溶胶-凝胶法MgF2紫外增透膜的制备和性能研究

 采用溶胶-凝胶法,以醋酸镁和氟化氢为原料,以甲醇为溶剂制备了MgF₂溶胶,利用浸渍提拉法在洁净石英基片上镀膜,考察了反应温度对溶胶微结构、薄膜结构和性能的影响。样品采用激光动态光散射、透射电镜、X射线粉体衍射仪、紫外-可见光谱仪、原子力显微镜进行表征。结果表明：通过该方法制备的表面平整的低折射率MgF₂薄膜,在紫外区具有很好的增透性能,同时在紫外波长355 nm激光的辐照下（脉宽6 ns）,薄膜具有较高的抗激光损伤性能,激光损伤阈值达10.85 J·cm^-2。     

硫酸盐对KDP晶体质量的影响

 利用“点籽晶”快速生长技术生长了掺杂硫酸钾（K₂SO₄）的磷酸二氢钾（KDP）晶体,并对硫酸根类杂质离子对晶体的结构及光学质量的影响进行了研究。结果表明：在掺杂相对含量为50×10^-6条件下,K₂SO₄开始对KDP晶体产生一定影响,主要表现在不同扇形区域的结构略有改变,其原因主要在于硫酸根与KDP晶体各扇形结构有关;杂质粒子对晶体透过率、单轴性没有明显影响,但是热膨胀系数增大,光损伤阈值略有降低。     

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%。     

氧分压对ZrO2薄膜激光损伤阈值的影响

 在不同的氧分压下用电子束热蒸发的方法制备了ZrO₂薄膜。分别通过X射线衍射、光学光谱、热透镜技术、抗激光辐照等测试，对所制备样品的微结构、折射率、吸收率及激光损伤阈值进行了测量。实验结果表明，薄膜中晶粒主要是四方相为主的多晶结构，并且随着氧分压的增加，结晶度、折射率以及弱吸收均逐渐降低。薄膜的激光损伤阈值开始随着氧分压增加从18.5J/cm²逐渐增加，氧分压为9×10^-3Pa时达到最大，值为26.7 J/cm²，氧分压再增加时则又降低到17.5 J/cm²。由此可见，氧分压引起的薄膜微结构变化是ZrO₂薄膜激光损伤阈值变化的主要原因。     

ZrO2薄膜的改性与抗激光损伤研究

 采用水热合成技术，制备了ZrO₂胶体，用旋涂法镀制了单层ZrO₂介质膜以及添加了有机粘合剂PVP的复合ZrO₂-PVP薄膜。采用X射线衍射(XRD)、椭偏仪、红外分光光度计（FTIR）、原子力显微镜（AFM）等仪器对干凝胶及薄膜进行了性能测试和表征，并用输出波长为1.064 μm、脉宽为10 ns的电光调Q激光系统产生的强激光测试其激光损伤阈值。测得ZrO₂和ZrO₂-PVP薄膜在300 ℃热处理60 min后的激光损伤阈值分别为24.5 J/cm²和37.8 J/cm²。研究表明：添加有机粘合剂后的复合薄膜具有平整的表面结构；有机粘合剂的添加有助于提高薄膜的折射率和激光损伤阈值，其中，ZrO₂-PVP 复合薄膜的折射率可高达1.75，激光损伤阈值达到37.8 J/cm²，比ZrO₂单层膜的激光损伤阈值提高50%。     

用1064nm激光增强HfO2/SiO2薄膜的抗激光损伤能力的实验研究

 用1 064nm激光实验研究了HfO₂/SiO₂薄膜的激光损伤增强效应，实验以薄膜激光损伤阈值70%的激光能量开始，采用N-ON-1方式处理薄膜，激光脉冲的能量增量为5J/cm²。实验结果表明，激光处理薄膜表面能使激光损伤阈值平均提高到3倍左右，并且薄膜的损伤尺度也明显减小。对有缺陷的薄膜，其缺陷经低能量激光后熔和消除，其抗激光损伤能力得到增强，但增强得并不显著，而薄膜本身的激光预处理，可以使其激光损伤阈值大大提高。     

溶胶-凝胶法制备高折射率TiO2薄膜

 采用溶胶- 凝胶法制备了TiO₂纳米晶溶胶,并以旋涂法（spin-coating）镀制了高折射率光学薄膜。借助光散射技术和透射电镜研究了溶胶的微结构。采用原子力显微镜、场发射扫描电镜、紫外-可见-近红外光谱仪、椭偏仪、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的表征。结果显示:纳米晶薄膜的折射率达到了1.9,而传统的溶胶-凝胶薄膜折射率只有1.6;同时纳米晶薄膜的抗激光损伤阈值与传统的溶胶-凝胶薄膜相差不大,在1 064 nm处分别为16.3 J/cm²(3 ns脉冲) 和16.6 J/cm²(3 ns脉冲);纳米晶溶胶薄膜可以在保持较高抗激光损伤阈值情况下,大幅度提高薄膜折射率。     

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。     

缓冲层对LBO晶体上1 064 nm，532 nm增透膜附着力的影响

 采用电子束蒸发方法在LBO晶体上制备了无缓冲层和具有不同缓冲层的1 064 nm,532 nm二倍频增透膜。利用分光光度计、纳米力学综合测试系统以及调Q脉冲激光装置对样品的光学性能、附着力以及抗激光损伤性能进行了测试分析。结果表明：所有样品在1 064 nm和532 nm波长的剩余反射率都分别小于0.1％和0.2％;与无缓冲层样品相比,预镀Al₂O₃缓冲层样品的附着力提高了43.1％,具有SiO₂缓冲层样品的附着力显著提高,而MgF₂缓冲层的插入却导致薄膜附着力降低。应用全塑性压痕理论和剪切理论对薄膜的附着力增强机制进行了分析。薄膜的抗激光损伤性能分析表明,SiO₂缓冲层也有助于改进薄膜的激光损伤阈值。     

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）。     

Ag/TiO2 sol prepared by a sol–gel method and its photocatalytic activity

Ag/TiO₂ sol with narrow particle size distribution was synthesized using TiCl₄ as the starting material. TiCl₄ was converted to Ti(OH)₄ gel. The Ag/TiO₂ sol was prepared by a process where H₂O₂ was added and then heated at 90–97 °C. After condensation reaction and crystallization, a transparent sol with suspended Ag/TiO₂ was formed. Ag/TiO₂ was characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, contact angle analysis, and X-ray photoelectron spectroscopy. The photocatalytic properties of Ag/TiO₂ film were evaluated by degradation of methylene blue in aqueous solution under UV light irradiation. The suspended Ag/TiO₂ particles were rhombus primary particles with the major axis ca. 40 nm and the minor axis ca. 10 nm. Ag nanoparticles were well dispersed on TiO₂ and the particle size was only 1–2 nm. Ag could restrain the recombination of photo-generated electrons and holes effectively. Transparent thin films could be obtained through dip-coating glass substrate in the sol. The thin film had strong hydrophilicity after being illuminated by UV light. Ag/TiO₂ film showed a significant increase in photocatalytic activity compared to the TiO₂ film. The high amount of surface hydroxyls on Ag/TiO₂ film also played an important role in its photocatalytic activity.     

Solid-state Fluorescence Emission and Second-Order Nonlinear Optical Properties of Coumarin-based Fluorophores

Some coumarin-based fluorophores were synthesized and characterized by elemental analysis, ¹H NMR, ¹³C NMR and MS. The solid-state photoluminescence properties were studied. The benzocoumarins display interesting solid-state emission properties with an emission at wavelengths ranging from 532 to 645 nm, when excited by a 325 nm helium–cadmium laser at room temperature. The results demonstrated that the luminescent colors can be tuned from green to red by simply varying molecular structure. The benzocoumarin-phenyl boronic acid hybrid, 4-(3-oxo-3-(2 -oxo-2H-1-naphtho[2,1-b]pyran-3-yl)-prop-1-enyl)phenyl boronic acid, showed obvious fluorescence response to water. Whereas the free compound was very weakly fluorescent in tetrahydrofuran (THF), the addition of water leads to an appearance of strong blue-green fluorescence and a dramatic increase of emission intensity. Besides, 3-(3-(3,4,5-trimethoxyphenyl)-prop-2-enoyl)-2H-1-benzopyran-2-one exhibited second order nonlinear optical response to laser pulses. A noticeable second harmonic generation (SHG) under pulsed excitation at 1064 nm was observed. Preliminary nonlinear measurements on powder samples showed that the second harmonic generation efficiency is roughly 5.8 times that of potassium dihydrogen phosphate (KDP).     

高功率激光宽光谱减反膜的溶胶-凝胶旋转法制备工艺

 采用溶胶-凝胶法用旋转镀膜工艺在K9玻璃基片上制备出了SiO₂和有机硅单层减反膜以及有机硅-SiO₂双层减反膜。考察了旋转速度对SiO₂和有机硅单层膜的中心透射波长、膜层折射率等基本光学性质的影响，实验确定了双层膜的涂敷工艺。透射光谱测量表明，采用本文工艺条件制备的有机硅 SiO₂双层膜在430～800nm范围内透射率达99％以上。     

溶胶凝胶法制备抗激光损伤SiO2疏水减反射膜

 通过溶胶-凝胶法，在碱性条件下水解缩聚正硅酸乙酯获得含有SiO₂颗粒的溶胶；以甲基三乙氧基硅烷在酸性条件下水解缩聚获得双链聚合物溶液，作为疏水基团的引入剂。用两者的混合物在玻璃片上旋转镀膜。利用光子相干光谱法、透射电子显微镜、小角X射线散射等方法研究了溶胶微结构，利用紫外-可见光谱仪和接触角测定仪测量薄膜的透射率和疏水性。单面反射率最低降至0.01%，对水接触角最高为118°。利用Nd:YAG激光（1 064nm）测量了薄膜的激光损伤阈值，随混合溶胶中双链聚合物含量的增加损伤阈值减小，但均高于20J/cm²（1ns脉冲）。由于薄膜既保持了纳米氧化硅薄膜的多孔性，又在颗粒及孔表面以甲基修饰，水对薄膜的浸润能力大大降低，因此薄膜的时间稳定性大大增强，同时也保证了较高的损伤阈值和透射率。     

高峰值功率KDP晶体四倍频266nm紫外激光器

报道了一种灯泵浦结构的Nd:YAG晶体电光调Q高峰值功率266nm紫外激光器。结合磷酸二氢钾(KDP)晶体性质,基于倍频理论,分析了考虑走离效应情况下存在相位失配量时KDP晶体长度对转换效率的影响。该激光器采用紧凑的平平腔结构,灯泵浦Nd:YAG晶体电光调Q 1064nm激光作为基频光,腔外采用Ⅱ类匹配磷酸钛氧钾(KTP)和Ⅰ类匹配KDP分别作为二倍频和四倍频晶体。利用能量计、示波器等仪器进行测量,激光器重复频率1Hz时,获得脉宽6.0ns,单脉冲能量35mJ的266nm紫外激光输出,峰值功率高达5.83 MW;当重复频率10Hz时,获得单脉冲能量28.9mJ的266nm紫外激光。532~266nm转换效率最高可达31.9%。利用该高峰值功率、窄脉宽266nm紫外激光器,能够实现激光打标、激光雕刻。     

压敏漆基质SiO2溶胶制备及其性能研究

以正硅酸乙酯为前驱体，乙醇为溶剂，盐酸为催化剂，采用溶胶-凝胶法制备了用于压敏漆基质薄膜材料的SiO2溶胶。不同的成膜助剂对SiO2溶胶的涂膜性能影响较大，其中以异丙醇作为添加剂的溶胶涂膜性能最好。吸收光谱测试结果表明SiO2溶胶不吸收激发光，同时发射光谱研究结果表明SiO2溶胶发光波长为415nm左右，不影响压敏漆探针分子的发光。     

笼形倍半硅氧烷NMR的研究

笼形倍半硅氧烷是一类典型的多面体有机-无机分子复合物. ²⁹Si NMR是测定这类含硅化合物结构的有效方法. 利用²⁹Si NMR对6种笼形八聚倍半硅氧烷的结构进行了研究,结合所得数据探讨了这类化合物中取代基电负性对²⁹Si NMR化学位移的影响.根据¹H,¹³C NMR数据及各峰归属可以进一步判断笼形倍半硅氧烷取代基R的类型和结构.     

Cascaded third-harmonic-generation converter based on a single ADP crystal

Based on a specially designed optical structure, an efficient cascaded third-harmonic-generation(THG) output of a 1064-nm, pico-seconds pulse laser is successively realized by using an NH_4H_2PO_4(ADP) crystal that acts as the secondharmonic-generation component and sum-frequency-generation component. The maximum THG output is 1.61 mJ, and the highest conversion efficiency from 1064 nm to 355 nm reaches 35%, which are obviously superior to the results obtained using a KDP crystal under the same circumstance. The further phase-matching analysis indicates that this THG configuration of ADP crystal can be applied to various fundamental wavelengths in a range of 1 μm–1.1 μm. Compared with the previously reported KDP THG converter, which is based on a similar principle, the present ADP THG converter is favorable for large-energy, high-efficiency operation because of the larger effective nonlinear optical coefficient deffand higher laser damage threshold.     

磷酸盐激光玻璃聚(CH3)2 Si(OC2 H5)2防潮膜

以（CH3）2Si（OC2H5）2为前驱体,采用溶胶-凝胶与有机合成相结合的方法,制得稳定性良好的涂膜液。采用旋转涂膜法在掺钕磷酸盐激光玻璃棒端面涂制防潮膜,膜层固化后透过率达96．5％,获得的膜层表面粗糙度优良,均方根表面粗糙度（RMS）为1．659nm,平均粗糙度（RA）平均为1．321nm;在激光波长1053nm,脉冲宽度1 ns条件下膜层的激光破坏闽值可达10～14 J／cm^2。经过“神光Ⅱ”高功率激光器物理实验运行,膜层使用期为五年,并且已经在我国“神光Ⅲ”原型装置上试用。     

Preparation of uniform TiO2 nanostructure film on 316L stainless steel by sol-gel dip coating

Sol was prepared by the mixing of tetra-η-butyle titanat, ethyl aceto acetate, and ethanol in an optimized condition. Polished 316L specimens were coated with the sol by dip-coating method. The influences of drying condition, withdrawal speed, calcination temperature, addition of dispersant, and pH of sol on TiO₂ nanostructure coating were investigated. Choosing of alcohol as drying atmosphere hindered the crack formation. The relation between coating thickness and withdrawal speed was evaluated. The optimum temperature to create a uniform distribution of nanoparticles of anatase was derived as 400 °C. Average roughness of coating was found about 10.61 nm by AFM analysis. Dispersant addition promoted formation of a uniform film as well as prevention of agglomeration. Acidic sol provided smaller particles than neutral sol.