Supramolecular structure formation of Langmuir-Blodgett films of comblike precursor and polyimide

The surface structure of Langmuir-Blodgett films of a comblike polyimide precursor—a rigid-chain polyamic acid alkylamine salt bearing multichains of tertiary amine—and films of the corresponding polyimide were studied by atomic force microscopy (AFM). An analysis of the images of the surface of three-layer films revealed a domain structure. It was found that the Langmuir-Blodgett film formation of the precursor occurs as a result of the layer-by-layer deposition of two-dimensional domains (composed of polyamic acid salt molecules on the water surface) onto a substrate. The formation of domains in a monolayer is associated with the chemical structure of the precursor, to be more precise, with the rigidity of the main chain and the presence of closely spaced aliphatic side chains in the polymer chain, whose total cross-section area is close to the surface area of the projection onto the plane of the repeating unit of the main chain. Polyimide films inherit the domain structure of the precursor films; the inhomogeneity of the film thickness substantially decreases, whereas the domain size and character of their distribution in the film remain unchanged.     

Formation of Langmuir-Blodgett films in solutions of comblike polymers

The structures have been analyzed of the monolayers of comblike precursor polymers of polyimides and mixed cellulose esters formed at the water/air interface and of the Langmuir-Blodgett films obtained by transfer of these condensed monolayers onto solid substrates. The important factors that ensure the structure control and supramolecular organization of these monolayers and films are established.     

Comparative Study of Mixed Monolayers of a Calixarene with a Fatty Acid and a Non-Amphiphilic Nematic Liquid Crystal

Abstract

Many nematic liquid crystals (NLCs) lack a polar headgroup and thus are not able to form stable monolayers at the air/water (a/w) interface. A way to obtain monomolecular films of these compounds is to incorporate them into host monolayers of amphiphilic molecules. We report a comparative investigation of mixed films of Calix[4]resorcinarene O-octacarboxymethylated (CRO) with the non-amphiphilic NLC MBBA and with the amphiphilic stearic acid (SA). The comparative study is useful for a better understanding of the characteristics of the CRO-MBBA mixed films. Surface-pressure and surface-potential measurements on the monolayers at a/w interface, as well as ellipsometric and spectroscopic measurements on transferred Langmuir-Blodgett (LB) films, confirm that MBBA is additively incorporated into CRO films.     

Model of packing of cellulose acetomyristinate in Langmuir-Blodgett films

The variation of the structural characteristics in the transition from a block polymer to a Langmuir-Blodgett film has been investigated for cellulose acetomyristinate by the methods of X-ray diffraction analysis. The effect of length and number of acid residues on the diffraction pattern of block cellulose acetomyristinate is studied. The role of acyl substituent in the formation of an ordered structure of multilayer Langmuir-Blodgett films is established. A model of packing of cellulose acetomyristinate molecules in the Y-type films is suggested. The model is based on a two-domain structure in which close-packed myristic-acid residues are located either normally or at a certain angle to the plane of glucoside rings on one side of the polymer chain.     

A Technique for the Characterisation of Langmuir-Blodgett Films

A method has been developed which allows the characterisation of Langmuir-Blodgett films. The technique utilises the liquid crystal aligning properties of the films and may be applied to films composed of any number of layers. Two materials were studied, ω-tricosenoic acid and cadmium arachidate. Differences between one and three layer samples of these materials are discussed and observed defects down to a size of approximately 1–2 microns are illustrated. Tentative explanations for the occurrence of some of the defects are put forward. The results of a preliminary study of electron beam damage in ω-tricosenoic acid are presented.     

On two-dimensional ferroelectricity in layered polymer films on substrates

A simple model for describing structural phase transitions in thin ferroelectric copolymer films on solid substrates obtained by the Langmuir-Blodgett method has been suggested. It is shown that the polymer-substrate interaction and surface tension considerably influence these transitions and, in particular, can induce additional low-temperature first-and second-order phase transitions depending on the material parameters and the film thickness. The main dimensionless parameter and its critical value, which control the formation of the additional order in very thin films, are determined.     

Two-dimensional crystallization of proteins on lipid monolayers at the air–water interface and transfer to an electron microscopy grid

The two-dimensional (2-D) crystallization of proteins on lipid monolayers at the air–water interface is a well established method for crystallizing soluble proteins. The transfer of 2-D crystals from the air–water interface to an electron microscopy (EM) grid constitutes a critical and ill-controlled step in the whole procedure, which is likely to be responsible for the high variability of results obtained with this method. In this paper, we address the following questions: (1) does the material observed on EM grids constitute a true representation of the material present at the air–water interface? (2) is there an optimal method of transfer to obtain well-ordered protein 2-D crystals? To answer these questions, we combine data obtained on three different protein systems, annexin V, streptavidin and cholera toxin, using two types of EM grids, coated with either holey carbon films or continuous carbon films. These combined observations help us draw a coherent picture of the state of the interfacial films at the air–water surface and provide new insight into the perturbing influence of the transfer step. The main conclusions are: (1) both annexin V and streptavidin form crystalline monolayers at the air–water interface, which are well preserved when transfer is performed by means of holey carbon films; (2) a major reorganization of the material present at the water surface accompanies transfer with continuous carbon films; the basal monolayer is extensively damaged, transforming into domains and vesicular structures, which do not pre-exist at the water surface; with the three protein systems studied here, these domains are often crystalline; (3) the most striking structural reorganization induced by transfer with continuous carbon films is observed with annexin V, for which the native p6 crystalline assembly is transformed into another crystal form more ordered, with p3 symmetry. It is most probable that these conclusions also apply to other protein 2-D crystals formed by the lipid monolayer method. The recent in situ observation of 2-D crystals of annexin V formed on solid-supported bilayers, by atomic force microscopy, supports our interpretation that monolayers transferred with holey carbon films represent the genuine material pre-exisiting at the air–water interface.     

单晶硅外延生长晶化硅薄膜的研究

采用P型单晶硅片为衬底,并经混合酸溶液腐蚀抛光、清洗后,利用射频磁控溅射镀膜系统在其表面制备非晶硅薄膜;再结合快速光热退火工艺,于N2气氛下480℃退火30 min,得到晶化硅薄膜;利用光学金相显微镜、XRD衍射仪和拉曼散射光谱(Raman)仪对单晶硅衬底和晶化硅薄膜进行结构和性能表征.研究了混合酸溶液对单晶硅表面腐蚀效果、籽晶诱导外延生长晶化硅薄膜的物相结构和薄膜带隙.结果表明:采用混合酸溶液腐蚀后得到表面平整、光滑的单晶硅衬底;非晶硅薄膜经过快速退火后受籽晶诱导生成晶化硅薄膜,其晶相沿单晶硅衬底取向择优生长;随着非晶硅薄膜厚度从80 nm增加到280 nm,晶化后硅薄膜的表面粗糙度逐渐减小,晶化率从90.0;逐渐降低到37.0;;晶粒尺寸从6.65 nm逐渐减小到1.71 nm;带隙从1.18 eV逐渐升高到1.52 eV.     

Spectroscopic and microscopic study of aggregate formation in the nano-dimensional Langmuir-Blodgett films of perylene with a fatty acid/polymer

Perylene (PYL) mixed with Behenic acid (BA) and Polymethyl methacrylate (PMMA) separately have been incorporated in the Langmuir-Blodgett film. The surface pressure versus area per molecule area isotherms are measured at various molar ratios. Stability of the mixed monolayer of PYL and BA/PMMA and their collapse pressure are much higher than that of pure PYL. Negligible amount of hysteresis observed in the compression-decompression isotherms indicate the formation of stable monolayer. Miscibility of the mixed systems is found to vary with the film composition. The formation of PYL aggregates in the mixed films is investigated using UV-Vis absorption spectroscopy, emission spectroscopy and atomic force microscopy (AFM).     

Study of structural order in porphyrin-fullerene dyad ZnDHD6ee monolayers by electron diffraction and atomic force microscopy

The structure of porphyrin-fullerene dyad ZnDHD6ee monolayers formed on the surface of aqueous subphase in a Langmuir trough and transferred onto solid substrates has been studied. The data obtained are interpreted using simulation of the structure of isolated molecules and their packing in monolayer and modeling of diffraction patterns from molecular aggregates having different sizes and degrees of order. Experiments on the formation of condensed ZnDHD6ee monolayers are described. The structure of these monolayers on a water surface is analyzed using π-A isotherms. The structure of the monolayers transferred onto solid substrates is investigated by electron diffraction and atomic force microscopy. The unit-cell parameters of two-dimensional domains, which are characteristic of molecular packing in monolayers and deposited films, are determined. Domains are found to be organized into a texture (the molecular axes are oriented by the [001] direction perpendicular to the substrate). The monolayers contain a limited number of small 3D domains.     

Photo-alignment Property of Azobenzene-containing Polyimide Films Swollen by Alkyl-amine

Photo-alignment efficiency of polyimide containing azobenzene in the backbone structure (Azo-PI) is significantly enhanced by exposing the precursor (polyamic acid: Azo-PAA) film to alkyl-amine vapor prior to photo-alignment. In this study, we have investigated the relationships between the alkyl-amine vapor treatment time, the swelling ratio of Azo-PAA films, and the photo-induced in-plane anisotropy. We found that: the Azo-PAA film swells on exposure to alkyl-amine vapor, and the swelling finally saturates; and the photo-induced in-plane anisotropy is correlated very closely with the swelling ratio. In addition, we pointed out the importance of the process order of alkyl-amine vapor treatment and photo-alignment.     

Investigation into the structure of Langmuir-Blodgett films prepared from salts of acetylenic acids

Langmuir-Blodgett films are prepared from lead, cadmium, and copper salts of carboxylic acids, namely, 23-tetracosynoic acid HC≡C(CH₂)₂₁COOH (with the terminal triple bond) and 2-docosynoic acid CH₃(CH₂)₁₈C≡CCOOH (with the internal triple bond). The structural transformations in the films during polymerization under exposure to UV radiation are investigated using X-ray reflectomertry. It is found that the X-ray reflectograms of the initial films prepared from salts of both acids exhibit no less than four or five pronounced intense Bragg reflections. This suggests that the initial films have good layer ordering. The bilayer periods for all the films are determined, and the influence of the salt type on the bilayer period is analyzed. It is established that, under exposure to UV radiation, the structural transformations in the films prepared from the salts of 23-tetracosynoic acid occur without substantial disturbances and defects, as can be judged from the absence of significant changes in the location and intensity of the Bragg reflections. An increase in the time of irradiation of the films prepared from the salts of 2-docosynoic acid leads to an increase in the bilayer period. This effect is especially pronounced for the lead and copper salts. However, upon long-term exposure to UV radiation, the salts undergo photolysis, the bilayer period decreases, and the structure of the film begins to break down.     

Atomic force microscopy study of the adsorption of protein molecules on transferred Langmuir monolayer

Ordered protein films have been obtained by the adsorption of protein molecules on a Langmuir monolayer, which had previously formed on a silicon substrate, using the Langmuir-Blodgett and molecular self-organization methods. A mixture of cholesterol with dipalmitoylphosphatidylcholine (DPPC) and a polymer—cellulose acetopivalinate—were used as immobilization materials. Protein molecules (catalase and alkaline phosphatase) immobilized on solid substrates have been investigated by atomic force micros-copy. It was shown that the developed combined technique provides a deposition of homogeneous ultrathin protein films with a high degree of filling.     

Highly Electrical Conductivity of Hybrid Langmuir-Blodgett Films of Transition Metal Dichalcogenide and Amphiphilic Compounds

Abstract

Hybrid alternate layered films of transition metal dichalcogenides and amphiphilic compounds were prepared by Langmuir-Blodgett (LB) technique. The conductivity at room temperature depended on the transition metal dichalcogenide species, showing the highest value for the hybrid LB films of MoS₂ system. This methodology was successfully applied to the fabrication of the hybrid LB films using various organic amphiphiles such as cyanine dyes, phthalocyanines, azobenzene, and ferrocene derivatives. The conductivity depended on the interlayer spacing: the conductivity decreased with increasing interlayer spacing of the film. The highest electrical conductivity of the hybrid LB films was over 100 Scm^?.     

Characterization of PDPA-b-PDMA-b-PDPA triblock copolymer Langmuir-Blodgett films for organic vapor sensing application

This study reports the synthesis, characterization, and gas sensing applications of the PDPA-b-PDMA-b-PDPA triblock copolymer material using NMR, UV-visible spectroscopy, atomic force microscopy (AFM), quartz crystal microbalance (QCM), and Langmuir-Blodgett (LB) thin film deposition techniques. The thin film deposition conditions of the copolymer material, which are prepared by LB film technique, are characterized by UV-visible spectroscopy, AFM, and QCM system. In this study, the swelling behaviors of the PDPA-b-PDMA-b-PDPA triblock copolymer Langmuir-Blodgett (LB) films were investigated with respect to volatile organic compounds (VOCs) at room temperature. The sensing responses of the films against VOCs were measured by QCM method. The swelling processes could be investigated using the early-time Fick's law of diffusion.     

X-ray diffraction study of gadolinium stearate Langmuir-Blodgett films

The comparative structural studies of gadolinium stearate Langmuir-Blodgett films prepared with the use of two different subphases (aqueous solutions of gadolinium chloride and gadolinium acetate) have been performed by the methods of X-ray diffractometry. The films were applied onto single-crystal silicon substrates coated with a native-oxide layer either with the use of buffer molecular stearic-acid layers or without such layers. It was established that the films obtained with the use of gadolinium acetate and the preliminarily formed buffer layers are, in fact, single-phase Y-type films with highly ordered molecular structure, and the thickness of the bimolecular layer d = (51.3 ± 0.5) Å.     

Planned Multilayer Assemblies by Adsorption

Adsorption at liquid solid interfaces is employed to construct organized multilayer structures on polar solid substrates. We have recently demonstrated that oriented compact monolayers of good quality can be obtained under suitable conditions either by physisorption or by chemisorption, using either pure compounds as adsorbates or mixtures of several components, and even using mixtures of both physisorbed and chemisorbed species.¹ Monolayer formation by adsorption offers certain important advantages as compared with the Lanmuir-Blodgett method; adsorption is a spontaneous process leading to thermodynamically equilibrated film structures, there is no mechanical manipulation of the films, water is not indispensable for monolayer formation, monolayer composition and structure are usually dependent on the chemical nature and microscopic organization of the solid surface, covalent binding to the substrate and intralayer polymerization may take place simultaneously with the monolayer formation process, there are no restrictions regarding the macroscopic shape and size of the substrate. However, the adsorption method has been so far shown to be suitable only for formation of single mono-layers,¹ which limited severely its usefulness in the construction of multilayer assemblies.     

Mg掺杂浓度对MgxZn1-xO薄膜结构和光学性能的影响

通过超声喷雾热解工艺在P型<100>Si衬底上制备了不同Mg掺杂浓度的纳米MgxZN1-xO薄膜.通过扫描电镜(SEM)、X射线光电子能谱(XPS)、X射线衍射(XRD)和光致发光(PL)谱的测试对不同Mg掺杂浓度下薄膜的表面形貌、成分、品体结构和光学性能进行了研究.SEM测试结果表明,低Mg掺杂浓度时,MgxZn1-xO表面平整致密,但随Mg浓度的增加,薄膜表而平整度降低.XRD测试结果表明在低浓度下MgxZn1-xO薄膜足ZnO的纤锌矿结构,而没有出现MgO的分相,ZnO的衍射峰峰强随Mg浓度的增加逐渐减弱.不同Mg掺杂浓度下的光致发光谱图均出现了近带边紫外发射峰和可见光发射峰,其中近带边紫外发射峰随掺杂浓度的增大出现了明显的蓝移.     

溶胶-凝胶法制备纳米ZnO薄膜的结构和光学性质

采用溶胶-凝胶方法制备纳米ZnO薄膜。X射线衍射(XRD)结果表明，薄膜具有六角纤锌矿多晶结构，且随水解时间的增加，粒子尺寸逐渐增大。室温下，观察到近带边紫外发射和较强的可见区(2．45eV)发射。红外吸收光谱研究表明ZnO薄膜表面存在单齿、双齿和桥状结构的醋酸锌副产物，阐述了不同结构醋酸锌副产物对ZnO薄膜可见区发光性质的影响。     

Restoration of structure of thin multilayer films from reflectivity data by stepwise model refinement

The computational experiment on the restoration of the model parameters of the cross-section profile of the scattering density of thin multilayer films is described. It is shown that the use of the stepwise model of the structure, which is described by the thickness, density, absorption, and roughness parameters makes the problem of profile restoration multimodal and ill-conditioned. The analysis of the numerical experiments performed allowed us to propose a procedure of consecutive refinement of the initial-model parameters using the results of the local minimization of the discrepancy functional applied for the characteristic segments of the reflectivity curve. The methods proposed were used to restore the structure of a multilayer film deposited on a silicon substrate by the Langmuir-Blodgett method.