Effect of oxygen partial pressure on the structural and optical properties of sputter deposited ZnO nanocrystalline thin films

We report the influence of deposition parameters such as oxygen partial pressure and overall sputtering pressure on the structural and optical properties of the as-grown ZnO nanocrystalline thin films. The films were prepared by dc magnetron sputtering using Zn metal target under two different argon and oxygen ratios at various sputtering pressures. Microstructure of the films was investigated using X-ray diffraction and scanning electron microscopy. Optical properties of the films were examined using UV-Visible spectrophotometer. The results show that the films deposited at low oxygen partial pressure (10%) contain mixed phase (Zn and ZnO) and are randomly oriented while the films deposited at higher oxygen partial pressure (30%) are single phase (ZnO) and highly oriented along the c-axis. We found that the oxygen partial pressure and the sputtering pressure are complementary to each other. The optical band gap calculated from Tauc's relation and the particle size calculation were in agreement with each other.     

Sulfidation growth and characterization of nanocrystalline ZnS thin films

Nanocrystalline ZnS thin films are prepared on glass and quartz substrates by sulfurizing ZnO thin films in the H₂S-containing mixture at 500 °C. These films are investigated by X-ray diffraction, scanning electron morphology, optical transmittance and photoluminescence spectra. The results show that the ZnS thin films have the hexagonal structure with a c-axis preferred orientation. Also, these nanostructure ZnS thin films with the grain size of ∼50 nm along the c-axis, exhibit the optical transparency as high as ∼80% in the visible region. It is found that sulfur replacement of oxygen sites in crystal lattices and recrystallization can take place during sulfidation, resulting in an evident increase of the grain size for the sulfurized films. Under the optimum sulfidation time of 2 h, the resultant ZnS thin films have a high crystallinity, low defect concentration and good optical properties with the band gap of 3.66 eV.     

Ag diffusion in ZnS thin films prepared by spray pyrolysis

ZnS thin films were deposited by spray pyrolysis method on glass substrates. Diffusion of Ag in ZnS thin films was performed in the temperature range 80-400 °C under a nitrogen atmosphere. The diffusion of Ag is determined with XRF, and the obtained concentration profile allows to calculate the diffusion coefficient. The temperature dependence of Ag diffusion coefficient is determined by the equation D = 8 × 10^− 9 exp(− 0.10 eV / kT). It was found that the as-grown undoped high resistive n-type ZnS thin films were converted to the p-type upon Ag doping with a slight increase in resistivity only by rapid thermal annealing at 400 °C in N₂ atmosphere. In addition, the band gap of the p-type film was decreased as compared with the undoped sample annealed under the same conditions. The results were attributed to the migration of Ag atoms in polycrystalline ZnS films by means of both along intergrain surfaces and intragrain accompanied by interaction with native point defect.     

Modification of sputter deposited solid-state electrolyte thin films

All solid-state thin film batteries (TFBs) consisting of amorphous lithium phosphorus oxynitride (LiPON) solid electrolyte, crystalline LiMn₂O₄ cathode and crystalline SnO₂ anode have been fabricated and characterized. All of the thin films are prepared by RF magnetron sputtering. By fabricating under different pressures and applying low temperature post-annealing (200 °C), the performances of the LiPON electrolytes and SnO₂/LiPON/LiMn₂O₄ TFBs are improved. Suitable working pressures results in pinhole-free amorphous LiPON films with smooth surface and dense micro-structure. The TFBs post-annealed at 200 °C show smooth interface contacts between electrode and electrolyte thin films. The low pressure deposited and post-annealed TFBs exhibits lower impedance and higher cycling stability. Initial open-circuit voltage of 3.8 V and initial capacity of 12 μAh/cm² are obtained.     

Biaxial alignment in sputter deposited thin films

Biaxially aligned thin films have not only a preferential crystallographic out-of-plane orientation, but also have an alignment along a certain reference direction parallel to the substrate plane. This type of film has been obtained by unbalanced reactive magnetron sputter deposition on both amorphous glass and randomly textured polycrystalline substrates tilted with respect to the incoming material flux.First, we focus on the development of microstructure and crystallographic out-of-plane orientation. The results are summarized in an extended structure zone model. Based on experimental results, a mechanism for the in-plane alignment is proposed which shows that an in-plane alignment can only be obtained when an overgrowth mechanism drives the microstructural evolution of the thin film. The quality of the in-plane alignment can be evaluated from X-ray diffraction pole figures. The influence of several deposition parameters (target-substrate distance, target-substrate angle, deposition pressure, and substrate bias) on the degree of in-plane alignment is discussed. The influence of these parameters can be traced to the influence of two main properties, i.e. the mobility of the adatoms at the growing surface and the angular spread of the incoming material flux. Finally, since impurities are hard to exclude during deposition, their influence on the microstructure, the preferential out-of-plane orientation, and the in-plane alignment is reported.     

ZnS薄膜的制备及性能研究

用射频溅射法在Si基片和石英基片上分别制备了490nm厚的ZnS薄膜,并在不同温度下进行退火处理.微结构分析表明:退火后的ZnS薄膜均呈多晶状态,晶体结构为立方闪锌矿结构的β-ZnS;随着退火温度的升高,薄膜的平均晶粒尺寸逐渐增大,由20℃的10.91nm增大到500℃的15.59nm,晶格常数在不同退火温度下均比标准值0.5414nm稍小.应力分析表明:退火后的ZnS薄膜应力减小,400℃时分布较均匀,平均应力为1.481×108Pa,应力差为1.939×108Pa.且400℃前为张应力,400℃以后转变为压应力.光学分析表明,随着退火温度的升高,ZnS薄膜的透过率增强,吸光度减弱.     

Preparation and properties of ZnO thin films deposited by sol-gel technique

Zinc oxide (ZnO) thin films were deposited on (100) Si substrates by sol-gel technique. Zinc acetate was used as the precursor material. The effect of different annealing atmospheres and annealing temperatures on composition, structural and optical properties of ZnO thin films was investigated by using Fourier transform infrared spectroscopy, X-ray diffraction, atomic force microscopy and photoluminescence (PL), respectively. At an annealing temperature of 400°C in N₂ for 2 h, dried gel films were propitious to undergo structural relaxation and grow ZnO grains. ZnO thin film annealed at 400°C in N₂ for 2 h exhibited the optimal structure and PL property, and the grain size and the lattice constants of the film were calculated (41.6 nm, a = 3.253 ? and c = 5.210 ?). Moreover, a green emission around 495 nm was observed in the PL spectra owing to the oxygen vacancies located at the surface of ZnO grains. With increasing annealing temperature, both the amount of the grown ZnO and the specific surface area of the grains decrease, which jointly weaken the green emission. Translated from Journal of Lanzhou University (Natural Science), 2006, 42(1): 67–71 [译自: 兰州大学学报 (自然科学版)]     

Physical properties of very thin SnS films deposited by thermal evaporation

SnS films with thicknesses of 20-65 nm have been deposited on glass substrates by thermal evaporation. The physical properties of the films were investigated using X-ray diffraction (XRD), scanning electron microscopy, X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and ultraviolet-visible-near infrared spectroscopy at room temperature. The results from XRD, XPS and Raman spectroscopy analyses indicate that the deposited films mainly exhibit SnS phase, but they may contain a tiny amount of Sn₂S₃. The deposited SnS films are pinhole free, smooth and strongly adherent to the surfaces of the substrates. The color of the SnS films changes from pale yellow to brown with the increase of the film thickness from 20 nm to 65 nm. The very smooth surfaces of the thin films result in their high reflectance. The direct bandgap of the films is between 2.15 eV and 2.28 eV which is much larger than 1.3 eV of bulk SnS, this is deserving to be investigated further.     

ZnS薄膜的水浴法制备及其光学性能

以酒石酸和柠檬酸钠为络合剂,采用水浴法(CBD)制备ZnS薄膜.利用X射线衍射(XRD)、X射线能谱仪(EDAX)、扫描电镜(SEM)、紫外-可见分光光度计(UV-vis)研究ZnS薄膜的结构、成分、形貌及光学性能.利用透射光谱计算了ZnS薄膜的光学禁带宽度.结果表明:ZnS薄膜呈立方相晶体结构,水浴沉积时间为3h的ZnS薄膜原子比Zn∶S为1∶0.85,薄膜表面均一致密,在可见光区有着好的透射性能,在300～800 nm的光谱范围内平均透射率达到80.8%,光学禁带宽度为3.78eV,适合作为太阳能电池过渡层.     

Investigation of the effect of temperature on growth mechanism of nanocrystalline ZnS thin films

In this paper the temperature effect on the growth mechanism of ZnS thin films prepared in a chemical bath containing zinc acetate, ethylenediamine, and thioacetamide aqueous solutions has been studied in the temperature range between 25 and 75 °C. These ZnS thin films possess a nanocrystalline structure, exhibit quantum size effects due to the small crystal size and produce a blue shift in the optical spectra. This blue shift was attributed to a decrease in crystal size by using X-ray diffraction and scanning electron microscopy. The growth mechanism of the thin films is suggested to proceed by two fundamental steps: in the first step, the ZnS nanocrystallites coalesce into small grains through homogeneous nucleation in the solution phase. In the second step, eventually, these small grains or large-sized clusters diffuse and stick to the surface of the substrate to form the ZnS thin film, in a way called a cluster-by-cluster manner, resulting in particulate thin film.     

Morphology of sputter deposited Al alloy films

Morphology of Al–2.0at%Ta and Al–2.0 at.% Nd alloy films before and after annealing was investigated for applications of interconnections for liquid crystal displays. It was found that the morphology and the microstructure of Al–2.0 at.% Nd alloy films changed markedly by annealing at the temperature region from 200°C to 300°C, while the morphology of Al–2.0 at.% Ta alloy films did not change by annealing up to 400°C. For the case of Al–2.0 at.% Nd alloy films, the incline of the <111> fiber texture to the substrate normal was observed during annealing. Structural characteristics of the Al films were investigated by TEM, SAD and XRD to determine the influence of alloying elements on the morphology and the fiber texture. From these results, it was concluded that the microstructures strongly influence the morphology and the grain orientation of Al alloy films.     

Size dependent optical characteristics of chemically deposited nanostructured ZnS thin films

ZnS thin films of different thicknesses were prepared by chemical bath deposition using thiourea and zinc acetate as S²⁻ and Zn²⁺ source. The effect of film thickness on the optical and structural properties was studied. The optical absorption studies in the wavelength range 250–750 nm show that band gap energy of ZnS increases from 3·68–4·10 eV as thickness varied from 332–76 nm. The structural estimation shows variation in grain size from 6·9–17·8 nm with thickness. The thermoemf measurement indicates that films prepared by this method are of n-type.     

Substrate temperature influence on ZnS thin films prepared by ultrasonic spray

ZnS thin films were deposited by ultrasonic spray technique. The starting solution is a mixture of 0.1 M zinc chloride as source of Zn and 0.05 M thiourea as source of S. The glass substrate temperature was varied in the range of 250 °C-400 °C to investigate the influence of substrate temperature on the structure, chemical composition and optical properties of ZnS films. The DRX analyses indicated that ZnS films have nanocrystalline hexagonal structure with (002) preferential orientation and grain size varied from 20 to 50 nm, increasing with substrate temperature. The optical films characterization was carried out by the UV-visible transmission. The optical gap and films disorder were deduced from the absorption spectra and the refractive indices of the films were determined by ellipsometric measurements. It is shown that the obtained films are generally composed of ZnO and ZnS phases with varied proportion, while at deposition temperature of 400 °C, they are near stoichiometric ZnS.     

Dielectric oxynitride LaTiOxNy thin films deposited by reactive radio-frequency sputtering

LaTiO_xN_y thin films have been deposited by RF sputtering on (001) Nb-doped SrTiO₃ and (001) MgO single-crystalline substrates at high temperature (T_S = 800 °C) under different nitrogen ratios in the plasma (vol.% N₂ = 0, 25, 71). The band gaps ranged from E_g = 3.30 eV for the epitaxial transparent film containing no nitrogen to E_g = 2.65 eV for the textured coloured film containing a moderate amount of nitrogen. Dielectric characterization in the frequency range [100 Hz-1 MHz], using a metal-insulator-metal structure, has shown a stable permittivity and loss tangent of the epitaxial low-nitrided LaTiO_xN_y film with values of ε′ = 135 and tanδ = 1.2 10^− 2 at 100 kHz (RT).     

Hardness of sputter deposited nanocrystalline Ni3Al thin films

Nanocrystalline thin films of nominal composition Ni-25 at.% Al have been sputter deposited from a target of the intermetallic compound Ni₃Al using different sputtering conditions. Increase in the pressure of sputtering gas resulted in a substantial reduction in the grain size of these nanocrystalline films and a consequent enhancement in their hardness. While films deposited onto heated substrates exhibited larger grain sizes as compared to those deposited on unheated substrates at the same sputtering pressure, the hardness of the former films was substantially higher. The reason for this enhanced hardness is the long-range chemical ordering in films deposited on heated substrates and the formation of L1₂-Ni₃Al, the thermodynamically stable phase for this composition.     

Mechanical and deformation behaviour of titanium diboride thin films deposited by magnetron sputtering

Nanoindentation studies have been carried out for TiB₂ films deposited on Si, glass and steel by sputtering for studying the influence of the substrates. It was observed that the modulus of the film was influenced by the substrates from 30 nm onwards. Plastic energy analysis has shown that as load increases more energy is absorbed by the substrate. Quantitative indentation depth limits for obtaining film only hardness, using a combination of log-log plot of load vs displacement and load vs (displacement)² functions, have shown the dependence on the threshold load for crack formation. Comparison of the hardness data with composite hardness models has been performed. Fracture toughness of the coatings was also evaluated using two methods which resulted in comparable results.     

Morphology and growth of e-beam deposited YSZ thin films

Yttria-stabilized zirconium (YSZ) thin films were grown from the tetragonal phase of ZrO₂ stabilized by 8 wt% of Y₂O₃ (8% of YSZ) ceramic powders using e-beam deposition technique (EB-PVD). The influence of the type of substrate on the microstructure of deposited YSZ thin films was analysed. YSZ thin films (2-3 μm of thickness) were deposited on three different types of substrates: optical quartz (SiO₂), porous Ni-YSZ substrates and Alloy 600 (Fe-Ni-Cr). The dependence of the substrate temperature (from 20 to 600 °C) on the thin film structure and the surface morphology were investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM). It was found that (i) the substrate temperature has an influence on the crystallite size, which varied between 12 and 50 nm, (ii) the substrate type has an influence on the growth mechanism of YSZ thin films, and (iii) a bias voltage applied to the substrate during the deposition of thin films has an influence on the densification of YSZ layers.     

化学水浴法制备ZnS薄膜光学性能

利用薄膜分析系统测量不同沉积时间制备的ZnS薄膜透射谱,通过分析薄膜透射谱,来确定ZnS薄膜光学常数和禁带宽度.实验结果表明,在线性生长阶段,薄膜的沉积速率大约为1 nm/min,具有很好的线性关系,沉积0.5 h的ZnS薄膜在可见光范围内光透过率为82%左右.     

Studies on sputtering process of multicomponent Zr-Ti-Cu-Ni-Be alloy thin films

Sputter deposition process of a multicomponent Zr-Ti-Cu-Ni-Be metallic alloy has been studied experimentally and by numerical simulations. Monte-Carlo simulations were performed using a model based on thermalization and diffusion of sputtered atoms. Incident energy and angle of sputtered atoms on substrate were obtained from simulations. The incident angular distribution was observed to be a normal distribution at all sputtering pressures. Average incident kinetic energy of the condensing atoms on the substrate was observed to be 0.2-0.3 eV indicating most of them are thermalized. Simulations were extended to predict compositional variations in films prepared at various process conditions. These results were compared with composition of films determined experimentally using Rutherford Backscattering Spectrometry (RBS). Contents of Zr, Ti, Cu and Ni quantified using RBS were in moderate agreement with the simulated composition. Be could not be quantified accurately by RBS largely due to very low energy peak of Be in the spectrum. These studies are shown to be useful in understanding the complexities in multicomponent sputtering.     

Influence of substrate temperature on N-doped ZnO films deposited by RF magnetron sputtering

Nitrogen-doped ZnO films were deposited by RF magnetron sputtering in 75% of N₂ / (Ar + N₂) gas atmosphere. The influence of substrate temperature ranging from room temperature (RT) to 300 °C was analyzed by X-ray diffractometry (XRD), spectrophotometry, X-ray photoelectron spectroscopy (XPS), secondary-ion mass spectrometry (SIMS) and Hall measurements setup. The XRD studies confirmed the hexagonal ZnO structure and showed that the crystallinity of these films increased with increasing substrate temperature (T_s). The optical studies indicate the average visible transmittance in the wavelength ranging 500-800 nm increases with increasing T_s. A minimum transmittance (9.84%) obtained for the films deposited at RT increased with increasing T_s to a maximum of 88.59% at 300 °C (500-800 nm). Furthermore, it was understood that the band gap widens with increasing T_s from 1.99 eV (RT) to 3.30 eV (250 °C). Compositional analyses (XPS and SIMS) confirmed the nitrogen (N) incorporation into the ZnO films and its decreasing concentration with increasing T_s. The negative sign of Hall coefficients confirmed the n-type conducting.