聚苯乙烯芪盐L—B膜的二阶非线性光学性质研究

首次合成了一种称之为聚苯乙烯芪盐的有机高分子材料.此材料可以在水面上形成稳定的单分子层膜,并且所形成的单分子层膜可以转移到固体衬底上去.对聚苯乙烯芪盐单分子层膜进行光学二次谐波产生测量,得到聚苯乙烯芪盐对应于每个发色团的二阶非线性极化率为1.2×10~(-28)esu.制备了该材料两种不同类型的多层膜,讨论了多层膜二次谐波产生信号不随层数增加而增加的可能原因.     

组装L-B膜光学二次谐波的实验研究

一种分子形成的多层L-B膜由于相邻层的分子取向相反而使非线性极化抵消,总的X~(2)=0.本文用光学二次谐波方法确定了带有不同极性基团的L-B单分子层的有效非线性系数的大小和符号,对有效非线性系数符号相反的两种单分子层交替组装,使相邻单分子层的非线性极化相互叠加,得到了具有较大二阶非线性系数的组装L-B膜.     

制备条件对Langmuir－Blodgett膜中分子聚集态的影响

通过对不同制膜条件下样品的π－Ａ曲线及紫外－可见吸收光谱的测量，研究ＬＢ单分子层膜中半花菁衍生物（ｈｅｍｉｃｙａｎｉｎｅｄｅｒｉｖａｔｉｖｅ简称ＨＤ）分子的聚集状态及其形成机制。纯半花菁衍生物单分子层膜中分子以Ｈ聚集体的形式存在导致吸收峰的兰移及有效分子二阶非线性极化率β（基频波长λ＝１．０６４μｍ）的减小。实验表明聚集体的形成主要发生在压膜过程。提高压膜速度或降低压膜终极压力（拉膜压力）可显著减小分子的聚集程度，从而提高单分子层膜的光学非线性极化率。     

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.     

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.     

LB膜的制膜条件优化及其对光学性能的影响

通过紫外-可见吸收光谱、二次谐波振荡和稳态荧光的测量,研究了半花菁(DAEP)Langmuir-Blodgett(LB)膜在不同制膜条件(压膜速度、半花菁和花生酸混合、亚相中加入碘离子)下,LB膜样品中半花菁分子的聚集体性质的改变和对非线性光学性能的影响.实验发现,纯半花菁LB膜中分子形成H-聚集体,从而导致吸收峰、荧光峰的蓝移和分子二阶非线性极化率β的减少.分子聚集程度的减少和分子二阶非线性系数β的增加可以通过增大压膜速度、半花菁和花生酸混合、亚相中加入碘离子等方法实现.     

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。     

双亲性席夫碱金属配合物LB膜的制备和结构特征

合成了双亲性席夫碱配体与Ｚｎ＾２＋,Ｃｄ＾２＋的配合物,用元素分析,红外光谱和紫外光谱对配合物进行了鉴定,以Ｌ－Ｂ技术得到了层状有序多层膜。ＬＢ膜的紫外可见吸收光谱表明膜中分子形成了Ｈ－聚集体,且具有特定取向,该膜在紫外光的照射下,膜内配体分子发生的烯醇－醌式结构转变能够提高分子的非线性极化率,该结果有利于这类配合物薄膜材料非线性光学性质研究。     

萘酞菁化合物LB膜的二阶非线性光学特性研究

研究了四种萘酞菁化合物LB膜的制备和二阶非线性光学特性 ,并对它们的二阶非线性产生机理进行了简单的讨论。不对称萘酞菁化合物的二阶非线性起源于电偶极子机制 ;对称萘酞菁化合物的二阶非线性起源于磁偶极子耦合机制。二阶非线性最大的三叔丁基氰基萘酞菁的二阶非线性极化率 χ( 2 ) 为 3 7× 10 - 8esu ,约为三叔丁基萘酞菁的 37倍     

稀土夹心双酞菁铽LB膜非线性光学特性

利用π-A等温曲线和-二次谐波产生方法研究了稀土夹心双酞菁铽(TbPcPc*)分子在Langmuir膜及Langmuir Blodgett(LB)膜中分子的排列状态及其非线性光学特性,并对非线性产生机制进行了简单的讨论.实验结果表明,TbPcPc*分子在亚相表面可形成稳定的Langmuir膜,凡以edge-on构型面对面倾斜排列.其X型LB膜具有较好的二次谐波信号,二次谐波信号的最大值在基频光入射角为55°的地方.其._二阶非线性极化率γ(2)和分子超极化率β分别为1.64×10'-8esu和6.21×10-30esu.通过测量样品二次谐波信号的偏振特性,并与理论分析相比较,其二阶仆线性起源于电四极子和电偶极子机制.     

不同表压下芪盐单层LB膜二次谐波的研究

在不同表压下制备芪盐的单层LB薄膜,测量LB膜的二次谐波信号.在低表压得到增强的二次谐波信号.对比芪盐的透射光谱,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)产生共振增强,四阶光学非线性现象对二次谐波信号产生影响.     

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。     

Low-energy electron diffraction study of the surface structures of adsorbed amino acid monolayers and ordered films deposited on copper crystal surfaces

Monolayer structures and ordered multilayer films of several amino acids on single-crystal substrates were studied using low-energy electron diffraction. At monolayer coverage, ordered layers of glycine, alanine, D- and L-tryptophan were observed on both Cu(100) and Cu(111). With increasing film thickness, ordered multilayer structures of the tryptophans were also seen on both substrates. The monolayer structures are considered in terms of molecular size and packing. The optically isomeric D- and L-tryptophans yielded surface structures which were related by mirror inversion. Ordered multilayer films, apparently unlike the bulk crystals, were obtained only for tryptophan. Electron beam damage was serious for both glycine and alanine multilayer films while tryptophan films remained unaffected in agreement with previously observed stabilization by conjugated electron systems.     

Formation of solid-state excitons in ultrathin crystalline films of PTCDA: from single molecules to molecular stacks

We directly follow the evolution of the absorption spectrum from a single molecule to a dimer and further to a one-dimensional molecular stack: We determine the optical absorption properties of ordered monolayer to multilayer films of PTCDA (3,4,9,10-perylenetetracarboxylic dianhydride) on muscovite mica(0001) surfaces by in situ differential reflectance spectroscopy. The data clearly show the transition from the single molecule to a dimer spectrum, followed by the exciton delocalization to a molecular crystal exciton. The accompanying spectral shifts compare favorably with recent model concepts.     

Surface analysis monitoring of polyelectrolyte deposition on Ba0.5Sr0.5TiO3 thin films

Thin films are currently gaining interest in many areas such as integrated optics, sensors, friction, reducing coatings, surface orientation layers, and general industrial applications. Recently, molecular self-assembling techniques have been applied for thin film deposition of electrically conducting polymers, conjugated polymers for light-emitting devices, nanoparticles, and noncentrosymmetric-ordered second order nonlinear optical (NOL) devices. Polyelectrolytes self-assemblies have been used to prepare thin films. The alternate immersion of a charged surface in polyannion and a polycation solution leads usually to the formation of films known as polyelectrolyte multilayers. These polyanion and polycation structures are not neutral. However, charge compensation appears on the surface. This constitutes the building driving force of the polyelectrolyte multilayer films.The present approach consists of two parts: (a) the chemisorption of 11-mercaptoundecylamine (MUA) to construct a self-assembled monolayer with the consequent protonation of the amine, and (b) the deposition of opposite charged polyelectrolytes in a sandwich fashion. The approach has the advantage that ionic attraction between opposite charges is the driving force for the multilayer buildup. For our purposes, the multilayer of polyelectrolytes depends on the quality of the surface needed for the application. In many cases, this approach will be used in a way that the roughness factor defects will be diminished. The polyelectrolytes selected for the study were: polystyrene sulfonate sodium salt (PSS), poly vinylsulfate potassium salt (PVS), and polyallylamine hydrochloride (PAH), as shown in Fig. 1. The deposition of polyelectrolytes was carried out by a dipping procedure with the corresponding polyelectrolyte. Monitoring of the alternate deposition of polyelectrolyte bilayers was done by surface analysis techniques such as X-ray photoelectron spectroscopy (XPS), specular reflectance infrared (IR), and atomic force microscopy (AFM). The surface analysis results are presented through the adsorption steps of the polyelectrolytes layer by layer.     

LB薄膜的线性电光效应

本文用电光微分表面等离子激元光谱研究芪盐单分子层LB薄膜在不同光波长处(488nm,633nm和832nm)的电光响应.指出这是一种十分有效,简便的评估厚度小于100nm超薄膜非线性光学特性的实验技术.     

微粗糙基底上多层涂层光散射偏振建模与特性研究

为满足多层涂层目标的偏振探测需求,基于一阶矢量扰动理论,结合偏振传输矩阵,建立微粗糙基底上多层涂层的光散射偏振双向反射分布函数模型,研究多因素影响下两种典型涂层目标,单层减反射涂层和多层高反射涂层的光散射偏振特性,结果表明单层减反射涂层目标的偏振度受观测位置影响,峰值左侧的偏振度较之裸基底增大,右侧反之,探测不同观测角下的偏振度可区分无涂层和涂层目标。不同观测角和入射波长下,多层高反射涂层目标的偏振度与涂层层数和涂层光学厚度显著相关,层数增加,多层涂层在镜反射附近具有去偏作用。仿真结果符合测量数据,验证了多涂层目标散射偏振模型的正确性与合理性,为实现多涂层目标偏振探测和反射隐身技术提供理论依据。     

Mo/Si软X射线多层膜中厚度均匀性的精细控制

为了获得光学性质均匀的大面积软X射线多层膜,必须控制好周期结构中单层膜的厚度均匀性。为此建立了磁控溅射薄膜沉积技术中单层膜厚度均匀性的分析和控制模型,解释了基底变速转动法可用来获得膜厚均匀的多层膜,并根据理论分析获得了基底的变速路径。将其应用于基底公转速度变速法来制备均匀性可控的大面积Mo/Si软X射线多层膜。小角X射线衍射测试结果表明,采用优化后的变速路径制备的多层膜,样品不同位置的各级次衍射峰位都能很好吻合,说明多层膜的周期厚度基本一致。计算表明该方法在直径200mm范围内可将周期结构中Mo层的不均匀性从20.6%修正到1.1%,Si层的不均匀性从27.0%修正到1.6%。