Growth of n-type ZnO thin films by using mixture gas of hydrogen and argon

High-quality oxide semiconductor ZnO thin films were prepared on single-crystal sapphire and LaAlOZnO薄膜 氩氢混合气体 薄膜生长 异质结构 薄膜物理学ZnO, PLD, heterostructureProject supported by the National Natural Science Foundation of China (Grant No 19974001) and the National Key Basic Research Special Foundation of China (Grant No NKBRSF G1999064604 and G2000036505).2005-05-309/3/2005 12:00:00 AMHigh-quality oxide semiconductor ZnO thin films were prepared on single-crystal sapphire and baAlO3 substrates by pulsed laser deposition （PLD） in the mixture gas of hydrogen and argon. Low resistivity n-type ZnO thin films with smoother surface were achieved by deposition at 600℃ in 1Pa of the mixture gas. in addition, ferromagnetism was observed in Co-doped ZnO thin films and rectification Ⅰ - Ⅴ curves were found in p-GaN/n-ZnO and p-CdTe/n-ZnO heterostructure junctions. The results indicated that using mixture gas of hydrogen and argon in PLD technique was a flexible method for depositing high-quality n-type oxide semiconductor films, especially for the multilayer thin film devices.     

外加气流对脉冲激光烧蚀制备纳米Si晶粒尺寸分布的影响

提出一种控制脉冲激光烧蚀制备纳米Si晶粒尺寸分布的新方法。在10Pa的Ar环境中,采用脉冲激光烧蚀高阻抗单晶硅靶沉积制备了纳米Si晶薄膜。在羽辉正上方2.0cm,距靶0.3～3.0cm范围内的不同位置引入氩气流,在烧蚀点正下方2.0cm处水平放置单晶Si(111)衬底来收集制备的纳米Si晶粒。利用扫描电子显微镜观察样品表面形貌,并对衬底不同位置上纳米Si晶粒进行统计。结果表明:在不引入气流时,晶粒的尺寸随靶衬间距的增加先增大后减小,晶粒尺寸峰值出现在距靶1.7cm处;引入气流后,晶粒尺寸分布发生变化,在距靶1.7cm引入气流时晶粒尺寸峰值最大,在距靶3.0cm引入气流时晶粒尺寸峰值最小,且出现晶粒尺寸峰值的位置随着引入气流位置的增加而增大。     

低压下气流对激光沉积纳米硅晶化及尺寸的影响

纳米硅具有明显的光致发光效应和量子尺寸效应,广泛的应用在现代电子工业和太阳能光伏工业中.尺寸影响着纳米硅的实际用途,因此制备尺寸可控的纳米硅晶粒具有很重要的实际意义.本文采用脉冲激光沉积(PLD)技术,在烧蚀点水平方向、距靶2 cm处引入一束流量为5 sccm的氩(Ar)气流,在0.01-0.5 Pa的Ar气压下烧蚀高阻抗单晶硅(Si)靶.在管口正下方1 cm处水平放置衬底来沉积纳米Si薄膜;并用同一装置,在0.08 Pa的Ar气压下分别引入流量为0,2.5,5,7.5,10 sccm的Ar气流沉积纳米Si薄膜.利用原子力显微镜(AFM)、X射线衍射(XRD)、Raman散射对样品表面形貌和微观结构进行分析表征.结果表明:不引入气流时出现纳米Si晶粒的阈值气压是0.1Pa,引入气流后出现纳米Si晶粒的阈值气压为0.05 Pa.晶粒尺寸随着气流流量的增大而减小.     

Effect of argon ion activity on the properties of Y2O3 thin films deposited by low pressure PACVD

Yttrium oxide thin films are deposited by microwave electron cyclotron resonance (ECR) plasma assisted metal organic chemical vapour deposition process using an indegeneously developed Y(thd)₃ {(2,2,6,6-tetramethyl-3,5-heptanedionate)yttrium} precursor. Depositions were carried out at two different argon gas flow rates keeping precursor and oxygen gas flow rate constant. The deposited coatings are characterized by X-ray photoelectron spectroscopy (XPS), glancing angle X-ray diffraction (GIXRD) and infrared spectroscopy. Optical properties of the films are studied by spectroscopic ellipsometry. Hardness and elastic modulus of the films are measured by load depth sensing nanoindentation technique. Stability of the film and its adhesion with the substrate is inferred from the nanoscratch test.It is shown here that, the change in the argon gas flow rates changes the ionization of the gas in the microwave ECR plasma and imposes a drastic change in the characteristics like composition, structure as well as mechanical properties of the deposited film.     

Deposition and characterization of sputtered ZnO films

Zinc oxide thin films were deposited by radio frequency magnetron sputtering at room temperature using a metallic zinc target in a gas mixture of argon and oxygen. Plasma power, oxygen /argon gas ratio, gas pressure, and substrate temperature were varied, and an experimental design method was used to optimize these deposition parameters by considering their interdependence. Crystalline structures and film stresses were examined. Post-deposition rapid thermal annealing was also carried out to observe its effects on the film properties. Statistical analysis was then used to find the optimal sputtering conditions. Results indicated that plasma power and gas pressure have the largest effects on film crystallization and stress and that postdeposition annealing can be used to improve the quality of the film properties.     

靶压对磁控溅射GeC薄膜折射率的影响

采用磁控溅射技术,以碳氢气体和氩气为工作气体,在Ge基底上制备了GeC薄膜。研究了靶压对薄膜折射率的影响,发现在较高的靶压下制备的GeC薄膜具有较低的折射率,而在较低的靶压下则得到了高折射率的薄膜。通过控制溅射靶压,制备了折射率在2．5～3．8之间可变的GeC薄膜。利用拉曼光谱研究了GeC薄膜的结构。薄膜样品的硬度测试表明,较低折射率的GeC薄膜具有较高的硬度。     

DC magnetron sputtered tungsten: W film properties and electrical properties of W/Si Schottky diodes

Deposition of metallic tungsten (W) thin films on silicon substrates has been carried out using dc magnetron sputtering in argon or xenon gas. The deposition of W films was investigated at various working gas pressures, while the entire deposited W films were obtained at fixed power. The stress, resistivity, and structure of the W films were systematically determined as a function of the pressure of both argon and xenon. A compressive-to-tensile stress transition is observed as the working gas pressure is increased. The transition occurs at a critical pressure and coincides with a significant decrease of the grain size and an increase of the W-film resistivity. The stress transition of W-sputtered films with argon is associated with the transformation of -W phase into -W phase. The films deposited in xenon always exhibit the -W structure. In addition, a change in the Schottky barrier height (SBH) on n-type silicon of about 40±10 meV is observed at the critical pressure. On the other hand, the barrier height on the p-type silicon remains constant under all the experimental conditions investigated. These last results indicate that the Fermi level at the interface is pinned with respect to the valence band edge. The observed variation of the barrier height on n-type Si is discussed in terms of defects, change of the work function of the metal (W), and modification of the band gap of Si. PACS 72.20.-i; 73.30.+y; 73.20.-m     

Characterization of DC reactive magnetron sputtered NiO films using spectroscopic ellipsometry

Thin NiO films were deposited at 500 °C on n-type Si(1 1 1) by a DC reactive magnetron sputtering in a gas mixture of oxygen and argon. The ratio between the flow rates of oxygen and argon was respectively set at 1:4, 1:2, and 1:1. The dependence of structures and optical properties of NiO films were investigated using grazing incidence X-ray diffraction and spectroscopic ellipsometry in the spectral region of 1.5-5.0 eV. Ni-rich NiO films were obtained when the ratio between the flow rates of oxygen and argon was 1:4 and 1:2 in sputtering process. And when the ratio was 1:1, a relatively pure NiO film was formed. The partial pressure of oxygen could significantly influence the thickness and roughness of films. Refractive index n, extinction coefficient k, and direct gap energy and indirect gap energy of the NiO films were also subject to the influence of the partial pressure of oxygen.     

Electron microprobe compositional analysis of sputtered tantalum-aluminium films

In the present paper the methods for measurement of the composition of two or more component tantalum-based thin sputtered films are summarized. The influence of the target construction on the composition of the films is discussed. The Ta-Al films were sputtered from composite Ta-Al targets. The composition of films was measured by means of the electron microprobe technique. From results it follows that using the composite targets for sputtering in argon at a pressure of 2×10^?2 torr and in its mixture with nitrogen (10^?3 torr), the composition of Ta-Al films is proportional to the ratio of the Ta and Al exposed surfaces on the target. The proportionality factor equals to the ratio of “effective” sputtering yields of target components measured at given sputtering conditions. The presence of nitrogen in sputtering gas decreases the value of Ta yield 2.2 times. If a small Al surface is sputtered together with much larger Ta surface, the sputtering yield of Al remains unchanged. In Ta-Al films the occluded argon was qualitatively determined. The presence of nitrogen was not proved. This seems to be caused by the absorption of nitrogen characteristic radiation in the investigated films.     

Magnetic properties of anisotropic Pr–Fe–B films with different deposition rates and pressures

Anisotropic Pr–Fe–B films with hard magnetic properties have been prepared by DC magnetron sputtering on heated Si (100) substrates. The influences of thickness, deposition rate and sputtering gas pressure on the magnetic properties of Pr–Fe–B films were investigated. It is found that the magnetic properties are sensitive to deposition rate and sputtering gas pressure. High deposition rate and argon pressure result in a high coercivity and a low remanence.     

The influence of residual gas on boron carbide thin films prepared by magnetron sputtering

Boron carbide (B₄C) thin films were prepared by magnetron sputtering and residual gas impurities in the films were analyzed by X-ray photoelectron spectroscopy. The impurities, mainly oxygen, decrease with improving vacuum. By using argon ion beam etching of the films, the atomic concentration was measured as a function of etching depth. The binding energy spectra were analyzed using wavelet transform and curve fitting, showing that most of the oxygen impurity is in the form of boron oxides, and that the impurities are physically trapped among columnar structures in the film. In order to improve the base vacuum before coating the film, a range of methods were used, including argon gas filling on the target surface and titanium pre-sputtering. The experimental results show that the latter is an efficient and feasible method. Based on the titanium pre-sputtering technology, the optical performance of W/B₄C multilayer was improved so much.     

Optimum packing density and crystal structure of tin-doped indium oxide thin films for high-temperature annealing processes

The influence of high-temperature annealing on the electrical properties and microstructure of tin-doped indium oxide (ITO) thin films was investigated as a function of oxygen gas flow ratio to argon gas during the sputtering deposition. The ITO thin films were annealed at 500 °C in air after the deposition. It was found that the ITO thin films, which were deposited in relatively low oxygen gas flow ratio, exhibited high Hall mobility and low-resistivity after the annealing. Furthermore, the X-ray reflectivity and diffraction measurement revealed that the ITO thin film with low-resistivity after annealing exhibited high packing density, smooth surface and low crystallization degree. It can be considered that the carrier electron scattering was suppressed with increasing in the packing density of the ITO thin film; as a result, the Hall mobility and resistivity were improved.     

Thick c-BN films deposited by radio frequency magnetron sputtering in argon/nitrogen gas mixture with additional hydrogen gas

The excellent physical and chemical properties of cubic boron nitride(c-BN) film make it a promising candidate for various industry applications. However, the c-BN film thickness restricts its practical applications in many cases. Thus, it is indispensable to develop an economic, simple and environment-friend way to synthesize high-quality thick, stable c-BN films. High-cubic-content BN films are prepared on silicon(100) substrates by radio frequency(RF) magnetron sputtering from an h-BN target at low substrate temperature. Adhesions of the c-BN films are greatly improved by adding hydrogen to the argon/nitrogen gas mixture, allowing the deposition of a film up to 5-μm thick. The compositions and the microstructure morphologies of the c-BN films grown at different substrate temperatures are systematically investigated with respect to the ratio of H_2 gas content to total working gas. In addition, a primary mechanism for the deposition of thick c-BN film is proposed.     

Surface properties of platinum thin films as a function of plasma treatment conditions

We examined the surface properties of platinum (Pt) thin films exposed to oxygen and argon plasma treatments and compared them to as-deposited Pt films. The surface wetting properties, refractive index and extinction coefficient of the Pt films were monitored as a function of time after different plasma treatments. Surfaces treated with an oxygen plasma were dramatically different from as-deposited Pt, whereas argon plasma treated surfaces were similar to as-deposited films. X-ray photoelectron spectroscopy confirmed the formation of platinum oxide on films treated with an oxygen plasma, while such oxide diminished after argon plasma treatment. Surface morphology studied with atomic force microscopy indicated a strong dependence of the surface roughness of the Pt films on the power and duration of the argon plasma used for the treatment. Based on these studies, an oxygen plasma treatment followed by a brief low-power argon plasma etch was developed for the purpose of regenerating clean and metallic Pt surfaces, and at the same time providing the smoothest possible surface morphology.     

XPS investigations achieved on the first cycle of V2O5 thin films used in lithium microbatteries

Vanadium pentoxide thin films, usable as positive electrode in microbatteries, have been prepared by radio frequency magnetron sputtering in a pure argon or mixed argon/oxygen plasma. Depending on the oxygen pressure in the discharge gas, we have obtained either crystallized or amorphous thin films. These two kinds of thin films having different electrochemical behavior, an extensive X-ray photoelectron spectroscopy (XPS) study (especially suited for thin films analysis) was carried out. The main redox processes occurring during the first discharge–charge cycle were identified. In addition, depending on the crystalline or amorphous character of the samples, we have noticed some differences concerning the kinetic of reduction. Furthermore, the growth of a surface layer between the cathode and the liquid electrolyte was evidenced upon the discharge as well as its partial dissolution upon the charge.     

Effects of oxygen partial pressure on optical properties of NiOX films deposited by reactive DC-magnetron sputtering

The influence of oxygen partial pressure on the optical properties of NiOX thin films deposited by reactive DC-magnetron sputtering from a nickel metal target in a mixture gas of oxygen and argon was presented.With the oxygen ratio increasing, the reflectivity of the as-deposited films decreased, and optical band gap increased. Thermogravimetric analysis (TGA) showed that the decompose temperature of the films was above 250 ℃. After annealed at 400 ℃, only films deposited at 5% O2/Ar ratio showed high opticalcontrast which was about 52%. Scanning electron microscope (SEM) results revealed that the changes ofsurface morphology were responsible for the optical property variations of the films after annealing. Itsthermal stability and high optical contrast before and after annealing made it a good potential write-onceoptical recording medium.     

Characterization of nanocrystalline gold/DLC composite films synthesized by plasma CVD technique

Composite films containing gold nanoparticles embedded in diamond-like carbon (Au-DLC) matrix were deposited on glass and Si (1 0 0) substrates by using capacitatively coupled plasma (CCP) chemical vapour deposition technique (CVD). Particle size and metal volume fraction were tailored by varying the relative amount of argon in the methane + argon gas mixture in the plasma. Optical constants of the films were evaluated. Bonding environment in these films were obtained from Raman and Fourier transformed infrared spectra (FTIR) studies. Blue-shift of the surface plasmon resonance peak in the optical absorbance spectra of the films could be associated with the reduction of the particle size while red shift was observed with the increase in volume fraction of metal particles in the DLC films. Absorption spectra recorded in the reflection mode indicated dichromatism in these films.     

Surface modification of polypropylene with an atmospheric pressure plasma jet sustained in argon and an argon/water vapour mixture

In this paper, an atmospheric pressure plasma jet sustained in pure argon and an argon/water vapour mixture has been used to modify the surface of polypropylene (PP) films. The gas temperature of the plasma jet was found to be 625 K in an active zone between the electrodes and was found to increase in the afterglow. Based on these results, the PP films are placed as close as possible to the edge of the capillary in order to avoid thermal damage to the polymer. XPS results on the untreated and modified PP samples revealed incorporation of a significant amount of oxygen on the polymer surface, however, this oxygen inclusion is more pronounced for the argon/water vapour jet due to the higher radicals density in the jet afterglow. One can therefore conclude that adding water vapour to an argon plasma jet can be a convenient way to increase the efficiency of plasma surface modification.     

H2 气对脉冲磁控溅射铝掺杂氧化锌薄膜性能的影响

实验采用脉冲磁控溅射法制备铝掺杂氧化锌(AZO)薄膜.为了进一步提高AZO薄膜的光电性能,在溅射过程中加入一定流量的氢气,以高纯ZnO ∶Al₂O₃陶瓷靶为溅射靶材,制备AZO/H透明导电薄膜.通过测试薄膜的结构特性、表面形貌及其光电性能,详细地研究了氢气流量对AZO薄膜性能的影响.溅射过程中引入氢气,可以促进薄膜的晶化,提高薄膜的迁移率和透过率(400—1100 nm).采用纯氩气溅射制备AZO薄膜的电阻率为5.664×10^-4 Ω·cm 关键词： 氧化锌 氢气流量 磁控溅射 太阳电池     

Study of hysteresis behavior in reactive sputtering of cylindrical magnetron plasma

In order to make sufficient use of reactive cylindrical magnetron plasma for depositing compound thin films, it is necessary to characterize the hysteresis behavior of the discharge. Cylindrical magnetron plasmas with different targets namely titanium and aluminium are studied in an argon/oxygen and an argon/nitrogen gas environment respectively. The aluminium and titanium emission lines are observed at different flows of reactive gases. The emission intensity is found to decrease with the increase of the reactive gas flow rate. The hysteresis behavior of reactive cylindrical magnetron plasma is studied by determining the variation of discharge voltage with increasing and then reducing the flow rate of reactive gas,while keeping the discharge current constant at 100 m A. Distinct hysteresis is found to be formed for the aluminium target and reactive gas oxygen. For aluminium/nitrogen, titanium/oxygen and titanium/nitrogen, there is also an indication of the formation of hysteresis; however, the characteristics of variation from metallic to reactive mode are different in different cases. The hysteresis behaviors are different for aluminium and titanium targets with the oxygen and nitrogen reactive gases, signifying the difference in reactivity between them. The effects of the argon flow rate and magnetic field on the hysteresis are studied and explained.