Y2O3稳定ZrO2薄膜的结构和光学特性

用电子束蒸发法制备出四种不同Y2O3含量的Y2O3稳定ZrO2（YSZ）薄膜,用X射线衍射和透射光谱测定薄膜的结构和光学性能.结果表明：随着Y2O3含量的增加,ZrO2薄膜从单斜相向高温相（四方相和立方相）转变,获得了结构稳定的YSZ薄膜；YSZ薄膜的晶粒尺寸都比ZrO2薄膜的大,但随着Y2O3加入量的增加,晶粒尺寸有减小的趋势,薄膜表面也趋向光滑平整.所有YSZ薄膜的透射谱线都与ZrO2薄膜相似,在可见光和红外光区都有较高的透过率.Y2O3的加入还可以改变薄膜的折射率,在一定范围内可得到所需的任意折射率.     

Influence of Ytterbia Content on Residual Stress and Microstructure of Y2O3--ZrO2 Thin Films Prepared by EB-PVD

Y2O3 stabilized ZrO2 （YSZ） thin films with different Y2O3 molar contents （0, 3, 7, and 12 mol%） are deposited on BK7 substrates by electron-beam evaporation technique. The effects of different Y2O3 contents on residual stresses and structures of YSZ thin films are studied. Residual stresses are investigated by means of two different techniques： the curvature measurement and x-ray diffraction method. It is found that the evolution of residual stresses of YSZ thin films by the two different methods is consistent. Residual stresses of films transform from compressive stress into tensile stress and the tensile stress increases monotonically with the increase of Y2O3 content. At the same time, the structures of these films change from the mixture of amorphous and monoclinic phases into high temperature cubic phase. The variations of residual stress correspond to the evolution of structures induced by adding of Y2O3 content.     

沉积温度对氧化钇稳定氧化锆薄膜残余应力的影响

采用自制掺摩尔分数12%的YzO2的ZrO2混合颗粒料为原料,在不同的沉积温度下用电子束蒸发方法沉积氧化钇稳定氧化锆(YSZ)薄膜样品.利用ZYGO MarkⅢ-GPI数字波面干涉仪对氧化钇稳定氧化锆薄膜的残余应力进行了研究,讨论了沉积温度对残余应力的影响.实验结果表明:随沉积温度升高,氧化钇稳定氧化锆薄膜中残余应力状态由张应力变为压应力.且压应力值随着沉积温度升高而增大;用X射线衍射仪表征了不同沉积温度下氧化钇稳定氧化锆薄膜的微观结构,探讨了薄膜微观结构与其应力的对应关系,并对比了纯ZrO2薄膜表现出的应力状念.     

Y2O3 stabilized ZrO2 thin films deposited by electron beam evaporation: Structural, morphological characterization and laser induced damage threshold

Four kinds of Y₂O₃ stabilized ZrO₂ (YSZ) thin films with different Y₂O₃ content have been prepared on BK7 substrates by electron-beam evaporation method. Structural properties and surface morphology of thin films were investigated by X-ray diffraction (XRD) spectra and scanning probe microscope. Laser induced damage threshold (LIDT) was determined. It was found that crystalline phase and microstructure of YSZ thin films was dependent on Y₂O₃ molar content. YSZ thin films changed from monoclinic phase to high temperature phase (tetragonal and cubic) with the increase of Y₂O₃ content. The LIDT of stabilized thin film is more than that of unstabilized thin films. The reason is that ZrO₂ material undergoes phase transition during the course of e-beam evaporation resulting in more numbers of defects compared to that of YSZ thin films. These defects act as absorptive center and the original breakdown points.     

电子束蒸发法制备ZrO2薄膜的相变模型分析

 用电子束蒸发方法制备了纯的ZrO₂薄膜和含Y₂O₃摩尔分数为7%和13%的ZrO₂薄膜,即YSZ薄膜,通过测定薄膜的损伤阈值来验证温度诱导相变模型;并用X射线衍射（XRD）来测定ZrO₂和YSZ镀膜材料和薄膜的结构特征。结果表明：ZrO₂镀膜材料和薄膜室温下都表现为单斜相,YSZ镀膜材料和薄膜室温下都以立方相存在;YSZ薄膜的损伤阈值远高于ZrO₂薄膜的损伤阈值,这是因为添加Y₂O₃后的YSZ材料的相比较稳定,在蒸发过程中不会发生相变,而ZrO₂材料则发生相变,产生缺陷,缺陷在激光作用下成为吸收中心和初始破坏点,导致ZrO₂薄膜的损伤阈值降低。     

电子束、离子辅助和离子束溅射三种工艺对光学薄膜性能的影响

 运用电子束、离子辅助和离子束溅射三种镀膜工艺分别制备光学薄膜，包括单层氧化物薄膜和增透膜，然后采取一系列测试手段，如Zygo轮廓仪、原子力显微镜、表面热透镜技术和X射线衍射等技术，来分析和研究不同的工艺对这些薄膜性能的不同影响，以判断合理的沉积工艺。     

离轴生长的MgB_2超导薄膜的研究

通过混合物理化学沉积法(hybrid physical-chemical vapor deposition,简称为HPCVD),我们在多种单晶衬底上制备出了MgB2超导薄膜.经测量发现MgB2薄膜在6H-SiC、c-Al2O3、MgO(111)和YSZ(111)衬底上基本是沿c轴外延生长的,形成单晶薄膜;在MgO(211)、MgO(100)和钇稳定氧化锆(YSZ)(110)衬底上,MgB2晶粒的生长表现出明显的择优取向生长方式,并与晶格常数匹配关系所预言的结果一致。     

YBCO涂层导体用YSZ缓冲层的快速制备研究

基于反应直流溅射法,采用镶嵌有钇粒的金属锆作为靶材,去离子水蒸汽为氧化反应气体,在有Y2O3种子层的双轴织构Ni-5at.%W基带上,系统地研究了温度和卷绕速度对YSZ阻挡层薄膜结构及表面形貌的影响。X射线衍射(XRD)分析表明,生长温度在700℃时制备的薄膜呈现明显的(002)取向;原子力显微镜(AFM)分析显示,该温度下制备的薄膜表面致密、无孔洞、无裂纹。在不同的卷绕速度下,虽然薄膜均为纯c轴取向,但其均方根粗糙度(RMS)和微粒大小均有较大差别。快速制备可达到抑制基片表面氧化、助于薄膜取向改善、提高薄膜制备效率的目的。     

ZrO2/SiO2溶胶-凝胶薄膜膜层间的渗透行为

 分别以丙醇锆和正硅酸乙酯为原料，采用溶胶-凝胶工艺制备了性能稳定的ZrO₂和SiO₂溶胶。用旋转镀膜法在K9玻璃上分别制备了单层SiO₂薄膜、单层ZrO₂薄膜、ZrO₂/ SiO₂双层膜和SiO₂/ZrO₂双层膜。采用原子力显微镜观察了薄膜的表面形貌，用椭偏仪测量薄膜的厚度与折射率，用紫外-可见光分光光度计测量了薄膜的透射率。对薄膜的透射光谱和椭偏仪模拟的数据进行分析，发现SiO₂/ZrO₂双层膜之间的渗透十分明显，而ZrO₂/SiO₂双层膜之间几乎不发生渗透。利用TFCalc模系设计软件,采用三层膜模型对薄膜的透射率进行模拟，得出的透射曲线与用紫外-可见光分光光度计测量的透射曲线十分符合。     

Determination of optical properties in nanostructured thin films using the Swanepoel method

We present the methodological framework of the Swanepoel method for the spectrophotometric determination of optical properties in thin films using transmittance data. As an illustrative case study, we determined the refractive index, thickness, absorption index, and extinction coefficient of a nanostructured 3 mol% Y₂O₃-doped ZrO₂ (yttria stabilized zirconia, 3YSZ) thin film prepared by the sol-gel method and deposited by dipping onto a soda-lime glass substrate. In addition, using the absorption index obtained with the Swanepoel method, we calculated the optical band gap of the film. The refractive index was found to increase, then decrease, and finally stabilize with increasing wavelength of the radiation, while the absorption index and extinction coefficient decreased monotonically to zero. These trends are explained in terms of the location of the absorption bands. We also deduced that this 3YSZ thin film has a direct optical band gap of 4.6 eV. All these results compared well with those given in the literature for similar thin films. This suggests that the Swanepoel method has an important role to play in the optical characterization of ceramic thin films.     

ZrO_2/SiO_2溶胶-凝胶薄膜膜层间的渗透行为

分别以丙醇锆和正硅酸乙酯为原料,采用溶胶-凝胶工艺制备了性能稳定的ZrO2和SiO2溶胶。用旋转镀膜法在K9玻璃上分别制备了单层SiO2薄膜、单层ZrO2薄膜、ZrO2/SiO2双层膜和SiO2/ZrO2双层膜。采用原子力显微镜观察了薄膜的表面形貌,用椭偏仪测量薄膜的厚度与折射率,用紫外-可见光分光光度计测量了薄膜的透射率。对薄膜的透射光谱和椭偏仪模拟的数据进行分析,发现SiO2/ZrO2双层膜之间的渗透十分明显,而ZrO2/SiO2双层膜之间几乎不发生渗透。利用TFCalc模系设计软件,采用三层膜模型对薄膜的透射率进行模拟,得出的透射曲线与用紫外-可见光分光光度计测量的透射曲线十分符合。     

ZrO2薄膜残余应力实验研究

采用ZYGO MarkⅢ-GPI数字波面干涉仪对电子束蒸发方法制备的ZrO2薄膜中的残余应力进行了研究,讨论了沉积温度、沉积速率等工艺参量对ZrO2薄膜残余应力的影响。实验结果表明：随着沉积温度及沉积速率的升高,ZrO2薄膜中残余应力状态由张应力变为压应力,且压应力值随着沉积温度升高而增大。同时用X射线衍射技术测量分析了不同沉积条件下ZrO2薄膜的微结构组织,探讨了ZrO2薄膜微结构与其应力的对应关系。     

Two-photon polymerization of titanium-containing sol–gel composites for three-dimensional structure fabrication

In this work, we have synthesized and characterized a novel, titanium-containing hybrid material that can be structured three-dimensionally using two-photon polymerization. We investigate the effect on the structurability of the increase of titanium isopropoxide and methacrylic acid in this photosensitive composite. We show that while it is possible to make transparent thin films with a titanium isopropoxide molar content as high as 90%, three-dimensional structures can be made only when the titanium isopropoxide molar content is less than 50%. We measure the refractive index of films with different titanium isopropoxide: methacrylic acid concentrations and we show that while the refractive index increases linearly with the titanium isopropoxide, the increase of the methacrylic acid content does not affect the refractive index of the material.     

多层膜界面结构探测技术

分别以丙醇锆和正硅酸乙酯为原料,采用溶胶-凝胶工艺制备了性能稳定的ZrO2和Si O2溶胶。用旋转镀膜法在K9玻璃上分别制备了Si O2单层膜、ZrO2单层膜和ZrO2/Si O2/ZrO2三层膜。采用椭偏仪测量薄膜的厚度与折射率,用紫外-可见分光光度计测量了薄膜的透过率,利用TFCalc_Demo模系设计软件,采用三层理论模型对薄膜的透过率进行模拟,用扫描电镜(SEM)观察了三层膜的断面结构,用X射线光电子能谱仪(XPS)测量了薄膜的成分随深度方向的变化,进一步验证了ZrO2/Si O2/ZrO2三层膜之间的渗透关系,同时对多层膜的界面结构探测方法起到了借鉴作用。     

Influences of oxygen partial pressure on structure and related properties of ZrO2 thin films prepared by electron beam evaporation deposition

ZrO₂ thin films were prepared by electron beam evaporation at different oxygen partial pressures. The influences of oxygen partial pressure on structure and related properties of ZrO₂ thin films were studied. Transmittance, thermal absorption, structure and residual stress of ZrO₂ thin films were measured by spectrophotometer, surface thermal lensing technique (STL), X-ray diffraction and optical interferometer, respectively. The results showed that the structure and related properties varied progressively with the increase of oxygen partial pressure. The refractive indices and the packing densities of the thin films decreased when the oxygen partial pressure increased. The tetragonal phase fraction in the thin films decreased gradually as oxygen partial pressure increased. The residual stress of film deposited at base pressure was high compressive stress, the value decreased with the increase of oxygen partial pressure, and the residual stress became tensile with the further increase of oxygen pressure, which was corresponding to the evolution of packing densities and variation of interplanar distances.     

TeO2-TiO2-Bi2O3系统玻璃的热学特性及光学带隙研究

采用熔融淬冷法制备了系列高折射率的TeO2-TiO2-Bi2O3系统玻璃,测试了样品的密度、转变温度、析晶温度、折射率、吸收光谱,利用经典的Tauc方程计算了样品光学带隙允许的直接跃迁、允许的间接跃迁及Urbach能量.讨论了玻璃的热稳定性与组成之间的关系、研究了摩尔折射度、金属标准值、光学带隙、Urbach能量、Bi2O3和TiO2含量及光学碱度对玻璃样品折射率的影响.结果表明TeO2-TiO2-Bi2O3玻璃具有较好的热稳定性、样品的折射率随着摩尔折射度增大而增大,而光学带隙及金属标准值有减小的趋势,此外高的光学碱度对玻璃的高的三阶非线性也有一定的贡献.     

Enhanced birefingence of MgF2 thin film at 193 nm by serial bideposition

Magnesium fluoride films were coated by serial bideposition with a varying number of sub-deposited layers. The deposition angle 70° remained constant throughout the process by a single electron-beam source. One, 4, 20, and 100 sub-deposition layers were prepared. The microstructure, residual stress, absorption of water, and linear birefringence of serial bideposition of anisotropic thin film at 193 nm were investigated and discussed. Microstructures of the films were observed by scanning electron microscopy. The residual stress was measured by phase-shifting interferometer. The water absorption bands of the thin films were measured by Fourier transform infrared (FTIR) spectroscopy, and refractive indices in two different directions (S- and P-polarized) were determined from a spectrometer equipped with a polarizer. The linear birefringence would increase and the stress would decrease when the sub-deposited layers were increased. When the number of layers was 100, the difference between the refractive indices for two different polarizations was able to reach 0.082.     

高折射率光学薄膜的化学法制备研究

 报道了一种以ZrOC₁₂·8H₂O为源,溶胶-凝胶法制备高激光负载高折射率薄膜的新方法。薄膜采用旋转镀膜法制备,对薄膜的结构、光学特性及激光损伤阈值进行了测量,有机粘接剂对薄膜折射率及机械强度的影响也作了探讨。以该薄膜与SiO₂溶胶凝胶膜交替涂覆制成的多层高反膜,剩余透过率仅0.98%,激光损伤阈值达16J/cm²（3ns）。     

二氧化锆薄膜表面粗糙度的研究

采用电子束蒸发工艺,利用泰勒霍普森相关相干表面轮廓粗糙度仪,研究了不同基底粗糙度、不同二氧化锆薄膜厚度以及不同的离子束辅助能量下所沉积的二氧化锆薄膜的表面粗糙度。结果表明：随着基底表面粗糙度的增加,二氧化锆薄膜表面粗糙度呈现出先缓慢增加,当基底的粗糙度大于10nm后呈现快速增加的趋势;随着二氧化锆薄膜厚度的增加,其表面均方根粗糙度（RMS）先减小后增大;随着辅助沉积离子能量的增加,其表面粗糙度呈现出先减小后增加的趋势。     

薄膜非均匀性及其对增透膜性能的影响

基于非均匀膜理论提出的折射率分层模型,将非均匀膜层分为N个均匀子层,应用光学薄膜特征矩阵对其进行理论分析。应用膜系设计软件模拟ZrO2和CeO2的负非均匀性对增透膜光谱特性的影响。研究结果表明:负非均匀性使多层增透膜的反射率增大,在参考波长处的光谱特性变差,使整个反射光谱曲线朝长波方向漂移,从而导致整个膜系的光谱特性偏离理想情形。