溶胶-凝胶SiO2酸性膜与碱性膜的激光损伤行为

 采用溶胶-凝胶技术分别在K9基片上镀制了光学厚度相近的单层SiO₂酸性膜和碱性膜。测试了两类薄膜的激光损伤阈值;分别采用透射式光热透镜技术、椭偏仪、原子力显微镜、扫描电镜和光学显微镜研究了两类薄膜的热吸收、孔隙率、微观表面形貌、激光辐照前薄膜的杂质和缺陷状况以及激光辐照后薄膜的损伤形貌。实验结果表明：相对于碱性膜,酸性膜有更大的热吸收和更小的孔隙率,因此其激光损伤阈值较小;两类薄膜不同的损伤形貌与薄膜的热吸收系数与微观结构有关。     

Experimental research of laser-induced damage of the monolayer ZrO2 PVD and sol–gel films

Monolayer zirconia physical vapor deposition (PVD) and sol–gel films on K9 glass substrates were prepared by electron beam evaporation and spin coating methods, respectively. The laser-induced damage threshold (LIDT) of each film was measured. Properties of the films were analyzed using Stanford photo-thermal solutions (SPTS), ellipsometry, atomic force microscopy (AFM) and optical microscopy to study the damage mechanism of films under laser irradiation. The experimental results showed that, compared with the monolayer zirconia sol–gel film, the monolayer zirconia PVD film had larger absorption and smaller porous ratio, and that it had smaller LIDT. The different damage morphologies of films were influenced by their different absorption and microstructure characteristics. The zirconia sol–gel film is more suitable for applications involving high-power lasers.     

Comparison of TiO2 and ZrO2 Films Deposited by Electron-Beam Evaporation and by Sol-Gel Process

TiO2 and ZrO2 films are deposited by electron-beam （EB） evaporation and by sol-gel process. The film properties are characterized by visible and Fourier-transform infrared spectrometry, x-ray diffraction analysis, surface roughness measure, absorption and laser-induced damage threshold （LIDT） test. It is found that the sol-gel films have lower refractive index, packing density and roughness than EB deposited films due to their amorphous structure and high OH group concentration in the film. The high LIDT of sol-gel films is mainly due to their amorphous and porous structure, and low absorption. LIDT of EB deposited film is considerably affected by defects in the film, and LIDT of sol-gel deposited film is mainly effected by residual organic impurities and solvent trapped in the film.     

物理法和化学法制备的单层ZrO2膜的激光损伤行为差异

 分别采用电子束热蒸发技术和溶胶-凝胶技术在K9基片上镀制了光学厚度相近的ZrO₂单层薄膜,测试了两类薄膜的激光损伤阈值。分别采用透射式光热透镜技术、椭偏仪、原子力显微镜和光学显微镜研究了两类薄膜的热吸收、孔隙率、微观表面形貌、激光辐照前薄膜的杂质和缺陷状况以及激光辐照后薄膜的损伤形貌。实验结果表明：两类薄膜的不同损伤形貌与薄膜的热吸收与微观结构有关， 物理法制备的ZrO₂膜结构致密紧凑，膜层的杂质和缺陷多；化学法制备的ZrO₂膜结构疏松多孔，膜层纯净杂质少，激光损伤阈值达26.9 J/cm²；因物理法制备的ZrO₂膜拥有更大的热吸收(115.10×10^-6)和更小的孔隙率(0.20)，其激光损伤阈值较小(18.8 J/cm²)，损伤主要为溅射和应力破坏，而化学法制备的ZrO₂膜的损伤主要为剥层。理论上对实验结果进行了解释。     

PECVD技术制备单层光学薄膜抗激光损伤特性研究

采用PECVD技术在BK7玻璃基底上沉积了不同厚度的单层SiO2（折射率为1.46）和SiNx（折射率为1.84）光学薄膜,并对这2种膜层进行抗激光损伤阈值（LIDT）测试,分析讨论了PECVD技术制备的单层光学薄膜与抗激光损伤特性之间的关系。实验结果表明:PECVD技术制备的单层SiO2薄膜有较高的LIDT,薄膜光学厚度在o/4~o/2之间时,在光学厚度为350 nm时,LIDT有最小值21.7 J/cm2,光学厚度为433 nm时,LIDT有最大值27.9 J/cm2。SiNx薄膜的LIDT随着光学厚度增加而减小,在光学厚度为o/4时,LIDT有最大值29.3 J/cm2,光学厚度为o/2时,LIDT有最小值4.9 J/cm2。     

Effect of polyvinylpyrrolidone on the structure and laser damage resistance of sol–gel silica anti-reflective films

The effect of polyvinylpyrrolidone (PVP) on the structure and laser-induced damage threshold (LIDT) of sol–gel silica anti-reflective films is investigated. The results of dynamic light scattering, transmission electron microscopy, and small angle X-ray scattering, show that the PVP molecules surrounded the silica sol particles through the strong hydrogen bonds between Si-OH groups and the PVP. As a result, the growth of silica particles was restricted and thus the interface layer between the silica particles and the solvent become thickened with PVP content. Furthermore, the PVP reduced the porosity of the film, so the anti-reflection properties of the film were weakened. A multi-fractal analysis showed that the appropriate addition of PVP, 1 weight percent (wt%), could improve the surface fractal structure of the film, but that higher PVP content resulted in reduced surface uniformity. The addition of PVP lead to improved LIDT.     

二氧化硅增透膜微观结构与激光损伤阈值的调控

采用溶胶-凝胶技术制备了二氧化硅增透膜,通过向溶胶中添加高分子聚乙烯醇缩丁醛（PVB）,调控胶体的粒径,进而控制膜层微观结构,研究膜层微观结构与激光损伤阈值的关系。纳米粒度仪和扫描探针显微镜测试表明:PVB加入溶胶后,控制了二氧化硅胶粒的生长,使二氧化硅胶粒生长更均匀,因而膜层的微观结构更均匀。当PVB质量分数为1%时,胶体粒径为15 nm,分散系数小于0.1。用该胶体镀膜,膜层均匀,表面粗糙度小于3.25 nm。并且PVB加入后增加了膜层胶粒间的黏附性,使得膜层强度增大。PVB加入使膜层的激光损伤阈值有所增加。当PVB的添加量为1%时,膜层的激光损失阈值从30.0 J/cm2增加到40.1 J/cm2。膜层激光损伤阈值的增加与膜层微观均匀性和物理强度的增加有关。     

横向电场下的类金刚石薄膜激光损伤

类金刚石(DLC)薄膜在红外区有很高的透过率,但激光损伤阈值低,严重限制了其应用领域。采用直接在DLC薄膜上沉积Ti电极,基于激光损伤阈值(LIDT)测试平台,用1-on-1零几率损伤法,研究了在不同偏置电场下DLC薄膜损伤阈值及损伤形貌的变化。发现电场强度从0增加到700V/cm,损伤阈值明显增大;进一步增大偏置电场,损伤阈值相对不变。分析认为偏置电场改变了激光辐照DLC薄膜区域的光生载流子漂移速度,减小了DLC薄膜的局部热累积,减缓了薄膜的石墨化进程,提高了DLC薄膜的抗激光损伤阈值。     

溶胶-凝胶ZrO2-TiO2高折射率光学膜层的抗激光损伤性能研究

采用溶胶-凝胶方法制备了ZrO₂-TiO₂(Ti含量为0—100mol%)高折射率光学薄膜. 借助激光动态光散射技术研究溶胶微结构. 采用傅里叶变换红外光谱、原子力显微镜、薄膜光学常数分析仪、漫反射吸收光谱及强激光辐照实验，对膜层的结构、光学性能及抗激光损伤性能进行了系统表征. 结果显示，溶胶-凝胶工艺可以在部分牺牲折射率的情况下，使膜层的抗激光损伤性能得到大幅度提升. 随Ti含量从0mol%增加至100mol%，膜层的平均损伤阈值呈下降趋势，当Ti含量从0mol%增加至60mol%时，平均损伤阈值从57.1J/cm²下降到21.1J/cm²(辐照激光波长为1053nm，脉冲宽度为10ns，“R/1”测试模式)，当Ti含量从60mol%增加至100mol%时，平均损伤阈值变化很小. 综合溶胶微结构、膜层光学性能和损伤实验结果可以推断，强激光诱导多光子吸收是引起膜层损伤的主要原因. 不同配比的复合膜之间光学带隙的显著差异导致相同辐照激光情况下多光子吸收的概率发生变化，从而导致损伤阈值的规律性变化. 关键词： 2-TiO₂薄膜')" href="#">ZrO₂-TiO₂薄膜 溶胶-凝胶 激光诱导损伤 光学带隙     

Ultraviolet laser-induced damage on fused silica substrate and its sol-gel coating

A comparative study of the laser-induced damage thresholds (LIDTs) of fused silica substrates and their sol-gel silica coatings was carried out with 355 nm laser irradiation. Chemical etching and superpolishing were employed in different ways to improve the substrate. The laser damage tests showed that the coated substrate was no more susceptible to laser damage than the bare substrate, showing that the substrate quality was the dominant factor limiting the LIDT for UV irradiation. In addition, it was found that high value of substrate microroughness was more harmful to the LIDT of the coated than the bare substrate, and that a proper combination of etching and superpolishing can optimize the LIDT.     

Effect of Process Parameters on Laser Damage Threshold of TiO2 Coatings

We investigate the laser damage behaviour of an electron-beam-deposited TiO2 monolayer at different process parameters. The optical properties, chemical composition, surface defects, absorption and laser-induced damage threshold （LIDT） of films are measured. It is found that TiO2 films with the minimum absorption and the highest LIDT can be fabricated using a TiO2 starting material after annealing. LIDT is mainly related to absorption and is influenced by the non-stoichiometric defects for TiO2 films. Surface defects show no evident effects on LIDT in this experiment.     

Influence of porosity on laser damage threshold of sol–gel ZrO2 and SiO2 monolayer films

Monolayer ZrO₂ sol–gel and physical vapor deposition (PVD) films were prepared by spin method and electron beam evaporation method, respectively. Monolayer sol–gel SiO₂ films were prepared with the dip-coating method from acid and base catalyzed SiO₂ sols, respectively. Some of the SiO₂ base films were subsequently treated in saturated ammonia gas for 20 h. The laser induced damage threshold (LIDT) of each film was measured. Properties of the films were analyzed by using Stanford photo-thermal solutions (SPTSs), ellipsometer, atomic force microscopy (AFM) and optical microscopy. The experimental results showed that porous ratio is an essential factor to decide the LIDT for sol–gel films, which benefits the pressure exerted on the film or substrate by the moving particle to dissipate. The films with lower thermal absorption and higher porous ratio have higher LIDT.     

Postprocessing treatments to improve the laser damage resistance of fused silica optical surfaces and SiO2 coatings

The combination of deep wet etching and a magneto-rheological finishing(MRF) process is investigated to simultaneously improve laser damage resistance of a fused-silica surface at 355 nm. The subsequently deposited SiO2 coatings are researched to clarify the impact of substrate finishing technology on the coatings. It is revealed that a deep removal proceeding from the single side or double side had a significant impact on the laser-induced damage threshold(LIDT) of the fused silica, especially for the rear surface. After the deep etching, the MRF process that followed does not actually increase the LIDT, but it does ameliorate the surface qualities without additional LIDT degradation. The combination guarantee both the integrity of the surface’s finish and the laser damage resistance of the fused silica and subsequent SiO2 coatings.     

钛酸镧薄膜的制备及工艺优化

为了获得制备钛酸镧（LaTiO3）薄膜的最优工艺条件,采用电子束热蒸发技术在K9基底上制备了单层LaTiO3激光薄膜。研究了不同工艺条件对LaTiO3薄膜激光损伤特性的影响。研究结果表明,对LaTiO3薄膜激光损伤阈值（laser-induced damage threshold, LIDT）影响最大的工艺条件是沉积温度,其次是工作真空度,最后是蒸发束流。获得了制备单层LaTiO3激光薄膜的最优工艺条件:沉积温度175 ℃、工作真空度2.010-2 Pa、蒸发束流120 mA（8 keV）;证明了最优工艺下制备的LaTiO3薄膜具有良好的激光损伤特性、稳定性以及重复性,所制备LaTiO3薄膜的激光损伤阈值为16.9 J/cm2（1 064 nm,10 ns）。     

化学法制备的HfO2薄膜的激光损伤阈值研究

 采用化学法制备了HfO₂介质膜，研究了热处理、紫外辐照以及Al₂O₃复合对HfO₂介质膜激光损伤阈值的影响。采用红外光谱（FTIR）和X射线衍射仪对薄膜进行了表征，并用输出波长为1.064 μm、脉宽为10 ns的电光调Q激光系统测试薄膜的激光损伤阈值。实验结果表明：采用150 ℃左右的温度对薄膜进行热处理可以提高薄膜的激光损伤阈值，所获得的薄膜的激光损伤阈值高达42.32 J/cm²，比热处理前的激光损伤阈值提高了82%；无机材料Al₂O₃的适量添加能够提高薄膜的激光损伤阈值，其中HfO₂与Al₂O₃的最佳质量配比约为95∶5；另外，对薄膜进行适当的紫外辐照也可改善HfO₂ 薄膜以及HfO₂-Al₂O₃复合薄膜的抗激光损伤性能。紫外辐照对提高HfO₂-Al₂O₃复合薄膜的激光损伤阈值效果尤为显著，辐照40 min后的激光损伤阈值达到44.33 J/cm²，比紫外辐照前的激光损伤阈值提高了90%。     

Influence of Annealing Temperature on Structure, Optical Loss and Laser-Induced Damage Threshold of TiO2 Thin Films

TiO2 thin films are prepared on fused silica with conventional electron beam evaporation deposition. After annealed at different temperatures for 4h, the spectra and XRD patterns of the TiO2 thin film are obtained. Weak absorption of coatings is measured by the surface thermal lensing technique, and laser-induced damage threshold （LIDT） is determined. It is found that with the increasing annealing temperature, the transmittance of TiO2 films decreases. Especially when coatings are annealed at high temperature over 1173K, the optical loss is very serious. Weak absorption detection indicates that the absorption of coatings decreases firstly and then increases, and the absorption and defects play major roles in the LIDT of TiO2 thin films.     

光学薄膜的激光损伤研究进展

从理论、实验两方面对薄膜的激光损伤机理和提高损伤阈值的手段进行了回顾。概括了现有理论模型及其适用范围,对缺陷的行为进行了多方面的论述,重点比较了各种制备方法及后处理手段的特点,分析了主要工艺参数对薄膜损伤阈值的影响。结合本实验室及国内外同行的工作,对溶胶-凝胶法制备高损伤阈值薄膜的工艺进行了总结。从吸收、热传导、抗拉强度等角度对物理膜和化学膜在结构与性能上进行了比较,提出了从化学键、成膜过程等方面分析损伤机理的建议,并结合真空污染、亚表面损伤等新问题提出了未来工作的发展方向。     

Preparation of sol-gel ZrO2-SiO2 highly reflective multilayer films and laser-induced damage threshold characteristic

Sol-gel (ZrO₂/SiO₂)¹² ZrO₂ films were prepared by spin coating method. The reflectivity spectrum of the films was measured with a Lambda 900 spectrometer. In order to investigate laser-induced damage threshold (LIDT) characteristic of highly reflective films, one-layer ZrO₂ and SiO₂ films, two-layer ZrO₂/SiO₂ and SiO₂/ZrO₂ films were also prepared by spin coating method. LIDT of each film was measured. Damage morphology after laser irradiation was characterized by optical microscopy (Nikon E600K). The experimental results showed that the reflectivity of (ZrO₂/SiO₂)¹² ZrO₂ film at 1064 nm and 355 nm wavelength is 99.7%. The LIDT results decreases as the number of layer of films increases. All the films have similar damage morphology. The experimental results are explained by the different temperature profiles of the films.     

Influences of SiO2 protective layers and annealing on the laser-induced damage threshold of Ta2O5 films

Ta2O5 films are prepared on BK7 substrates with conventional electron beam evaporation deposition.The effects of SiO2 protective layers and annealing on the laser-induced damage threshold (LIDT) of the films are investigated.The results show that SiO2 protective layers exert little influence on the electric field intensity(EFI)distribution,microstructure and microdefect density but increase the absorption slightly.Annealing iS effective on decreasing the microdefect density and the absorption of the films.Both SiO2 protective layers and annealing are beneficial to the damage resistance of the films and the latter is more effective to improve the LIDT.Moreover,the maximal LIDT of Ta2O5 films is achieved by the combination of SiO2 protective layers and annealing.     

缺陷对HfO2薄膜的激光弱吸收与损伤阈值的影响

激光弱吸收是导致光学薄膜损伤的重要原因。在(5~43)mPa的氧分压下制备并测试了一组HfO2薄膜。实验发现,当氧分压小于20mPa时,薄膜弱吸收越大,损伤阈值越低;当氧分压大于20mPa时,薄膜的损伤阈值与弱吸收并不一一对应,具有较高弱吸收的薄膜可能同时具有较高的损伤阈值。建立了缺陷模型,采用有限元法模拟了缺陷对弱吸收测量和损伤阈值测量的影响,分析了缺陷尺寸、密度、吸收系数对弱吸收和损伤阈值的影响。研究结果显示,吸收系数高于薄膜1 000倍的缺陷可以降低薄膜的损伤阈值1 000倍,却并不影响薄膜的弱吸收。缺陷对HfO2薄膜的激光弱吸收与损伤阈值测试有完全不同的影响,是导致某些薄膜弱吸收与损伤阈值背离的原因。