新型红外非线性光学晶体BaGa2GeSe6的生长与器件制备

钡镓锗硒(BaGa₂GeSe₆,BGGSe)晶体是由中国科学家发明的一种性能优异的新型红外非线性光学材料.目前国内未见到关于该晶体的大尺寸制备报道.本研究采用自制的双温区管式炉成功合成出BGGSe多晶,单次合成量达到400 g;采用坩埚下降法生长出大尺寸高质量BGGSe单晶,尺寸为φ30 mm×90 mm,为国内首次;通过定向、切割和抛光等处理工艺,成功制备出BGGSe晶体器件,为该晶体下一步的应用研究打下了坚实基础.     

Growth and characterization of semicarbazone of cyclohexanone

A new organic single crystal of semicarbazone of cyclohexanone (SCCH) has been synthesized and grown as a bulk single crystal by low temperature solution growth technique for the first time in the literature. The grown crystal has been confirmed by X‐ray diffraction and proton nuclear magnetic resonance spectral analyses and also characterized by FT‐ir and FT‐Raman studies. Thermal properties of the grown crystals were studied by thermogravimetric and differential thermal analyses. Optical transmittance was studied by ultraviolet‐visible spectrum and the second harmonic generation property was tested by using Q switched Nd: YAG laser as a source. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Optical and microhardness studies of semiorganic nonlinear optical material: L‐ histidine tetrafluoroborate

L‐histidine tetrafluoroborate (L‐HFB) a semiorganic nonlinear optical material has been synthesized in aqueous solution at 50°C and characterized by FT‐IR and FT‐Raman spectroscopy studies. The solubility was determined in different solvents such as water, methanol and water mixture of methanol. The single crystals with dimensions 15x12x3 mm³ were grown by slow evaporation method within four weeks with approximate growth rate of 0.25 mm/day. The grown crystals have been subjected to single crystal X‐ray diffraction studies to determine the unit cell dimensions and morphology. The Kurtz powder second harmonic generation test shows that the compound is a potential candidate for frequency conversion. The refractive index has been measured using He‐Ne laser. The microhardness test was carried out and the load dependence hardness was observed. The material has a wide transparency in the entire visible region. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

新型红外非线性光学晶体LiGaTe2的多晶合成与晶体生长

采用直接合成方法无法得到纯相的碲镓锂( LiGaTe2)多晶原料,因此提出了两步合成法进行LiGaTe2多晶原料合成,即先合成二元相Ga2Te3,再以Ga2Te3、Li、Te为原料按化学计量比配料在较低温度(850℃)下合成纯相的碲镓锂多晶料,并对具体的反应机理进行了讨论.对所得碲镓锂多晶料进行了XRD分析,结果显示合成的多晶为单相高纯LiGaTe2.差示扫描量热分析(DSC)表明,LiGaTe2的熔点为674.78℃.初步开展了LiGaTe2晶体的生长研究,对晶体生长结果进行了探讨.     

Growth and characterization of Bis Thiourea Zinc Acetate (BTZA)

Single crystals of BTZA have been grown by low temperature solution growth method using slow cooling process at an optimized pH of 3.5. The grown crystals have been examined under an optical microscope to study its surface morphology. The morphological studies show that the growth takes place by spreading of growth layers. Formation of rectangular shaped etch pit on the as‐grown crystal has been explained in relation to the growth conditions. Single crystal X‐ray diffraction analysis has been carried out to confirm the monoclinic system. Transmission spectrum reveals that the crystal has a low UV cut off of 434.5 nm and has a transmittance of 100%. Dependence of micro hardness on load has been studied. Powder X‐ray Diffraction and FT‐IR have been carried out to characterize the grown crystals. BTZA forms metal – sulfur bond and has good optical transmission in the entire visible region, which is the essential requirement for a non‐linear crystal. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

AgGaS2单晶生长石英安瓿镀碳工艺研究

研究了镀碳工艺参数对碳膜的表面形貌、厚度、碳膜与石英管内壁结合力的影响,发现在气体流量为30～40ml/min, 镀碳温度为1040～1060℃,镀碳时间为30～40min,冷却时间为10～12h的条件下,可获得均匀、致密且结合牢固的碳膜层.用此工艺镀碳的石英安瓿生长出的AgGaS2晶体表面光洁,完整性好,缺陷较少.     

新型有机非线性光学晶体-L-苹果酸脲晶体生长的初步探讨

本文初步探讨了新型非线性光学晶体-L-苹果酸脲的晶体生长,研究结果表明,L-苹果酸脲晶体在甲醇、乙醇和水三种介质中的溶解度温度系数均较大,同温度下L-苹果酸脲晶体在水中的溶解度最大,无水甲醇次之,无水乙醇中最小.L-苹果酸脲晶体在无水甲醇中的成核自由能比在无水乙醇中的低得多,因此在无水甲醇中易于成核,晶核数多,晶体尺寸小,而在无水乙醇介质中,虽然成核相对比较困难一些,但有利于制备大的单晶,且发现低温有利于大晶体的生长.因此宜选择无水乙醇为晶体生长介质.L-苹果酸脲晶体在介质中以非均匀成核方式在试管壁成核长大,晶体呈棱柱状,生长过程中呈现台阶生长的特征.     

BiIO_4:一种新型红外非线性光学晶体

本文采用水热法,将两种含孤对电子的元素基团I(Ⅴ)与Bi(Ⅲ)复合到一起,合成出一种新型红外非线性光学晶体BiIO4,该晶体属正交晶系,空间群Pca21(29),晶胞参数为a=0.5645(2)nm,b=1.1036(4)nm,c=0.5731(2)nm,α=β=γ=90°。并对其进行了SEM-EDS、XRD、TG-DSC、FT-IR、UV-Vis-NIR、SHG等测试。结果表明,其二阶非线性光学效应(SHG)约为KDP的10倍,红外吸收边可以达到远红外波段(13μm)。     

非线性光学晶体的研究进展

本文比较了无机、有机、半有机三类非线性光学晶体的性能、研究进展以及面临的主要问题和发展趋势;评述和展望了近年来出现的半有机非线性光学晶体的研究意义、潜在优势和发展前景.     

Growth and Optical Properties of Tm:GdVO4 Single Crystal

Thulium-doped gadolinium vanadate (Tm:GdVO₄) single crystal has been successfully grown by a modified Czochralski (CZ) technique. Effective distribution coefficient of Tm was determined to be 0.74. Absorption characterization was performed in the 800 nm region and the maximum absorption peak was found at 799 nm for p polarization. Fluorescence spectra for tuning at the maximum absorption were obtained around 1.8-2.0µm region with 100 nm bandwidth. This suggests that a Tm:GdVO₄ crystal is expected as a new promising LD pumped solid-state laser in the 2µm region.     

4-氨基二苯甲酮晶体的定向生长及光学性能研究

采用过冷熔体定向约束生长法生长了尺寸约为30 mm×14 mm×7 mm的块状4-氨基二苯甲酮晶体,并对生长晶体的光学均匀性、光学透过率、二次谐波转换效率以及激光损伤阈值等性能进行了测试.结果表明:定向生长的4-氨基二苯甲酮晶体在650~1200 nm波段内具有90;以上的光学透过率;最高二次谐波转换效率达到64.9;;单点激光脉冲损伤阈值分别为205.4 GW/cm2(输入光波为1064 nm)和267.2 GW/cm2(输入光波为532 nm).采用过冷熔体定向约束生长的4-氨基二苯甲酮晶体适合于用作Nd: YAG激光的二次倍频器件,也适合于用作650~1200 nm波段的光学调制器件.     

红外非线性光学晶体CdSe生长与性能表征

采用垂直无籽晶气相法(VUVG)生长出尺寸达26 mm×45 mm的CdSe单晶体,对CdSe晶体的稳态气相生长速率进行了深入讨论.采用气相升华法提纯后的CdSe多晶原料的X射线粉末衍射谱与PDF卡片值(65-3436)吻合,生长出的单晶体{100}和(110)面XRD衍射峰尖锐,无杂峰,且{100}面出现3级衍射峰.晶锭密度为5.74 g/cm3,与理论计算值接近.退火处理后的晶片在1000～7000 cm-1 红外波段范围内透过率达到70;.采用VUVG法生长的CdSe单晶体,结晶性能好、结构致密、尺寸大和红外透过率高,可用于制备红外非线性光学器件.     

L-苹果酸脲光学晶体的台阶生长机制

L-苹果酸脲是一种新型的有机非线性光学晶体,具有广阔的应用前景.研究表明,L-苹果酸脲晶体在乙醇介质中生长时,晶体形态为棱柱形.L-苹果酸脲晶体生长呈现明显的台阶生长,当过饱和度比较低时,其台阶生长机制为螺旋机制;当过饱和度较大时,L-苹果酸脲晶体台阶生长机制为二维成核机制.     

Te2HPO7晶体的非线性光学特性研究

采用水热法合成了一种具有非中心对称结构的已知化合物Te2HPO7,并用波长为1064 nm的激光测试了其粉末倍频效应,发现相同颗粒尺寸下其倍频效应近似为KH2PO4的0.27倍,并且满足相位匹配条件.偶极矩计算表明,该化合物倍频效应主要源于含有孤立电子的TeO4多面体非对称单元.另外,本文用高温差示扫描量热法研究了晶体的热稳定性,在紫外-可见-近红外分光光度计上测量了它的透过光谱.     

非线性光学晶体Ba2B5O9Cl的合成、晶体生长及性能的研究

首次以LiF-H3BO3为助熔剂,用顶部籽晶法,生长出尺寸为12 mm×13mm×5mm的Ba2B5O9Cl透明单晶.通过热性能分析证实该晶体为非同成分熔融化合物,属于正交晶系,空间群Pnn2,晶胞参数为a=1.1576(2) nm,b=1.1619(2)nm,c =0.66874(13) nm,V=0.8994(3) nm3,Z=4.该晶体中含有BO3和BO3基团,具有三维网状的晶体结构.Ba2B5O9Cl粉末的非线性光学效应约为KDP的3.5倍,同时还进行了红外、漫反射光谱性能的研究.     

新型红外非线性光学晶体SrCdGeSe4生长与性质表征

锶镉锗硒(SrCdGeSe4)晶体是近期被发现的一种性能优异的新型红外非线性光学材料.本研究采用自制的双温区管式炉成功合成出SrCdGeSe4多晶,单次合成量达到300 g;采用坩埚下降法首次生长出SrCdGeSe4单晶,尺寸为φ27 mm×80 mm;通过定向、切割和抛光等程序,得到几个不同尺寸的定向SrCdGeSe4晶片,选取一片8×8 ×2 mm3双面抛光(110)晶片测试了摇摆曲线、红外透过光谱和激光损伤阈值.结果 显示:(220)摇摆曲线半峰宽为44.8",该晶体的短波透过截止边为596 nm,且在1～ 14 μm波长范围内透过率超过68;;另外,晶体在Nd∶ YAG脉冲激光,脉宽5 ns,重复频率1 Hz,光斑直径0.15 mm测试条件下,激光损伤阈值为530 MW/cm2.     

A Novel Nonlinear Optical Complex Crystal with an Organic Ligand Coordinated through an O Atom: Tetrathiocyanatocadmiummercury‐Dimethyl Sulfoxide

A novel nonlinear optical complex crystal with an organic ligand coordinated through an O atom: tetrathiocyanatocadmiummercury‐dimethyl sulfoxide, [CdHg(SCN)₄(H₆C₂OS)₂], (CMTD) is reported for the first time. Single crystals have been grown by temperature‐lowering method, the crystals tructure has been determined, and some physical properties are given. The relations between the crystal structure and nonlinear optical properties are also discussed.     

新型非线性光学晶体BaAIBO3F2的生长及组分挥发的研究

采用高温熔液法生长BaAlBO3F2晶体(简称BABF)时,组分挥发严重.本文分析了晶体生长前后的组分中相关元素的重量损失,发现易挥发的物质可能是硼的氧化物和氟化物;X射线衍射分析确定挥发物中还含有少量的NaCl.通过改变助熔剂与熔质的配比,明显降低了晶体的生长温度,减少了组分挥发,优化了晶体生长条件,得到24mm×20mm×6mm尺寸的晶体.     

新型非线性光学晶体BaAlBO3F2的生长及组分挥发的研究

采用高温熔液法生长BaAlBO3F2晶体(简称BABF)时,组分挥发严重.本文分析了晶体生长前后的组分中相关元素的重量损失,发现易挥发的物质可能是硼的氧化物和氟化物;X射线衍射分析确定挥发物中还含有少量的NaCl.通过改变助熔剂与熔质的配比,明显降低了晶体的生长温度,减少了组分挥发,优化了晶体生长条件,得到24mm×20mm×6mm尺寸的晶体.     

红外非线性晶体材料AgGa1-xInxSe2的生长和性能表征

AgGa1-xInxSe2是近几年来研制的新型红外非线性光学晶体材料,其主要特点是借着Ga和In含量,即x值的变化,改变材料的折射率、双折射,实现三波共线非线性作用的非临界(90°)相位匹配.我们用垂直布里奇曼法生长单晶,获得了φ35mm×50mm的AgGa1-xInxSe2单晶棒.对生长出晶体棒In的浓度分布进行了测试.晶体元件用红外观察镜和分光光度计分别进行了观察和测试,晶体透光率良好.用一台TEA CO2激光泵浦一块5×6×16mm3的AgGa1-xInxSe2(x=0.3234)晶体元件,成功地实现了10.6μm非临界相位匹配倍频,输出5.3μm的中红外激光.