Evolutions of residual stress and microstructure in ZrO2 thin films deposited at different temperatures and rates

The residual stress in ZrO₂ thin films prepared by electron beam evaporation was measured by viewing the substrate deformation using an optical interferometer. The influences of deposition temperature and deposition rate on the residual stress have been studied. The results show that residual stress in ZrO₂ thin films varies from tensile to compressive depending on deposition temperature and deposition rate, respectively. The value of compressive stress increases with the increasing of deposition temperature and deposition rate. At the same time, X-ray diffraction measurement was carried out in order to examine the crystallization behavior of the ZrO₂ thin films as a function of deposition temperature and deposition rate. The relationship between the residual stress and the microstructure has also been discussed.     

Fabrication of YSZ thin films from suspension by electrostatic spray deposition

This work describes a novel fabrication technique to prepare yttria-stabilized zirconia (YSZ) thin films by electrostatic spray deposition (ESD) from suspension. A detailed discussion on the formulation of colloidally stable suspension to prepare dense and uniform YSZ thin films is presented in this study. X-ray diffraction (XRD) and scanning electron microscopy (SEM) are used to analyze the structure and morphology of the YSZ thin films. The results show that a mixture of acetylacetone and ethanol in a ratio of 1:1 by volume is an effective suspension medium for YSZ fine particles to produce colloidally stable suspension, and the YSZ thin films with uniform in thickness about 2 μm and densely packed can be obtained by ESD from the suspension.     

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.     

Y2O3 stabilized ZrO2 thin films deposited by electron-beam evaporation: Optical properties, structure and residual stresses

This paper describes the preparation and the characterization of Y₂O₃ stabilized ZrO₂ thin films produced by electric-beam evaporation method. The optical properties, microstructure, surface morphology and the residual stress of the deposited films were investigated by optical spectroscopy, X-ray diffraction (XRD), scanning probe microscope and optical interferometer. It is shown that the optical transmission spectra of all the YSZ thin films are similar with those of ZrO₂ thin film, possessing high transparency in the visible and near-infrared regions. The refractive index of the samples decreases with increasing of Y₂O₃ content. The crystalline structure of pure ZrO₂ films is a mixture of tetragonal phase and monoclinic phase, however, Y₂O₃ stabilized ZrO₂ thin films only exhibit the cubic phase independently of how much the added Y₂O₃ content is. The surface morphology spectrum indicates that all thin films present a crystalline columnar texture with columnar grains perpendicular to the substrate and with a predominantly open microporosity. The residual stress of films transforms tensile from compressive with the increasing of Y₂O₃ molar content, which corresponds to the evolutions of the structure and packing densities.     

氧分压对掺钼氧化铟透明导电薄膜光电性能的影响

采用射频磁控反应溅射法在k9玻璃衬底上制备了In2O3∶Mo(IMO)透明导电薄膜,分析了不同氧分压条件下IMO薄膜的晶体结构、化学成分及光电性能.结果表明:不同氧分压下制备的IMO薄膜具有不同晶粒的取向性;随着氧分压的增加,薄膜的载流子浓度、载流子迁移率先增加后减小;薄膜的电阻率呈现先增加再减少然后再增加的趋势.在可...     

Comparison of residual stress measurement in thin films using surface micromachining method

Conductive, dielectric, semiconducting, piezoelectric and ferroelectric thin films are extensively used for MEMS/NEMS applications. One of the important parameters of thin films is residual stress. The residual stress can seriously affect the properties, performance and long-term stability of the films. Excessive compressive or tensile stress results in buckling, cracking, splintering and sticking problems. Stress measurement techniques are therefore essential for both process development and process monitoring. Many suggestions for stress measurement in thin films have been made over the past several decades. This paper is concentrated on the in situ stress measurement using surface micromachining techniques to determine the residual stress. The authors review and compare several types of stress measurement methods including buckling technique, rotating technique, micro strain gauge and long-short beam strain sensor.     

沉积气压对电弧离子镀制备MgO薄膜的结构及性能的影响

采用阴极真空电弧离子沉积技术在玻璃及Si衬底上成功地制备了具有择优结晶取向的透明MgO薄膜。利用X射线衍射仪（XRD）、扫描电子显微镜（SEM）及紫外-可见吸收光谱仪分别对MgO薄膜微观结构、表面形貌及可见光透过率进行了测试与分析。XRD结果表明,所制备的MgO薄膜具有NaCl型立方结构的（100）、（110）和（111）3种结晶取向,在沉积气压为0.7～3.0Pa的范围内,薄膜的择优结晶取向随沉积气压的升高先由（100）转变为（110）,最后变为（111）。SEM图表明随着沉积气压的升高,MgO薄膜的晶粒逐渐变小,薄膜结晶质量变差。在380～900nm范围内,沉积气压为0.7Pa下制备的MgO薄膜其可见光透过率高于90%,随着沉积气压的升高,薄膜的可见光透过率有所下降。     

氮流量对TaN薄膜微结构及性能的影响

采用反应直流磁控溅射法在Al2O3陶瓷基片上制备TaN薄膜,研究了氮流量(N2/(N2+Ar))对TaN薄膜微结构及性能的影响。结果表明,随氮流量的增大,TaN薄膜的氮含量、电阻率、方阻以及TCR的绝对值逐渐增大,而沉积速率逐渐降低。当N2流量较低(2%～4%)时,TaN薄膜中主要含有电阻率和TCR绝对值较低的六方Ta2N相(hcp),薄膜的电阻率在344μΩ.cm到412μΩ.cm范围内,薄膜的TCR绝对值约为几十ppm/℃。当氮气流量较高(5%～6%)时,薄膜中Ta2N相消失,薄膜中主要含有TCR绝对值较大的体心四方结构(bct)的TaN和四方结构(bct)的Ta3N5相,薄膜的电阻率在940μΩ.cm到1030μΩ.cm范围内,薄膜的TCR绝对值约为几百ppm/℃。     

Effect of oxygen pressure on the structural and optical properties of ZnO thin films on Si (111) by PLD

ZnO thin films were grown on Si (111) substrates by pulsed laser deposition (PLD) at various oxygen pressures in order to investigate the structural and optical properties of the films. The optical properties of the films were studied by photoluminescence spectra using a 325 nm He-Cd laser. The structural and morphological properties of the films were investigated by XRD and AFM measurements, respectively. The results suggest that films grown at 20 Pa and 50 Pa have excellent UV emission and high-quality crystallinity. The research of PL spectra indicates that UV emission is due to excitonic combination, the green band is due to the replacing of Zn in the crystal lattice for O and the blue band is due to the O vacancies.     

Effects of oxygen flow rate on microstructure and optical properties of aluminum oxide films deposited by electron beam evaporation technique

Reactive evaporation technique has been used to deposit thin films of alumina (Al₂O₃) on crystalline Si substrates at ambient temperatures in an electron beam (e-beam) evaporation system using alumina granules as evaporant material. The loss of oxygen due to dissociation of alumina has been compensated by bleeding high purity oxygen gas into the system during evaporation. A set of samples were prepared at different flow rates of oxygen and the films have been characterized by Spectroscopic Ellipsometry (SE), Atomic Force Microscopy (AFM), Grazing Incidence X-ray Reflectivity (GIXR) and X-ray Photoelectron Spectroscopy (XPS) measurements. The density and optical properties of the films showed interesting variation with oxygen flow rates.     

后处理工艺对BST薄膜残余应力的影响的分析

采用射频磁控溅射在Pt/Ti/SiO2/Si（100）衬底上制备了钛酸锶钡（BST）薄膜，利用气氛炉对薄膜进行晶化处理，晶化后薄膜的应力采用XRD表征。研究其残余应力随退火气氛、退火温度以及退火降温速率变化的趋势，通过对不同后处理工艺参数实验结果的分析，得到较优化的工艺参数，以制备较小残余应力的优质BST薄膜。     

YSZ薄膜的制备及应用

研究了在ＮＡＳＩＣＯＮ基板上使用溅射法制备的ＹＳＺ薄膜的结构,晶相和导电性,实验表明,刚制备的ＹＳＺ薄膜７５０℃常规退火处理后,薄膜表面致密、均匀、无裂纹,具备良好的导电性能,ＹＳＺ／ＮＡＳＩＣＯＮ组合再加上Ｂａ（ＮＯ３）２辅助电极构成的ＮＯｘ气体传感器在４５０℃下响应迅速（响应时间约为３ｍｉｎ）、稳定、能检测到１０ｐｐｍ量级的ＮＯ２气体。     

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.     

Effect of oxygen partial pressure on the microstructural and physical properties on nanocrystalline tin oxide films grown by plasma oxidation after thermal deposition from pure Sn targets

In this work, microstructural and physical properties were studied in the tin oxide films deposited by thermal evaporation of Sn films on stainless steel substrates followed by in situ D.C. plasma oxidation at 200 °C substrate temperature. The surface properties were studied by scanning electron microscopy, X-ray diffraction, atomic force microscopy and four-point probe electrical resistivity. The typical calculated grain size of the films deposited by thermal evaporation was between 28 nm and 66 nm and the texture structure was found to be dependent on the thermal deposition pressure. A cassiterite structure of SnO₂ was produced by D.C. plasma oxidation with the main diffraction peaks of the (101), (200), (211), (310) and (221) planes at the 25% and 50% O₂ partial pressure conditions. However, at 12.5% O₂ partial pressure oxidation conditions, amorphous tin oxide structure and crystalline SnO phases were detected. Increasing thermal deposition pressure resulted in preferential texture formation at (211) and (310) planes. The surface structure investigation of the produced films by SEM and AFM studies showed large SnO₂ islands with approximately 1.0 μm and 1.5 μm sized nodules, and they are called as grape-like structures. The grape-like grains possess nano grains, which are between 20 nm and 30 nm in diameter calculated by Scherer's formula. The grape-like grains were seen to be separated by large cavities and the size of these cavities and nano grains was seen to be larger when the O₂ partial pressure is increased. The four-point probe resistivity of the films, grown at different oxidation temperatures, decreased with the increase in oxygen partial pressure. The values of resistivity for SnO₂ phase were measured as low as 10⁻⁵ Ω-cm and observed to decrease with increasing thermal deposition pressure and oxygen partial pressure.     

氧压对脉冲激光沉积LaNiO_3薄膜结构和电学性能的影响

通过改变氧分压,利用脉冲激光沉积方法在Si(100)衬底上制备了系列LaNiO3导电氧化物薄膜;经XRD测试研究发现,通过调控氧压,可获得具有高(100)取向薄膜,且氧压对薄膜结晶性有很大影响,在氧分压为7.5Pa时获得结晶性最好的薄膜。经XRF分析表明,La、Ni元素化学成分计量比随氧压增大而减小。经四探针法测试,薄膜电阻率最小为2.03×10-4Ω.cm,表现出了良好的金属导电性。经SEM和AFM分析表明,薄膜晶粒为柱状晶,排列均匀致密,薄膜表面均匀,粗糙度较小,表明LaNiO3薄膜可以用作一种良好的铁电薄膜底电极材料。     

Effect of the oxygen partial pressure on the microstructure and optical properties of ZnO:Cu films

Cu-doped zinc oxide (ZnO:Cu) films were deposited on Si substrates using radio frequency reactive magnetron sputtering at different oxygen partial pressures. The effect of oxygen partial pressure on the microstructures and optical properties of ZnO:Cu thin films were systematically investigated by X-ray diffraction (XRD), atomic force microscopy (AFM) and fluorescence spectrophotometer. The results indicated that the grain orientation of the films was promoted by appropriate oxygen partial pressures. And with increasing oxygen partial pressure, the compressive stress of the films increased first and then decreased. The photoluminescence (PL) of the samples were measured at room temperature. A violet peak, two blue peaks and a green peak were observed from the PL spectra of the four samples. The origin of these emissions was discussed and the mechanism of violet emission of ZnO:Cu thin films were suggested.     

沉积气压对电弧离子镀制备ZnO薄膜的结构和性能影响

采用阴极真空电弧离子镀技术在玻璃衬底上制备出了具有择优取向的透明ZnO薄膜. 利用X射线衍射仪、扫描电子显微镜及紫外-可见吸收光谱仪分别对ZnO薄膜的结构、表面形貌及可见光透过率进行了分析.XRD结果表明,所制备的ZnO薄膜具有六角纤锌矿结构的(002)和(101)两种取向,在沉积气压＞1.0Pa时所制备的ZnO薄膜具有(002)择优取向,并且非常稳定.SEM图表明,ZnO晶粒大小较为均匀,晶粒尺寸随着气压升高而变小.在400～1000nm范围内,ZnO薄膜的可见光透过率超过80%,吸收边在370nm附近,所对应的光学带隙约为3.33～3.40eV,并随着沉积气压上升而变大.     

The effect of argon pressure, residual oxygen and exposure to air on the electrical and microstructural properties of sputtered chromium thin films

Chromium thin films were deposited on SiO₂/Si wafers using two sputtering systems with different levels of cleanliness, and at argon sputtering pressures varying between 0.13 and 0.93 Pa. Films from the two systems grown under identical sputtering conditions had significantly different resistivity values that are shown to be due to differences in residual oxygen in the chambers. Electrical transport measurements were conducted on the series of grown films to investigate the influence of argon pressure on film electrical resistivity. The films morphology, microstructure and composition were characterized using scanning electron microscopy and X-ray photoelectron spectroscopy. Significant differences were found in Cr thin films sputtered at different sputtering pressures; differences in resistivity performance and microstructure were noted. This change was shown to be due to the transition from porous structure to a denser microstructure. The Cr films sputtered at high pressure contained large quantities of oxygen when exposed to air. Some of the oxygen is added to the film during the deposition depending on the deposition rate and the base pressure of the sputtering system. The rest is incorporated into the film once it is exposed to air. The amount of oxygen added at this stage depends on the structure of the film and would be minimal for the films deposited at low sputtering pressures.     

Texture, residual stress and structural analysis of thin films using a combined X-ray analysis

Advanced thin films for today's industrial and research needs require highly specialized methodologies for a successful quantitative characterization. In particular, in the case of multilayer and/or unknown phases a global approach is necessary to obtain some or all the required information. A full approach has been developed integrating novel texture and residual stress methodologies with the Rietveld method (Acta Cryst. 22 (1967) 151) (for crystal structure analysis) and it has been coupled with the reflectivity analysis. The complete analysis can be done at once and offers several benefits: the thicknesses obtained from reflectivity can be used to correct the diffraction spectra, the phase analysis help to identify the layers and to determine the electron density profile for reflectivity; quantitative texture is needed for quantitative phase and residual stress analyses; crystal structure determination benefits of the previous. To achieve this result, it was necessary to develop some new methods, especially for texture and residual stresses. So it was possible to integrate them in the Rietveld, full profile fitting of the patterns. The measurement of these spectra required a special reflectometer/diffractometer that combines a thin parallel beam (for reflectivity) and a texture/stress goniometer with a curved large position sensitive detector. This new diffraction/reflectivity X-ray machine has been used to test the combined approach. Several spectra and the reflectivity patterns have been collected at different tilting angles and processed at once by the special software incorporating the aforementioned methodologies. Some analysis examples will be given to show the possibilities offered by the method.