Influence of size effect and sputtering conditions on the crystallinity and optical properties of ZnO thin films

The effects of the thickness variation, substrate type and annealing on the crystallinity parameters, luminescent and optical properties of the zinc oxide (ZnO) thin films were reported. The thin films were deposited on the glass and the amorphous quartz substrates by the standard RF-magnetron sputtering method using ZnO targets in the argon atmosphere. It has been found that the films deposited on the glass substrate manifest a clear size effect. Both the structural and the optical parameters show clearly minima on their thickness dependences. It has been shown that annealing of the comparatively thick ZnO films leads to increase of the crystallite sizes that are followed by a considerable rise of the cathodoluminescence intensity. The corresponding model of the crystallite growth is proposed.     

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.     

Optoelectronics and formaldehyde sensing properties of tin-doped ZnO thin films

Sn-doped ZnO thin films were deposited on clean glass substrates using the chemical spray pyrolysis technique. XRD analyses confirm stable ZnO hexagonal wurtzite structure of the films with crystallite size in the range of 20–28 nm. The surface roughness of the films increases on Sn doping, which favors to higher adsorption of oxygen species on the film surface, resulting in higher gas response. Optical studies reveal that the band gap decreases on Sn doping. All the films show near band edge emission, and on Sn doping the luminescence peak intensity has been found to increase. Photocurrent in the 1.5 at.% doped film enhances about three times to that observed in the undoped ZnO film. Among all the films examined, the 1.5 at.% Sn-doped film exhibits the maximum response (～94.5 %) at the operating temperature of 275?°C for 100 ppm concentration of formaldehyde, which is much higher than the response (～35 %) in the undoped film. The gas response of the film is attributed to the chemisorption of oxygen on the film surface and the subsequent reaction between the adsorbed oxygen species and the formaldehyde molecules.     

Sol–gel derived zinc oxide films: Effect of deposition parameters on structure, microstructure and photoluminescence properties

ZnO films were prepared by sol–gel method and deposited onto glass substrates with spin coating system. XRD patterns and FESEM analysis were used to investigate the effect of deposition parameters such as spin speed and molar concentration on the crystallinity and surface morphology of the films. XRD patterns show that ZnO films are polycrystalline with type-wurtzite hexagonal structure. The film which is deposited at 4000 rpm and with 0.5 M sol has the best crystallinity. The FESEM micrographs showed that the surface morphology of the films was not significantly affected from the spin speed. FESEM micrographs showed that the crystallite sizes of 1000, 4000 and 5000 rpm are almost same. But 2000 and 3000 rpm have lower crystallite sizes than the others. Also, the amount of voids in the 1 M was found higher. The effect of spin speed and molar concentration on the optical properties of ZnO films was investigated by PL spectroscopy. The electrical properties of the ZnO films were investigated by using two probe methods in dark. The highest conductivity values were obtained for ZnO films prepared by 4000 spin speed and 0.5 M of concentration.     

Properties of Eu-doped zinc oxide thin films grown on glass substrates by radio-frequency magnetron sputtering

Eu-doped ZnO (EZO) thin films were prepared on glass substrates at various growth temperatures by radio-frequency magnetron sputtering. The properties of deposited thin films showed a significant dependence on the growth temperature. The preferential growth orientation of all the thin films was occurred along the ZnO (002) plane. The maximum crystallite size and the minimum average transmittance in the wavelength range of 450–1100 nm were observed for the EZO thin film deposited at 25 °C. A red shift of the optical band gap was observed in the growth temperature range of 25–300 °C. The highest figure of merit, an index for evaluating the performance of transparent conducting thin films, was obtained at 200 °C of growth temperature. These results indicated that the high-quality EZO film was obtained at a growth temperature of 200 °C.     

Ge薄膜特性及其在光子计数成像系统中的应用

利用电子束真空蒸镀方法制作了Ge薄膜,用作感应读出方式光子计数成像系统的电荷感应层,研究了石英玻璃衬底和陶瓷衬底上Ge薄膜的结构特征、表面形态以及各种工艺参数对薄膜电阻的影响.X射线衍射(XRD)测试表明,两种衬底上沉积的Ge薄膜均为立方相非晶态.场发射扫描电子显微镜(FESEM)图像表明石英玻璃衬底上的薄膜致密平整,陶瓷衬底上的薄膜比较粗糙,厚度较薄时,陶瓷晶界处薄膜不连续导致电阻较大.通过改变沉积速率、薄膜厚度及采用退火的方法可以控制薄膜电阻.对比了采用不同阻值电荷感应层时系统的性能,发现阻值对探测器的分辨率影响小,对计数率影响较大.     

The comparison between CdS thin films grown on Si(111) substrate and quartz substrate by femtosecond pulsed laser deposition

Two kinds of cadmium sulfate (CdS) thin films have been grown at 600 °C onto Si(111) and quartz substrates using femtosecond pulsed laser deposition (PLD). The influence of substrates on the structural and optical properties of the CdS thin films grown by femtosecond pulsed laser deposition have been studied. The CdS thin films were characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), photoluminescence (PL) and Raman spectroscopy. Although CdS thin films deposited both on Si(111) and quartz substrates were polycrystalline and hexagonal as shown by the XRD , SEM and AFM results, the crystalline quality and optical properties were found to be different. The size of the grains for the CdS thin film grown on Si(111) substrate were observed to be larger than that of the CdS thin film grown on quartz substrate, and there is more microcrystalline perpendicularity of c-axis for the film deposited on the quartz substrate than that for the films deposited on the Si substrate. In addition, in the PL spectra, the excitonic peak is more intense and resolved for CdS film deposited on quartz than that for the CdS film deposited on Si(111) substrate. The LO and TO Raman peaks in the CdS films grown on Si(111) substrate and quartz substrate are different, which is due to higher stress and bigger grain size in the CdS film grown on Si(111) substrate, than that of the CdS film grown on the amorphous quartz substrate. All this suggests that the substrates have a significant effect on the structural and optical properties of thin CdS films. PACS 81.15.Fg; 81.05.Ea; 78.20.-e; 78.67.-n; 42.62.-b     

Thin films of Cu(II)-o,o′-dihydroxy azobenzene nanoparticle-embedded polyacrylic acid (PAA) for nonlinear optical applications developed by matrix assisted pulsed laser evaporation (MAPLE)

Thin films based on two different metal-organic systems are developed by MAPLE and their nonlinear optical applications are explored. A complex of o,o′-dihydroxy azobenzene with Cu²⁺ cation is found to organize as a non-central symmetric crystallite. A simple protocol is developed for the in situ fabrication of highly monodisperse copper-complex nanoparticles in a polymer film matrix of polyacrylic acid. The thin films were deposited on quartz substrates by MAPLE (matrix assisted pulsed laser evaporation) using a Nd:YAG laser working at 355 nm. Atomic force microscopy (AFM), Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS), and optical second harmonic generation (SHG) were performed on the samples. The optical limiting capability of the nanoparticle-embedded polymer film is investigated.     

Determination of the element distribution in films deposited using the plasma focus facility by Rutherford backscattering

The C, Cu and W element profiles in films deposited using a plasma focus facility are studied by the Rutherford backscattering of 2-MeV He⁺ ions. The films are deposited onto glass substrates in Ar plasmaforming gas. The element profiles are found to depend significantly on the kinetic energy of particles. The penetration depth of particles with the velocity ~10⁵ m/s is about 1.5 μm. The corresponding element profiles showing the distribution of elements over the thickness of the glass are non-linear. For each element, the maximum layer depth is observed under the glass surface. The formation of Cu, W and C layers under the glass surface and their overlapping is a feature of films deposited using the plasma focus facility. Such an arrangement of layers evidences the significant difference between this method of film deposition and conventional techniques at low rates of atom deposition, as well as diffusion-based methods. The obtained films are found to have dielectric properties.     

Photoluminescence of ZnO films prepared by r.f. sputtering on different substrates

Polycrystalline ZnO films with good orientation were deposited on sapphire, quartz, Si and 7059 glass substrates by r.f. magnetron sputtering. A strong UV photoluminescence (PL) peak (located at 356 nm) and a weak blue emission peak (located at 446 nm) were observed at room temperature (RT) for the films deposited on sapphire, quartz and Si substrates when excited with 270 nm light. For the films prepared on Corning 7059 glass, only a strong 446 nm blue emission peak was found, and the PL intensity decreased with increasing oxygen pressure during films deposition. The intensity of the UV emission increased 7 and 14 times, respectively, for the films on sapphire and quartz substrates after high temperature annealing in vacuum. The UV emission originates from the inter-band transition of electrons and the blue emission is due to transition of electrons from the shallow donor level of the oxygen vacancies to the valence band.     

Effect of substrate temperature and oxygen partial pressure on microstructure and optical properties of pulsed laser deposited yttrium oxide thin films

Yttrium oxide thin films were deposited on Si (1 1 1) and quartz substrates by pulsed laser deposition technique at different substrate temperature and oxygen partial pressure. XRD analysis shows that crystallite size of the yttrium oxide thin films increases as the substrate temperature increases from 300 to 873 K. However the films deposited at constant substrate temperature with variable oxygen partial pressure show opposite effect on the crystallite size. Band gap energies determined from UV-visible spectroscopy indicated higher values than that of the reported bulk value.     

Growth of crystalline quartz films with AT-cut plane by means of catalyst-enhanced vapor-phase epitaxy under atmospheric pressure

Crystalline quartz films with an AT-cut plane have been grown by catalyst-enhanced vapor-phase epitaxy, at atmospheric pressure, using two quartz buffer layers on a sapphire (110) substrate. In this method, the first quartz buffer layer was deposited on the sapphire (110) substrate at 773 K. After annealing at 823 K, the second buffer layer was deposited at 723 K. The crystal quartz epitaxial layer was then grown at 843 K. The X-ray full-width-at-half-maximum (FWHM) value of the crystalline quartz film obtained was smaller than that of crystalline quartz prepared using a hydrothermal process. The crystalline quality of the quartz films was dependent on the thickness of the buffer layers. Furthermore, it was found that angle control of the cut plane depended on the film thickness of the second buffer layer. The quartz films grown by vapor phase epitaxy show good oscillation characteristics at room temperature.     

N掺杂ZnO薄膜的荧光特性研究

以N2为掺杂源,通过改变O2∶N2比,利用射频磁控溅射法在玻璃衬底上制备了具有[002]择优取向的N掺杂ZnO薄膜,研究了ZnO薄膜的光致发光谱随着N掺入量的不同而变化的规律.结果表明,薄膜主衍射峰为402 nm处的发光峰;由于N掺杂量的不同,有的薄膜在445 nm和524 nm处也有发光发存在,但随着薄膜N含量的不同,其发光峰强度明显不同,其峰位也发生了相应的红移或者蓝移.当O2∶N2为10∶ 15时,制备的薄膜N掺杂量最大,光学性能最好,此工艺为研究ZnO薄膜的缺陷类型及导电类型提供了重要的研究参考.     

Effect of precursors on structure, optical and electrical properties of chemically deposited nanocrystalline ZnO thin films

Nanocrystalline ZnO thin films were chemically deposited on glass substrates using two different precursors namely, zinc sulphate and zinc nitrate. XRD studies confirm that the films are polycrystalline zinc oxide having hexagonal wurtzite structure with crystallite size in the range 25-33 nm. The surface morphology of film prepared using zinc sulphate exhibits agglomeration of small grains throughout the surface with no visible holes or faulty zones, while the film prepared using zinc nitrate shows a porous structure consisting of grains with different sizes separated by empty spaces. The film prepared using zinc sulphate shows higher reflectance due to its larger refractive index which is related to the packing density of grains in the film. Further, the film prepared using zinc sulphate is found to have normal dispersion for the wavelength range 550-750 nm, whereas the film prepared using zinc nitrate has normal dispersion for the wavelength range 450-750 nm. The direct optical band gaps in the two films are estimated to be 3.01 eV and 3.00 eV, respectively. The change in film resistance with temperature has been explained on the basis of two competing processes, viz. thermal excitation of electrons and atmospheric oxygen adsorption, occurring simultaneously. The activation energies of the films in two different regions indicate the presence of two energy levels - one deep and one shallow near the bottom of the conduction band in the bandgap.     

Deposition of carbon films using close space sublimation

Carbon films are fabricated for the first time using an inexpensive and ecologically safe modified method of close space sublimation at atmospheric pressure. They are deposited onto quartz, glass, glass ceramic (Pyroceram), and silicon substrates. The main properties of the films (such as the growth rate, morphology and structure, optical properties, the dependences of these properties on the deposition temperature and the substrate material) are studied by X-ray diffraction, atomic force microscopy, multiangular ellipsometry, and the measurement of transmission and reflectance spectra in the visible and near ultraviolet regions. The growth rate is 5 nm/min at a film nucleation temperature of 800°C. The film thickness varies from 0.2 to 2.2 μm, and the minimum surface roughness is 0.5 nm. The refractive indices of the films range from 1.3 to 1.8 depending on the growth and subsequent heat treatment conditions. The optical energy gap is 5.4 eV.     

The morphology and structural properties of InP thin films deposited by spray pyrolysis method

InP film samples were prepared by spray pyrolysis technique using aqueous solutions of InCl₃ and Na₂HPO₄, which were atomized with compressed air as carrier gas onto glass substrates at 500 °C with different thicknesses of the films. The structural properties of the samples have been determined by using X-ray diffraction (XRD). It was found that the crystal structure of the InP films is polycrystalline hexagonal. The orientations for all the obtained films are along the c-axis perpendicular to the substrate. It is observed that the crystallite sizes of the films increase with the thickness of the film up to 616 nm. The changes observed in the morphology and structural phases related to the film thickness have been discussed in detail.     

石英衬底上GaN薄膜沉积及其光学性能的研究

GaN薄膜材料广泛应用于发光二极管(LED),激光二极管(LD)等光电器件。但是GaN基器件的制备与应用以及器件推广很大一部分取决于其器件的价格,常用的方式是在单晶蓝宝石衬底上沉积制备GaN薄膜样品,单晶蓝宝石衬底晶向择优,可以制备出高质量的GaN薄膜样品,但是单晶蓝宝石衬底价格昂贵,一定程度上限制了其GaN基器件推广使用。如何在廉价衬底上直接沉积高质量的GaN薄膜,满足器件的要求成为研究热点。石英玻璃价格廉价,但是属于非晶体,没有择优晶向取向,很难制备出高质量薄膜样品。本研究采用等离子体增强金属有机物化学气相沉积系统在非晶普通石英衬底上改变氮气反应源流量低温制备GaN薄膜材料。制备之后采用反射高能电子衍射谱、X射线衍射光谱、室温透射光谱和光致光谱对制备的薄膜进行系统的测试分析。其结果表明：在氮气流量适当的沉积参数条件下,所制备的薄膜具有高C轴的择优取向,良好的结晶质量以及优异的光学性能。     

Effect of Temperature and Oxygen on Luminescence Spectra and Polarization of Divinylbenzoxazolylbiphenyl Thin Films

H-type molecular aggregation as assembly with chromophore dipoles arranged parallel to each other has been observed in absorption and luminescence spectra of divinylbenzoxazolylbiphenyl thin films deposited on quartz glass substrate by thermovacuum method. The reversible changes of fluorescence anisotropy have been observed under film heating below the glass transition temperature correlating with lifetime changes. The addition of oxygen was found to cause an essential luminescence quenching. The hexyloxy group in the side chain of dibenzoxazolylbiphenyl molecule decreases H-type molecular aggregation and energy migration, and increases luminescence quenching induced by adsorbed oxygen owing to the formation of more porous film morphology.     

低温制备微晶硅薄膜生长机制的研究

采用热丝化学气相沉积技术制备了一系列处于不同生长阶段的薄膜样品，用原子力显微镜系 统地研究生长在单晶硅衬底和玻璃衬底上薄膜表面形貌的演化.按照分形理论分析得到：在 玻璃衬底上的硅薄膜以零扩散随机生长模式生长；而在单晶硅衬底上，薄膜早期以有限扩散 生长模式生长，当膜厚超过某一临界厚度时转变为零扩散随机生长模式.岛面密度与膜厚的 依赖关系表明，在临界厚度时硅衬底和玻璃衬底上的岛面密度均出现了极大值.Raman谱的测 量证实，玻璃衬底上薄膜临界厚度与非晶/微晶相变之间存在密切的关系.不同的衬底材料直 接影响反应 关键词： 生长机制 微晶硅薄膜 表面形貌 热丝化学气相沉积     

N掺杂ZnO薄膜的荧光特性研究

以N₂为掺杂源,通过改变O₂∶N₂比,利用射频磁控溅射法在玻璃衬底上制备了具有[002]择优取向的N掺杂ZnO薄膜,研究了ZnO薄膜的光致发光谱随着N掺入量的不同而变化的规律.结果表明,薄膜主衍射峰为402 nm处的发光峰;由于N掺杂量的不同,有的薄膜在445 nm和524 nm处也有发光发存在,但随着薄膜N含量的不同,其发光峰强度明显不同,其峰位也发生了相应的红移或者蓝移.当O₂∶N₂为10∶15时,制备的薄膜N掺杂量最大,光学性能最好,此工艺为研究ZnO薄膜的缺陷类型及导电类型提供了重要的研究参考.