磷锗锌晶体的热处理研究

采用改进垂直布里奇曼法生长出的磷锗锌(ZnGeP2,ZGP)晶体中存在各种缺陷,导致其红外透过率较低,刚生长的晶体不能直接用于制备红外非线性光学器件.分别采用真空、同成分粉末包裹和真空-同成分粉末包裹的复合退火工艺对生长的ZGP晶体进行了退火热处理研究.应用傅立叶红外光谱仪(FTIR)、高阻仪(HRM)、X射线能谱仪(EDS)等对退火前后的晶体性能和成分进行了测试分析.结果表明,三种方法退火后晶体的红外透过率和电阻率都得到改善,其中复合退火工艺的改善效果最为显著,晶体红外透过率由41;提高到60;,电阻率由2.5×108 Ω·cm提高到7.2 ×108 Ω·cm,晶体成分接近ZGP理想化学配比,退火后晶体的光学和电学性能得到显著改善,可用于ZGP-OPO器件制作.     

AgGa1-xInxSe2晶体热处理研究

结合差示扫描量热曲线(DSC)和相图确定出热处理的温度范围.分别在真空和AgGa1-xInxSe2(x=0.2,0.6,0.8)多晶粉末包埋下,对ASGa0.4In0.6Se2晶体进行了热处理实验,分析了热处理对晶体性能的影响.结果表明:用x=0.6和0.8的多晶粉末包埋,在680℃下保温120 h后再淬火处理的晶片,其红外透过率在550～5500 cm-1波数范围内整体提高到65;以上,光学质量显著提高;EDX和XRD分析表明,采用AgGa0.2In0.8Se2多晶粉末包埋,能够补充晶片中的In缺失,成分更接近AgGa0.4In0.6Se2化学计量比,同时晶片结晶质量也得到明显改善.     

高能电子辐照和退火对磷锗锌晶体红外光学性质的影响

对采用改进的垂直布里奇曼法生长出的磷锗锌(ZnGeP2)单晶体样品,在300 K,10 MeV高能电子束下进行辐照实验,测试辐照前后其红外透过率.同时,对样品进行同成分粉末包裹退火处理,对比两种工艺对磷锗锌晶体红外透过率的影响.实验结果表明,退火和高能电子辐照都能对磷锗锌晶体的红外光学性质产生影响,提高其红外透过率.在本文的实验条件下,退火工艺对磷锗锌晶体红外透过率的提高更为明显.     

AgGa1-xInxSe2单晶的生长研究

采用高纯(99.9999;)Ag、Ga、In和Se单质为原料,按化学计量比富Se0.3～0.5;配料,通过机械振荡和温度振荡相结合的方法合成出单相高致密AgGa1-xInxSe2多晶材料.以此为原料采用布里奇曼法生长出外观完整的尺寸为φ15mm×25mm的AgGa1-xInxSe2单晶锭(x=0.2).沿自然显露面对晶体进行了解理和X射线衍射分析,发现该面是(101)面.同时进行了红外透过率测试,其红外透过率为41;.     

中远红外非线性光学晶体AgGaS2、AgGaSe2和AgGa1-xInxSe2研究进展

综合报道了本实验室关于黄铜矿类I-III-VI2型系列晶体的研究进展。采用两温区气相输运温度振荡法合成出高纯、单相、致密的多晶材料,在三温区立式炉中用坩埚旋转下降法生长出AgGaS2、AgGaSe2和AgGa1-xInxSe2等系列单晶体,X射线单晶衍射谱和回摆谱表明晶体的结晶性好,结构完整;红外透过率接近理论值,吸收系数低于0.017 cm-1,表明生长的晶体光学质量高。研究出一种新的能对AgGa1-xInxSe2晶体(112)晶面进行择优腐蚀的腐蚀剂:(30 g CrO3+10 mL H2O)∶H4PO4(85%)∶HNO3(65～68%)∶HF(40%)=10∶10∶10∶2(体积比),在60℃下腐蚀40 min,能够清晰地显示出AgGa1-xInxSe2晶体(112)面取向一致的三角形腐蚀坑,边界清晰,蚀坑密度大约为105/cm2数量级。采用自行研制的晶体定向切割新方法,加工出AgGa1-xInxSe2-OPO器件,获得了3～5μm的激光输出,光-光转换效率达21%。     

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.     

新型AgGa1-xInxSe2晶体用于CO2激光倍频研究

本实验室用布里奇曼方法成功生长出有应用前景的新型四元非线性AgGa1-xInxSe2晶体,对晶体光学透过,红外低倍显微成像,反射损耗和吸收系数进行了研究和计算.基于纯AgGaSe2和AgInSe2的Sellmeier方程,用线性内插方法计算了不同In含量的AgGa1-xInxSe2在0.9～19μm的Sellmeier色散系数并建立了Sellmeier方程.计算和描绘了Ⅰ型相位匹配CO2激光二次谐波产生的调谐曲线,并标出我们的倍频实验数据.在近似非临界相位匹配条件下,进行了TEA CO2激光10.6μm在AgGa1-xInxSe2中的倍频实验研究,并与AgGaSe2进行了比较,测量的1#AgGa1-xInxSe2相位匹配角θ及相位匹配接收外角△θext·L分别为88.2°和7.7°·cm,AgGa1-xInxSe2的倍频效率比AgGaSe2高出近3倍.     

CdGeAs2晶体退火与红外光学均匀性分析

采用AIM-8800红外显微镜观察了CdGeAs2晶体的面扫描红外透过图像,分别在2.3～4μm、4～8 μm和8～18μm三个波段对退火前后的CdGeAs2晶片红外透过率和面扫描红外透过图像进行了对比分析,研究了晶体的红外均匀性.结果表明,CdGeAs2晶体在多晶粉末包裹下经450℃退火150 h后,其红外透过率和红外透过均匀性都得到较大程度的改善,其中在2.3 ～4μm和4～8μm波段的改善效果尤为显著;分析了影响晶体红外透过率和均匀性的主要因素,探讨了改善晶体均匀性的可能途径.研究结果对于快速评判CdGeAs2晶片质量具有重要的实用价值.     

CdSiP2单晶退火研究

以高纯(6N) Cd、Si、P单质为原料,采用双温区气相输运法和改进的垂直布里奇曼法合成生长出等径尺寸为φ17 mm×65 mm的CdSiP2单晶锭,经切割抛光得到CdSiP2晶片.将样品分别置于真空、镉气氛、磷气氛和在同成分粉末包裹中进行了退火试验.采用X射线能量色散谱仪(EDS)和傅里叶红外分光光度计(FTIR)对退火前后的晶片组分及红外透过谱进行了测试分析.结果表明:四种氛围退火前后样品的组分变化不大,原子比接近理想的化学计量比;镉气氛下退火对晶片的红外透过率改善较为显著,在1600 ～ 4500 cm-1范围内的红外透过率由46;～52;提高到51; ～57;,接近CdSiP2晶体红外透过率的理论值.     

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.     

Spectroscopy of Charge Transfer Complexes of Aniline Blue

Charge transfer (CT) complexes of aniline blue (AB) were prepared with standard organic acceptors such as TCNQ, TCNE, DDQ, and chloranil and studied with UV-VIS-NIR spectra showing σ→π* and π→π* transitions along with free-carrier absorption due to scattering of light particles which has been found involving phonon–photon, electron–photon, and electron–electron scattering. Infrared spectra contain half power beta density due to hopping conduction and an asymmetric band corresponding to A(k) = A₀k exp(?bk) as absorption associated with diffraction of IR light from the crystalline particles.     

Raman and Infrared Spectra of Nd-Doped Barium Sodium Niobate Crystals

Neodymium-modified barium sodium niobate (Ba₂Na)_1-xNd_xNb₅O₁₅(BNN:Nd), with x = 0.025, crystallizes with a filled tungsten bronze (TB) type structure in the tetragonal system, conforming to the space group P4bm and Z = 2. The lattice constants are a = 1.2446(1) and c = 0.3991(1) nm at room temperature. Tc = 537 +- 2 °C. The experiments show that the Nd-ions effectively improve crystal structural quality. The lattice vibrational spectrum, studied by Raman and infrared reflectivity spectroscopy, shows that the crystal microscopic structure and lattice dynamics, thereby the microstrain and microstress, are very stable in a temperature range from 22 to approaching 500 °C.     

CsGeCl3: A new IR nonlinear material

Oxides and chalcopyrites, typically semiconductor materials, have their self-inherited properties to be strictly in the infrared region. CsGeCl₃ has attracted attention because of its very wide-band transparency range and its higher nonlinear optical coefficient. This paper reports a new synthesis method and research work for crystal growth conditions on the CsGeCl₃. These results show that CsGeCl₃ is a potential applications prospective material for frequency-doubling in the infrared region.     

ZnGeP2晶体轴向成分均匀性对其红外光学性质的影响

运用X射线衍射(XRD)和X射线光电子能谱(XPS)对垂直布里奇曼法生长的ZnGeP2晶体的轴向组成进行分析,发现晶体的成分不均匀。采用Rietveld全谱拟合精修定量分析各物相的相对含量,发现晶体轴向组成分布存在较大差异。晶体肩部和尾部含有Ge和Zn3P2杂相,而主体部分为单相ZnGeP2、质量相对较高。傅里叶变换红外光谱(FTIR)的测试结果表明,晶体轴向成分的差异对其红外透过率有较大影响。经过适当的热处理工艺,可以提高晶体的均匀性,改善其光学性能。     

Tautomeric investigations and crystal structure analysis of chlorzoxazone

The crystal structure and infrared spectra of the compound has been reported. Infrared spectra of the compound were examined in various solvents. The results of the crystal structure analysis and IR spectra assignments showed that the compound has the amino tautomeric form in the solid state and in studied solutions.     

Crystal structure,thermal analysis,and IR spectroscopic investigation of bis(2-amino-6-methyl) pyridinium sulfate

Synthesis, crystal structure refinement, phase transitions studied by thermal analysis, and IR spectroscopic investigation of 2C₆H₉N₂ < eqid2 > ⋅SO₄²⁻ are reported. The title compound crystallizes in the monoclinic space group C2/c (no. 15) with a = 10.5068(4) Å, b = 10.2225(5) Å, c = 14.0422(7) Å, and β = 104.489(3)^∘. A crystal packing diagram shows layers built by all the components of the structure and centered by planes z = 1/4 and 3/4. The pyridine substituents stack forming channels parallel to the c direction with dimensions of 4.163(1) Å and 5.148(4) Å. Thermal analysis shows that the anhydrous compound possesses an irreversible weak phase transition.     

Crystal structure,thermal analysis and IR spectrometric investigation of bis (2‐amino‐6‐methyl) pyridinium sulfate

The synthesis method, crystal structure determination, phase transitions studied by thermal analysis and IR spectrometric investigation of 2C₆H₉N₂⁺.SO₄^2– are reported. The compound crystallizes in the monoclinic space group C2/c (no. 15) with a = 10.5068(4) Å, b = 10.2225(5) Å, c = 14.0422(7) Å, and β = 104.489(3)°. The atomic arrangement can be described by layers built by all the components of the structure and centered by planes z = 1/4 and 3/4. The organic molecules form channels parallel to the c direction with dimensions of 4.163(1)Å and 5.148(4)Å. Thermal analysis shows that the anhydrous compound presents an irreversible weak phase transition. The IR study, based on theoretical analyses and on the literature data allows the interpretation of the IR spectrum. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structural study of thiosaccharin by single crystal X-ray diffraction and infrared spectroscopy

The structure of thiosaccharin (1,2-benzisothiazol-3(2H)-thione 1,1-dioxide) has been investigated by X-ray diffraction and infrared spectroscopic methods. The compound crystallizes in the orthorhombic space groupFdd2 witha=26.591(3),b=25.058(3),c=4.934(5) Å,Z=16. The structure consists of thiosaccharin molecules bonded to each other through N–H...O intermolecular hydrogen bonds. The infrared spectra of the thiosaccharin at room and liquid-nitrogen temperature were recorded. The spectral features in the N–H stretching region were correlated with the crystallographic data on the geometry of the N–H...O hydrogen bonding. In an attempt to assign the bands due to the SO₂ stretching modes, the spectrum of thiosaccharin was compared with that of saccharin (1,2-benzoisothiazole-3(2H)-one, 1,1-dioxide).     

铁、钴掺杂氧化锌纳米材料及其红外吸波性能研究

以氢氧化钠、氯化锌、氯化铁及氯化钴为原料,采用水热法制备了Fe、Co掺杂的片状氧化锌材料,并采用XRD、SEM、EDS、FT-IR等手段对它们的理化性质进行了表征分析.结果表明,该氧化锌片具有纳米级的空间尺度(其厚度约为10～20 nm).掺杂铁和钴的纳米氧化锌的红外光谱在3500 cm-1和1600 cm-1处的吸收峰发生红移,在430 cm-1与500 cm-1处的峰形和位置出现了明显的宽化现象,同时掺杂钴的材料在670cm-1和1040 cm-1左右处出现了新的吸收峰,表现出良好的红外吸波特性.     

9α-Fluoro-11β,17α,21-trihydroxy-1,4-pregnadiene-3,20-dione-21-acetate (9-fluoroprednisolone-21-acetate)

The synthetic steroid 9α-fluoro-11β,17α,21-trihydroxy-1,4-pregnadiene-3,20-dione-21-acetate (9-fluoroprednisolone-21-acetate), formula C₂₃H₂₉O₆F, is related to substances which are potent inducers of hepatic microsomal enzymes and anti-inflammatory agents. The structure was determined at 294 K from counter-collected data by direct methods. Crystals are tetragonal, space groupP4₁2₁2,a, b=9.214(2),c=49.452(39) Å,V=4198(4), Å,D _x =1.33μg/m³ forZ=8;R (onF) 0.063 for 915 independent intensities (I>2σ₁). The structure shows H-bonding and packing of the mean molecular plane approximately perpendicular to the crystallographic 4-fold axis.