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。     

LB膜的各向异性与二次谐波超平方增长

用偏振紫外－可见吸收及旋转样品二次谐波方法研究了半花菁／花生酸Ｙ型交替ＬＢ多层膜中由垂直浸渍过程诱导和层间相互作用增强的分子在基板平面内的定向排列，提出并证实了随层数增长的平面内附加偶极矩导致光学二次谐波强度随ＬＢ膜厚度的超平方增长关系。     

4－戊基－4＇－氰基联苯液晶的分子二阶非线性光学极化率测量方法

在玻璃衬底上制得单层硬脂酸的Ｌａｎｇｍｕｉｒ－Ｂｌｏｄｇｅｔｔ（ＬＢ）膜，做为４－戊基－４＇－氰基联苯（５ＣＢ）液晶的取向层，在取向层上旋涂一层５ＣＢ液晶，用透射二次谐波方法测量出５ＣＢ液晶分子二阶非线性光学极化率，其值为β＝７×１０－２９ｅｓｕ．对比文献值，测量得到的结果符合较好．     

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。     

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。     

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     

1—苄基—9—氢富勒烯—60LB多层膜的制备及其光学非线性性质

利用π－Ａ等温线，小角Ｘ射线衍射和光学测量方法研究了一种取代富勒烯ＬＢ膜的结构特性。纯Ｃ６０－Ｂｅ分子以体相的形式存在于气－液界面上。氮冠分子作为隔层材料，与Ｃ６０－Ｂｅ分子相混合可以制备性能优良的ＬＢ膜。     

1－苄基－9－氢富勒烯－60LB多层膜的制备及其光学非线性性质

利用π－Ａ等温线、小角Ｘ射线衍射（ＳＡＸＤ）和光学测量方法研究了一种取代富勒烯（Ｃ６０－Ｂｅ）ＬＢ膜的结构特性。纯Ｃ６０－Ｂｅ分子以体相（ｂｕｌｋｐｈａｓｅ）的形式存在于气－液界面上。氮冠（醚）（ＮＣ）分子作为隔层材料，与Ｃ６０－Ｂｅ分子相混合可以制备性能优良的ＬＢ膜。π－Ａ、吸收和小角Ｘ光衍射测量表明：这种混合膜结构的改善是由于Ｃ６０－Ｂｅ分子镶嵌在ＮＣ分子的双脂链之间造成的。通过测量三次谐波产生（ＴＨＧ）可以推出Ｃ６０－Ｂｅ的三阶非线性系数χ（３）＝２．１×１０－１１ｅｓｕ。     

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     

半花菁LB多层膜的光致各向异性研究

用光学线性和非线性方法研究了Ｙ型半花菁／花生酸交替ＬＢ多层膜的光致光学各向异性。在纳秒紫外偏振脉冲激光照射下，ＬＢ多层膜中半花菁分子发色团长轴向紫外光偏振方向重新取向。加热可以使ＬＢ多层膜平面内各向异性消失及Ｈ－聚集体分解。     

盐LB单分子层膜的非线性光学性质

合成了一种能够形成单分子层膜,又具有很大分子二阶非线性极化率的有机分子材料——菧盐。对菧盐单分子层膜进行了光学二次谐波信号的测量,得到其分子二阶非线性极化率=1.2×10~(-27)esu。但它很难构成稳定的多层膜结构。本文首次报道菧盐/花生酸混合Langmuir-Blodgett(简计L-B)膜的制备及其非线性光学性能研究,混合膜就一般分子材料不能既具有较大的二阶非线性极化率,又能形成稳定的多层膜结构这一难题的可行性进行了探索。实验证明,混合膜是制备高倍频系数的稳定多层膜的可行措施之一。     

Fabrication and Spectroscopic Characterization of Langmuir-Blodgett Films with Luminescent Rare Earth Complexes of Long Chain Double Functional Ligands Mono-L Phthalate (L = Hexadecyl, Octadecyl and Eicosyl)

In this paper, some novel long chain amphiphillic monoester molecules were designed to afford double functions: film-formation ability and luminescent sensitization ability. Subsequently organized molecular films of rare earth complexes with these functional ligands formulated as ML2NO3 were fabricated by the Langmuir-Blodgett film (LB) technology, where RE denotes rare earth ions Eu3+, Tb3+ and Dy3+; L denotes the long chain carboxylic ligands monohexadecyl phthalate (16-Phth), monooctadecyl phthalate (18-Phth) and monoeicosyl phthalate (20-Phth). The average molecular area was obtained according to the π-A isotherms. The layer structure of the LB films was demonstrated by low-angle X-ray diffraction and the average layer spacing was determined from the Bragg equation. UV absorption intensity increases linearly with the number of LB films layers, which indicates that the LB films are homogeneously deposited. The fluorescence spectra of these LB films were quite different from those of their solid complexes. It reveals that the long chain ester ligands are suitable for the excited states of Tb3+ and Dy3+ in the LB films as well as in the solid complexes, but not match with the europium ion in the LB films.     

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。     

Ftir Studies on LB Film of Amphiphile with Schiff Base as Headgroup and Its Copper Complex

Two different ways to form monolayers and LB films (surface film and subphase film) of the complex have been used, where a novel amphiphile containing Schiff base as a headgroup was used as a ligand. the monolayer behavior at the air/water interface was characterized by π-A isotherms and two-dimensional molecular orientation of alkyl chains in LB films and thermal stability were measured by polarized and variable temperature FTIR transmission spectra, indicating that the LB film of the novel amphiphile and its copper(II) complex are very stable as well as stearic acid. Because incorporating the metal ion into the monolayer makes it more condensed, thermal stability of the LB film was enhanced. as can be compared from their structure and properties, subphase films are superior to surface films.     

Langmuir-Blodgett 膜中分子聚集行为的偶极作用模型

基于经典静电场理论，描述了Langmuir-Blodgett (LB)膜中棒状分子聚集行为的偶极作用模型，给出了LB膜结构与光谱性质的关系. 讨论了X型或Z型膜中分子间距、层间距、分子取向、膜层数等结构参数对分子聚集行为的影响. 理论结果与实验值符合较好. 关键词： Langmuir-Blodgett膜 聚集体 偶极相互作用 半花菁     

Fabrication and spectroscopic properties of Langmuir-Blodgett films of novel zinc complexes with long chain mono (hexadecyl, octadecyl, eicosyl, and docosyl) phthalate

In this paper, some novel long chain amphiphillic monoester molecules were designed to afford double functions: film-formation and luminescent sensitization. Subsequently, organized molecular films of zinc complexes with these functional ligands formulated as ZnL₂ were fabricated by the Langmuir-Blodgett film (LB) technology, where L denoted the long chain carboxylic ligands monohexadecyl phthalate (16-Phth), monooctadecyl phthalate (18-Phth), monoeicosyl phthalate (20-Phth) and monodocosyl phthalate (22-Phth). The average molecular area was obtained according to the π-A isotherms. The layer structure of the LB films was demonstrated by low-angle X-ray diffraction and the average layer spacing were obtained according to the Bragg equation. The characteristic luminescence behaviors of LB films have been discussed compared with those of their corresponding solid complexes.     

聚丁二炔Langmuir—BLodgett薄膜的光声谱研究（Ⅱ）光谱综合分析和荧 …

本文用光声谱结合光吸收谱,荧光光谱等对在工业上在潜在应用前景的聚十炔（ｐｏｌｙｄｉａｃｅｔｙｌｅｎｅ,ＰＤＡ）Ｌａｎｇｍｕｉｒ－Ｂｌｏｄｇｅｔｔ（ＬＢ）薄膜进行了研究。     

两种烷基取代喹吖啶酮衍生物LB膜的荧光特性

制备了两种烷基取代喹吖啶酮衍生物C6DHQA和C16DMQA的X型Langmuir-Blodgett(LB)膜,采用紫外-可见吸收、稳态荧光和时间分辨荧光的方法研究其溶液及LB的光学特性。研究结果表明,C16DMQA比C6DHQA的吸收谱整体红移,说明烷基链加长减小了分子的能级间隔;两者LB膜的吸收谱较溶液整体红移,说明在LB膜中形成了"J-聚集体"。两种材料的溶液及LB膜都有较强的荧光发射,溶液的荧光谱与吸收谱有很好的镜像对称关系,形成LB膜后,镜像对称关系被打破,两者第三个荧光峰相对强度差别很大。C6DHQA溶液中的荧光寿命为21ns左右,C16DMQA溶液中的荧光寿命为22ns左右,形成LB膜后,荧光寿命明显较少,两者第三个荧光峰对应的荧光寿命差别较大。其原因应归于C16DMQA分子在基板上的排列更密,分子间的相互作用力强,从而对能级结构的影响更大。     

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.     

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.