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     

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.     

有机分子多层LB膜中聚集体理论和实验研究H

文中采用经典偶极相互作用模型讨论了多层Z型LB膜中分子聚集体的类型 ,给出了分子偶极相互作用能的表达式;并对理论结果与紫外可见吸收光谱的实验值进行了比较,理论结果和实验值符合较好.     

半花菁分子激发态的动力学特性研究

本文利用不同波段的时间分辨荧光和三维荧光谱对半花菁分子激发态的动力学特性进行了研究。在半花菁／花生酸交替的Y型多层膜中,半花菁分子形成的H－聚集体引起其三维荧光谱蓝移,并且荧光峰随时间的变化逐渐向红光方向移动。由于聚集体内所有分子间的相互作用（耦合）相干叠加,使得LB膜中的半花菁分子的激发态寿命比溶液寿命要短,由激发态较高振动能级向低能级过渡较快,因而不同波段的起始发光时间相差也较小。     

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.     

萘酞菁LB膜取向液晶研究

利用二(3-叔丁基硅氧基)萘酞菁硅 (SiNc) Langmuir-Blodgett (LB) 膜对丝状液晶的定向进行了研究,发现在不同膜压下沉积的SiNc LB膜具有不同的定向效果.在15mN/m低膜压下沉积的LB膜上丝状液晶主要呈沿膜面水平排列,而30mN/m高膜压下沉积的LB膜则取垂直膜面取向.原子力显微镜(AFM)对相应的LB单层膜和多层膜进行的分子尺度上的形貌研究发现,高膜压条件下SiNc分子以分离的单体或聚集体形式非连续地在基片上呈线性堆积排列,形成一定的分子“纳米线”,并且大环平面垂直于基片 关键词：     

螺芴氧杂蒽LB膜的制备及光谱特性研究

为了研究聚芴材料DSFX-SFX分子在气液两相表面的行为,分子处于溶液、LB膜及粉末状态的光学特性,以及分子有序排列对其发光特性的影响,制备了聚芴材料DSFX-SFX的X型LB膜,研究了π-A等温曲线,测量了其紫外-可见吸收谱和稳态荧光光谱。结果表明,分子以face-on形式平躺在亚相表面,单分子面积为4.78 nm2。在氯仿溶液中吸收峰位在354 nm,归属于分子中三聚氧杂蒽部分与芴环间π-π*电子跃迁;荧光发射峰位在396,419,445 nm(肩峰),归属于发色团三聚氧杂蒽,是芴环与氧杂蒽环之间的电荷转移。在LB膜中,吸收谱和荧光光谱与其溶液光谱相比,整体红移6 nm。结果表明:在LB膜中,两个分子形成激基缔合物,与单分子状态相比,激基缔合物的HOMO升高而LUMO降低。与粉末状态相比,该材料在LB膜中有很强的荧光发射,表明该材料形成有序排列超薄膜有利于荧光发射。     

温度对半花菁LB多层膜的光致荧光特性的影响

利用稳态荧光谱和时间分辨荧光技术研究了温度对半花菁Langmuir-Blodgett(LB)多层膜光致荧光特性的影响.半花菁分子在半花菁/花生酸、半花菁/花生酸镉交替及纯半花菁Z-型LB多层膜中均形成了H-聚集体,加热能使聚集体部分离解.由于Z-型膜中没有花生酸或花生酸镉的屏蔽,分子间具有较强的偶极相互作用,加热使聚集体的离解的程度较小.镉离子的加入对半花菁LB多层膜的稳态荧光谱也有一定的影响.     

中心对称萘酞菁分子的LB膜及其聚集特性研究

研究了三种中心对称的萘酞菁分子LB膜的制备及其聚集特性。三种萘酞菁化合物均能制成很好的LB膜。在稀溶液中,四叔丁基萘酞菁以单体为主要存在形式;对四叔丁基萘酞菁锌,由于金属锌原子的作用,在稀溶液中不仅能形成H-聚集体,而且还能形成J-聚集体,且主要以聚集体的形式存在。在LB膜中,这两种化合物均形成了H-聚集体。对于双四叔丁基萘酞菁铒不论在稀溶液中还是在LB膜中均主要以单体的形式存在。     

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.     

新型花菁染料Langmuir-Blodgett膜的椭偏光谱研究

利用椭偏光谱法(SE)对Y型花菁染料LB膜在紫外—可见光范围内(λ=2755—8266nm)的光学特性进行了表征,同时得到了该薄膜的光学常量(复介电常数、消光系数、吸收系数、反射系数、折射率等).讨论了LB薄膜对不同频率光的较高吸收特性及其成膜结构之间的关系,对其物理机理给予了解释.此外,采用洛伦兹振子模型对所得的光学参量进行了理论拟合,结果发现：其理论拟合与实验数据符合得非常好. 关键词： Langmuir-Blodgett膜 椭圆偏振光谱法 洛伦兹振子模型     

Molecular assembly and photophysical properties of Langmuir-Blodgett films with novel lanthanide complexes of long chain para-dodecanoyl and para-myristoyl oxybenzoate

Several ultrathin luminescent Langmuir-Blodgett (LB) films have been prepared by using the subphase containing the rare earth ions (Eu³⁺, Dy³⁺). The effect of the rare earth ions on the monolayer of p-dodecanoyloxybenzoate (12-OBA) and p-myristoyloxybenzoate (14-OBA) was investigated. IR spectra showed the rare earth ions were bound to the carboxylic acid head groups and the coordination took place between the polar head group and the rare earth ions. The layer structure of the LB films was demonstrated by low-angle X-ray diffraction. The AFM study revealed that the LB films were uniform and crack free, and the films mainly consisted of closely packed grains with an average size of 241 nm. The LB films can give off strong fluorescence, and the signal can be detected from a single layer. The characteristic luminescence behaviors of LB films have been discussed compared with those of the complexes.     

Incorporation of a liquid crystal to enhance the luminescence properties of Langmuir–Blodgett films of OC1OC6-PPV

The control of molecular architecture provided by the Langmuir–Blodgett (LB) method allows one to obtain enhanced luminescence properties in polymer films, which can be exploited in polymer light emitting diodes (PLEDs). In this study, we show that incorporating a liquid crystal (LC) (PCH302/304) into poly-(2-methoxy-5-hexyloxy-p-phenylene-vinylene) (OC₁OC₆-PPV) in LB films leads to a 4-fold increase in photoluminescence and 2-fold increase in electroluminescence for (ITO/OC₁OC₆-PPV(LC5%)/Al) devices for emission at 585 nm, with the current vs. voltage (I vs. V) characteristics exhibiting a typical behavior of rectifying diode. The enhanced luminescence was attributed to an efficient separation of emitting OC₁OC₆-PPV units induced by the LC in the LB film, which were less ordered than LB films from neat OC₁OC₆-PPV.     

Langmuir and Langmuir-Blodgett (LB) films of tetrapyridyl metalloporphyrins

We report on the formation of Langmuir films of 5,10,15,20-tetra(4-pyridyl) 21H,23H-porphine, hereafter named tetrapyridyl porphyrins with distinct central ions (2H⁺, Zn²⁺, Cu²⁺, Ni²⁺). The films were characterized with surface pressure and surface potential isotherms and in situ UV-vis absorbance. The measurements indicated strong aggregation of porphyrin monomers at the air-water interface, with a red shift of the Soret band in comparison with the spectrum obtained from CHCl₃ solutions. The shift was larger for the non-substituted H₂TPyP, and depended on the metal ion. Significantly, aggregation occurred right after spreading of the Langmuir film, with no further shifts in the UV-vis spectra upon compression of the film, or even after transferring them onto solid substrates in the form of Langmuir-Blodgett (LB) films. The buildup of LB films from H₂TPyP and ZnTPyP was monitored with UV-vis spectroscopy, indicating an equal amount of material deposited in each deposition step. Using FTIR in the transmission and reflection modes, we inferred that the H₂TPyP molecules exhibit no preferential orientation in the LB films, while for ZnTPyP there is preferential orientation, with the porphyrin molecules anchored to the substrate by the lateral pyridyl groups.     

Fundamental studies of molecular depth profiling and 3D imaging using Langmuir-Blodgett films as a model

Molecular depth profiling and three-dimensional imaging using cluster projectiles and SIMS have become a prominent tool for organic and biological materials characterization. To further explore the fundamental features of cluster bombardment of organic materials, especially depth resolution and differential sputtering, we have developed a reproducible and robust model system consisting of Langmuir-Blodgett (LB) multilayer films. Molecular depth profiles were acquired, using a 40-keV C₆₀⁺ probe, with LB films chemically alternating between barium arachidate and barium dimyristoyl phosphatidate. The chemical structures were successfully resolved as a function of depth. The molecular ion signals were better preserved when the experiment was performed under cryogenic conditions than at room temperature. A novel method was used to convert the scale of fluence into depth which facilitated quantitative measurement of the interface width. Furthermore, the LB films were imaged as a function of depth. The reconstruction of the SIMS images correctly represented the original chemical structure of the film. It also provided useful information about interface mixing and edge effects during sputtering.     

Structural and surface morphological studies of long chain fatty acid thin films deposited by Langmuir–Blodgett technique

In the present work we aim to study the structural and surface morphological characteristics of divalent cation (cadmium ion, Cd²⁺) induced thin mono- to multilayer films of fatty acids such as arachidic acid and stearic acid prepared by the Langmuir–Blodgett (LB) technique. These ultra thin films of various numbers of layers were studied by X-ray diffraction (XRD), X-ray reflectivity (XRR) and Atomic Force Microscopy (AFM). In this specific Y-type deposition, it was found that as the individual layer thickness increases, the corresponding layer by layer interfacial electron density of the thin films decreases. Since the fatty acid chain tries to maintain its minimum value of cross-sectional area, tilting occurs with respect to its nearest neighbor. The tilt angle calculated for 9 layers of cadmium arachidate (CdA₂) and cadmium stearate (CdSt₂) are 18° and 19.5°, respectively. An asymmetric air gap of thickness ∼3 Å was also seen between the tail parts of 2 molecular chains. The RMS roughness and average height factors calculated through AFM studies show non-uniform surface morphology of both CdA₂ and CdSt₂, although the calculated topographic variations were found to have more irregularity in case of CdSt₂ than in case of CdA₂.     

羟基卟啉衍生物LB膜的紫外可见光谱表征

研究了两种具有两条脂链的羟基卟啉在气液界面上的成膜性能及其ＬＢ膜。ＵＶ－Ｖｉｓ光谱表明,两种卟啉在ＬＢ膜中的聚集态不同,卟啉环上脂链和羟基呈对称了代时形成Ｊ－聚体,呈同侧取代时形成氢键聚集体。利用偏振ＵＶ－Ｖｉｓ吸收谱测定了ＬＢ膜中卟啉环的取向。结果表明,侧链和羟基的相对位置对环的取向没有影响,但影响膜中平均分子截面积的大小和环间的距离,因而影响膜中分子的聚集态。     

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。     

Role of various LB parameters on the optical characteristics of mixed Langmuir-Blodgett films

This communication reports the spectroscopic characterizations of mixed Langmuir-Blodgett (LB) films of non-amphiphilic N,N-bis (2,5-di-tert-butylphenyl)- 3,4,9-perylenedicarboximide (DBPI) molecules, mixed with polymethyl methacrylate (PMMA) and stearic acid (SA). J- aggregates of DBPI molecules in the mixed LB films have been confirmed by UV-Vis absorption spectroscopic study. Formation of organized structure of molecular stacking in the mixed LB films gives rise to the strong excimeric emission, which is manifested by a broad structureless band in the longer wavelength region of the fluorescence spectra and is confirmed by excitation spectroscopic study. A weak hump at around 576 nm due to monomeric emission is observed in the fluorescence spectra of 0.1 M of DBPI-PMMA mixed LB films of lower number of layers. The intensity of the 0-0 band at 530 nm in the fluorescence spectra is observed to be a function of the molefraction, number of layers, surface pressure of lifting and the matrix materials.