial pressures (ranging from 10(-5) mbar to 3 mbar) and substrate temperatures. When the substrate temperature is 500 degrees C and O2 partial pressure (pp) approximately 3 mbar, randomly oriented ZnO hexagons were observed on glass substrate, whereas, dense ZnO hexagonal rod like structures (diameter ranging from 200-500 nm) were observed on Si substrate. The photoluminescence (PL) characterization of ZnO film grown on Si exhibited an intense defect free narrow excitonic emission in the UV region (Full width half maximum (FWHM) approximately 11.26 nm) as compared to broad emission (FWHM approximately 57.06 nm) from that grown on glass. The parent film emission was found to shift from UV to blue region on doping ZnO with Vanadium.     

Deposition of nanocrystalline ZnO by wire explosion technique and characterization of the films' properties

ZnO films deposited on glass, quartz and Al on silicon mono-crystal Si (100) substrates by using the wire explosion technique were investigated by X-ray diffraction (XRD), UV–VIS spectroscopy, scanning electron (SEM) and atomic force microscopy (AFM) measurements. X-ray diffraction measurements have shown that ZnO films are mainly composed of (100), (002) and (101) orientation crystallites. The post-deposition thermal treatment at 600 °C temperature in air has shown that the composite of Zn/ZnO film was fully oxidized to ZnO film. The XRD spectra of the film deposited in oxygen atmosphere at room temperature present high intensity dominating peak at 2h = 36, 32° corresponding to the (101) ZnO diffraction peak. The small fraction of the film (7%) corresponds to the (002) peak intensity at 2h = 34, 42°. This result indicates the good crystal quality of the film and hexagonal wurtzite-type structure deposited by zinc wire explosion. The optical absorption spectra shows the bands at 374, 373 and 371 nm corresponding to deposition conditions. The SEM analysis shows that ZnO films presented different morphologies from fractal network to porous films depending on deposition conditions. AFM analysis revealed the grain size ranges from 50 nm to 500 nm. The nanoneedles up to 300 nm in length were found as typical structures in the film. It was demonstrated that the wire explosion technique is a feasible method to produce ZnO crystalline thin films and nanostructures.     

ZnO thin films prepared by pulsed laser deposition

Zinc oxide (ZnO) thin films were deposited on soda lime glass substrates by pulsed laser deposition (PLD) in an oxygen-reactive atmosphere. The structural, optical, and electrical properties of the as-prepared thin films were studied in dependence of substrate temperature and oxygen pressure. High quality polycrystalline ZnO films with hexagonal wurtzite structure were deposited at substrate temperatures of 100 and 300 °C. The RMS roughness of the deposited oxide films was found to be in the range 2-9 nm and was only slightly dependent on substrate temperature and oxygen pressure. Electrical measurements indicated a decrease of film resistivity with the increase of substrate temperature and the decrease of oxygen pressure. The ZnO films exhibited high transmittance of 90% and their energy band gap and thickness were in the range 3.26-3.30 eV and 256-627 nm, respectively.     

Effect of doping on properties of Zno:Cu and Zno:Ag thin films

ZnO:Cu and ZnS thin films were grown by metal-organic chemical vapour deposition (MOCVD) under atmospheric pressure onto glass substrates. The ZnO:Ag films were fabricated from ZnS films by non-vacuum method that consists of simultaneous oxidation and Ag-doping by the close spaced evaporation (CSE) of silver at the temperature of 500–600 °C. Photo-assisted rapid thermal annealing (PARTA) at ambient air during 10–30 s at the temperature of 700–800 °C was used for the ZnO:Cu films. The samples were studied by X-ray diffraction technique (XRD), atomic force microscopy (AFM), and photoluminescence (PL) measurements. The grain size of ZnO:Cu films increased with an increase of Cu concentration. PL spectra of as-deposited ZnO:Cu films depended on Cu concentration and contained the bands typical for the copper. After PARTA at high temperature the emission maximum shifted towards the short-wave region. During the fabrication of ZnO:Ag films the grain growth process was strongly affected by the Ag loading level. The grain size increased with an increase of Ag concentration and ZnO:Ag films with surface roughness of 8 nm were obtained. Observed 385 nm PL peak for these samples can be attributed to the exciton–exciton emission that proves the high quality of the obtained ZnO:Ag films.     

Effects of thermal annealing in oxygen plasma for buffer layers on properties of ZnO thin films

ZnO thin films with ZnO buffer layers were grown by plasma-assisted molecular beam epitaxy (PA-MBE) on p-type Si(100) substrates. Before the growth of the ZnO thin films, the ZnO buffer layers were deposited on the Si substrates for 20 minutes and then annealed at the different substrate temperature ranging from 600 to 800 degrees C in oxygen plasma. The structural and optical properties of the ZnO thin films have been investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), and room-temperature (RT) photoluminescence (PL). A narrower full width at half maximum (FWHM) of the XRD spectra for ZnO(002) and a larger grain are observed in the samples with the thermal annealed buffer layers in oxygen plasma, compared to those of the as-grown sample. The surface morphology of the samples is changed from rugged to flat surface. In the PL spectra, near-band edge emission (NBEE) at 3.2 eV (380 nm) and deep-level emission (DLE) around 1.77 to 2.75 eV (700 to 450 nm) are observed. By increasing the annealing temperatures up to 800 degrees C, the PL intensity of the NBEE peak is higher than that of the as-grown sample. These results imply that the structural and optical properties of ZnO thin films are improved by the annealing process.     

Optical characterization of ZnO thin films deposited by Sol-gel method

In this paper, ZnO thin film is deposited on Pt/TiO₂/SiO₂/Si substrate using the sol-gel method and the effect of annealing temperature on the structural morphology and optical properties of ZnO thin films is investigated. The ZnO thin films are crystallized by the heat treatment at over 400°C. The ZnO thin film annealed at 600°C exhibits the greatest c-axis orientation and the Full-Width-Half-Maximum (FWHM) of X-ray peak is 0.4360°. A dense ZnO thin film is deposited by the growth of uniform grains with the increase of annealing temperature but when the annealing temperature increases to 700°C, the surface morphology of ZnO thin film becomes worse by the aggregation of ZnO particles. In the results of surface morphology of ZnO thin film using atomic force microscope (AFM), the surface roughness of ZnO thin film annealed at 600°C is smallest, that is, approximately 1.048 nm. For the PL characteristics of ZnO thin film, it is observed that ZnO thin film annealed at 600°C exhibits the greatest UV (ultraviolet) exciton emission at approximately 378 nm, and the smallest visible emission at approximately 510 nm among ZnO thin films annealed at various temperatures. It is deduced that ZnO thin film annealed at 600°C is formed most stoichiometrically, since the visible emission at approximately 510 nm comes from either oxygen vacancies or impurities.