4-硝基-4′-氨基偶氮苯的光学性质研究

采用紫外可见吸收和二次谐波产生技术研究了“推-拉”型偶氮苯分子Langmuir-Blodgett(LB)膜的光谱和二阶非线性光学特性.4-硝基-4′-氨基偶氮苯(NAA)分子能制成很好的LB多层膜,在稀溶液中以单体的反式异构体形式存在,在膜中主要以J-聚集体的形式存在,LB膜的紫外可见吸收谱的吸收峰较之溶液的发生了52 nm的红移.NAALB膜的二阶非线性极化率χ(2)为19.59×10－8 esu,一阶超极化率β值较大,约为1.974×10－29 esu.其光学二阶非线性起源于电偶极子机制.     

温度对稀土夹心双萘酞菁LB膜光学性质的影响

 采用线性吸收谱和二次谐波产生技术研究了温度对具有中心对称结构的稀土夹心双萘酞菁化合物LB膜光学特性及其LB膜结构的影响。研究发现,加热可以使其LB膜的结构及分子间的相互作用发生变化,并形成J聚集体,从而使得吸收峰发生红移。稀土夹心双萘酞菁化合物约在40 ℃时其二次谐波信号有一个极小值,约在65 ℃时该化合物发生相变,使得二次谐波信号产生极大值,二次谐波信号最小时温度可高达180 ℃,说明该化合物的化学结构较为稳定。     

半花菁／氮冠（醚）交替LB多层膜的二阶光学非线性性质

对一种新型的，具有双脂链的盘状非活性分子氮冠（醚）（ＮＣ）ＬＢ膜进行了表征。小角Ｘ射线衍射（ＳＡＸＤ）结果表明：纯ＮＣ分子可以形成非常好的ＬＢ膜有序结构。将它与活性分子半花菁（ＤＡＥＰ）制备成Ｙ型交替多层膜，由于半花菁分子的单脂链（长尾）可以镶嵌在ＮＣ分子的双脂链之间，改善了多层膜的结构有序性及稳定性，从而得到二次谐波强度随层数的变化在１￣１１６双层范围内显示出较理想的平方关系。通过二次谐波的测量     

LB膜混合聚集体中极性基团相互作用对光学非线性的影响

通过紫外－可见吸收光谱、压力－面积等温线、二次谐波的测量，研究了不同活性分子混合聚集体的形成对ＬＢ膜光学性质的影响。分子极性基团间的相互作用，使激发态能量及平均偶极矩发生变化，导致ＬＢ膜的光学非线性明显地增强或减弱。     

稀土夹心双萘酞菁LB膜的非线性光学特性研究

研究了中心对称稀土夹心双萘酞菁化合物LB膜的光谱及其二阶非线性光学特性.双(四叔丁基萘酞菁)铒能制成很好的LB膜,不论在稀溶液中还是在LB膜中均主要以单体的形式存在,分子具有较大的超极化率β.由于分子为中心对称结构,所以它们的二次谐波产生机制不同于不对称萘酞菁化合物,研究证明它的二阶非线性光学特性起源于电四极子模型,其LB膜的有效二阶非线性极化率χ(2)为1.1×10-8 esu.     

半花菁衍生物LB膜的非线性光学性能研究

本文利用二次谐波产生、紫外－可见吸收光谱、Ⅱ－Ａ曲线等方法，探讨了四种分子结构相近的半花菁染料衍生物ＬＢ膜的非线性光学性能。研究了它们的分子结构与β值大小的关系，分析了引起β值变化的主要原因，证实了极性基团的强弱顺序。并讨论了ＬＢ膜中聚集效应程度不同的原因。通过光学二次谐波信号强度与膜层数的关系，对比了样品的成膜性能。     

光学非线性LB膜的时间稳定性与光致漂白效应的关系

用光学二次谐波产生（ＳＨＧ），拉曼散射和紫外－可见吸收光谱等方法研究了偶氮，苯腙及半花菁三种有机染料Ｚ型Ｌａｎｇｍｕｉｒ－Ｂｌｏｄｇｅｔｔ（ＬＢ）多层膜的时间稳定性问题，发现：随着放置时间的推延，其中ＬＢ膜的二次谐波产生信号强度下降，然后逐渐达到稳定；在高压汞灯光照射下，粉末样品中Ｎ＝Ｎ（偶氮），Ｃ＝Ｎ（苯腙），Ｃ＝Ｃ（半花菁）键伸缩振动所对应的拉曼峰强度以及这三类染样在ＬＢ膜样品中对所应的生色团     

氰基团修饰的苯腙类有机分子掺杂极化聚合膜光学非线性的研究

采用实时测量光学二次谐波产生（ＳＨＧ）和吸收光谱的方法对苯腙类有机分子ＮＤＡ及一种新合成的经氰基团修饰的有机分子ＣＮＤＡ掺杂ＰＭＭＡ极化聚合膜的非线性光学性质进行了研究。实验中发现两种掺杂极化聚合膜的最佳电晕极化温度均低于它们的玻转温度,ＣＮＤＡ／ＰＭ－ＭＡ极化掺杂聚合膜的χ（２）较ＮＤＡ／ＰＭＭＡ极化聚合膜的大。结合极化前和极化后吸收峰强度的变化,得到ＣＮＤＡ分子的非线性极化率β约为１４６×１０－３０ｅｓｕ。在撤离极化场后,ＣＮＤＡ／ＰＭＭＡ的二次谐波强度的弛豫也比ＮＤＡ／ＰＭＭＡ的慢     

LB膜的变入射角透射光学二次谐波产生研究

给出了不同基频光和倍频光偏振态组合情况下，淀积在固体基板上的Ｌａｎｇｍｕｉｒ－Ｂｌｏｄｇｅｔｔ单分子层膜在面对入射光方向和背对入射光方向时，反射及透射光学二次谐波产生随入射角变化关系的理论公式。在此基础上，对一种芪盐ＬＢ膜样品进行变入射角的透射二次谐波产生研究。     

一种液晶化合物LB膜中的分子取向及膜结构

"利用LB技术制备出MPUOPM的Langmuir和LB膜．随着表面压力的升高,在?-A曲线上的可观察到一个明显的折点．通过与分子刚性基团的理论截面积相比较,发现该折点反映的是单层膜向多层膜的转变．紫外可见、偏振红外等光谱被用来研究膜的结构,发现烷基链与基片法线夹角为48o,C＝N基团互相平行,与基片法线呈51o夹角排列．"     

Structure and Orientation of 1-Hydroxyl-5-Hexadecyloxy-Naphthalene LB Films Studied By UV-VIS and FTIR Spectroscopy

Ultraviolet-visible (UV-Vis), infrared transmission, and reflection absorption(RA) spectra have been measured for one-and multi-monolayer Langmuir-Blodgett(LB) films of C₁₆H₃₃30Naph(1,5)OH at various temperature to investigate dependencies of the aggregation and phase transitions on the number of monolayers. The UV-vis spectra of the LB films have revealed that the C₁₆H₃₃ONaph(1,5)OH forms aggregates in the LB film. From the temperature dependence of UV-vis absorption spectra, it is clear that the aggregate is gradual converted to monomer upto 80 °C. A comparison of the infrared transmission and RA spectra reveals that the hydrocarbon chains are tilted considerably in the LB film. As for the naphthalene ring part, the result suggest that the ring plane is oriented approximately perpendicular to the substrate surface. The Temperature dependence of infrared transmission spectra have been measured for 1-, 3-, and 11-monolayer LB films to investigate dependence of phase transitions on the number of monolayers. These observations show that the one-monolayer LB films does not have a clear order-disorder transition, while the three-and eleven-monolayer films have a phase transition near 60 °C. Therefore, it seems that the title angles of both the alkyl chain and chromophore part change largely concomitantly with the conversion from the aggregate to the monolayer.     

直流电场诱导LB膜中分子重新取向研究

用旋转二次谐波产生方法研究了半花菁/花生酸Y型交替LB多层膜中由外加法向直流电场诱导的分子的重新取向.外加法向直流电场能够有效地改变LB膜中光学活性半花菁分子的取向,迫使其长轴转向电场的方向.随着极化电场的增大,分子在基板平面内的各向异性逐渐减小,而二次谐波强度的增量则随外加电场的增大而呈现平方增长的规律.在室温下,用1.3×10⁶V/m的电场极化10min,可以使半花菁LB多层膜的二次谐波强度增大一个量级.     

不同表压下芪盐LB膜二阶光学非线性的研究

研究了芪盐在不同表压下制备的ＬＢ膜的二阶光学非线性。测量得到在低表压增强的二次谐波信号。对比芪盐的π－Ａ曲线和透射光谱，认为在ＬＢ膜中芪盐以固相态存在，低表压时的固相态聚集体的吸收峰３５１ｎｍ使四阶非线性极化率Ｘ＾（４）（－２ω：ω，ω，ω，－ω）产生共振强，四阶光学非线性现象对二次谐波信号产生影响。     

Frequency doubling with periodically poled KTiOPO4 at the fundamental wave of cesium D2 transition

We report the continuous wave (CW) second harmonic generation (SHG) with a periodically poled KTiOPO4 (PPKTP) pumped by a diode laser at 852.356 nm, which is exactly resonant on the cesium D2 transition.     

共轭双键结构不同的三种有机染料分子的拉曼光谱研究

共轭双键结构不同的三种有机染料分子的拉曼光谱研究姚文华（复旦大学分析测试中心上海２００４３３）马世红，刘丽英，王文澄（三束材料改性国家重点实验室，复旦大学物理系上海２００４３３）ＲａｍａｎＳｐｅｃｔｒｏｓｃｏｐｙｓｔｕｄｉｅｓｏｆＴｈｒｅｅＯｒｇａｎ...     

Electron-beam poling in undoped, N- or Ge-doped MDECR H:SiO2 films

Amorphous N- or Ge-doped H:SiO₂ films deposited on silica by the matrix distributed electron cyclotron resonance-PECVD method were irradiated by an electron-beam with different doses in order to pole the material and induce second harmonic generation (SHG). SHG was measured using the Maker-fringe method. When irradiated at an acceleration voltage of 25 kV, an incident current of 5 nA during 480 s, the N-doped H:SiO₂ films exhibited a maximum second harmonic signal in the order of 0.003 pm/V, but when irradiated with an acceleration voltage of 30 kV, at 5 nA during 240 s, the films exhibited a maximum second harmonic signal of 0.006 pm/V. With a smaller current of 0.5 nA during 25 s and 25 kV acceleration voltage, the Ge-doped H:SiO₂ films (3.8 at. % Ge) showed a maximum second-order nonlinearity of 0.0005 pm/V. But an H:SiO₂ films with a smaller Ge content (1.0 at. % Ge), showed a large SHG: d₃₃=0.09 pm/V when irradiated at 25 kV, 0.5 nA during 15 s. PACS 78.66.J; 42.65.K; 68.60.D     

稀土夹心双酞菁铥的LB膜及其光谱特性

采用表面压-面积(π～A)等温曲线和紫外-可见吸收光谱研究了稀土夹心双酞菁铥(TmPc2)分子在Langmuir膜及其Langmuir-Blodgett(LB)膜中分子的排列状态和光谱特性。发现TmPc2分子在纯膜中以edge-on方式面对面的排列,在与花生酸(AA)的混合膜中TmPc2分子以face-on方式平躺排列。纯的TmPc2分子在亚相表面可以形成稳定的Langmuir膜,但不易转移到固体基片上,加入花生酸混合后不仅可以在亚相表面形成稳定的Langmuir膜,而且可以较好地转移到固体基片上,制成多层LB膜。TmPc2氯仿溶液和LB膜的紫外-可见吸收光谱具有明显的Soret吸收带和Q吸收带,Soret吸收带有2个吸收峰,分别对应184—187*和178—186的轨道电子跃迁。而Q吸收带有4个吸收峰,分别对应于186—189*,190*和185—187*,188*的轨道电子跃迁。由于分子间的相互作用,TmPc2分子在LB膜中紫外-可见吸收谱的各个吸收峰与氯仿溶液中的吸收峰相比较都发生了红移。层内分子的相互作用比层间分子的相互作用强。     

染料J聚集体Langmuir-Blodgett膜光致发光谱的温度影响与多声子跃迁

在20—300K的范围内测量了三种花青染料聚集体Langmiur-Blodgett(LB)膜的光致发光谱。随着温度下降零声子线J峰强度的增大,观察到声子伴带的异常加强。分析表明生长不均匀的聚集体B膜具有低维晶体的特性,声子耦合强,且无辐射跃迁起着重要的作用。     

Application of differential charging in XPS for structural study of Langmuir-Blodgett films

Differential charging in XPS was recently shown to be a novel technique for studying in-depth structural information of discrete cadmium layers in Langmuir-Blodgett?(LB) multilayer films. Here we report structural modification in multilayer LB films after sulfidation using differential charging in angle-dependent XPS that are not observable by the x-ray reflectivity technique. An AFM study suggests less modification in compact LB films in comparison to the non-compact ones. The differential charging in the LB multilayers changes after sulfidation due to the formation of cadmium sulfide nanostructures in the cadmium arachidate LB matrix, which was reflected prominently in the differential charging of Cd?3d(5/2) XPS peaks. It was found that, even after sulfidation, the compact multilayer LB films were differentially charged in the out-of-plane (in-depth) direction, whereas this kind of differential charging was not apparent in rough and non-compact films. Our results clearly indicate that for LB films with compact structure a partial layered structure survives the impact of particle formation, whereas for non-compact films the modification is large and no specific conclusion could be drawn. While x-ray reflectivity cannot provide specific information about the internal structure of the post-sulfidation films it shows that the total thickness of the films reduces in all cases.     

Effect of thermal treatment on the nonlinear optical response and stability of hybrid inorganic-organic films

Hybrid inorganic-organic second-order nonlinear optical (NLO) materials have been obtained through hydrolysis and co-condensation between tetraethyl silicate (TEOS), Vinyltriethoxysilane (VTES) and an alkoxysilane dye (ICTES-DR1). The hybrid materials showed a thermal stability up to 306 °C in thermogravimetric analysis (TGA) thermograms and no visible glass transition temperature (T_g) was observed in the range 50-200 °C in differential scanning calorimetry (DSC) thermograms. The poling profiles of the hybrid films were investigated by using the in situ second harmonic generation (SHG) measurement. The thermal stability of the second order NLO properties of the poled films were also investigated by the in situ SHG intensity probing. It has been shown that the NLO response and its thermal stability were strongly dependent on the thermal pretreatment of the films.