Microstructure and Ion Exchange in Stearic Acid Langmuir-Blodgett Films Studied by Fourier Transform Infrared-Attenuated Total Reflection Spectroscopy

Fourier transform infrared-attenuated total reflection (FTIR-ATR) spectra have been recorded of 11-layer Langmuir-Blodgett (LB) films of stearic acid deposited at various surface pressures (0.1, 15, and 35 mN/m), and the molecular orientation angles were evaluated quantitatively, which supplied insight into the molecular order with the alkyl chains tightly packed like crystal in the LB films deposited at the zero and higher surface pressures. These experimental results indicate that, in the Langmuir film as the precursor of LB films, stearic acid molecules self-aggregate to form two-dimensional crystalline domains already even at the zero surface pressure, which results in the inhomogeneity of monolayer. The analysis of dependence of nu(C=O) intensity on the surface pressure, surface density, and subphase temperature leads to the conclusion that the defects in LB films originate from the Langmuir film and be conserved upon deposition. Annealing below 50 degrees C and cooling could improve the monolayer homogeneity, and thus a defect-free or low-defect LB films can be deposited. Furthermore, ion exchange conducted in the LB films, on the other hand, confirms the existence of structure defects in LB films of stearic acid. The polar plane microstructure, lateral transport along the polar planes and the coordination types of stearic acid/cation system may be the rate-limiting process. The results have implication on the possible uses of stearic acid LB films as ion-exchange materials or sensors. Copyright 2001 Academic Press.     

Langmuir‐Blodgett Films of Alkanethiolate Gold Nanorods

Colloidal multilayers of octadecanethiol‐capped Au nanorods were prepared using the Langmuir‐Blodgett technique. Uniform growth of the films with increasing number of deposition has been observed. Vertical transfer efficiency indicates efficient transfer for immersion of hydrophobic substrates and poor transfer for emersion of such substrates. The vertically transferred film has an order parameter S = 0.027, which suggests that the orientation of the nanorods in the film is somewhat isotropic about the dipping direction. Horizontal transfer of the Langmuir monolayer on Formvar/carbon‐coated Cu grids, however, gave scattered domains of Au nanorods aligned in parallel stacks. Such behavior is probably related to the rigidity of the Langmuir monolayer.     

Temperature dependence of the structure of Langmuir films of normal-alkanes on liquid mercury

The temperature dependent phase behavior of Langmuir films of n-alkanes [CH3(CH2)(n-2)CH3, denote Cn] on mercury was studied for chain lengths 19< or =n< or =22 and temperatures 15< or =T< or =44 degrees C, using surface tensiometry and surface x-ray diffraction methods. In contrast with Langmuir films on water, where molecules invariably orient roughly surface normal, alkanes on mercury are always oriented surface parallel and show no long-range in-plane order at any surface pressure. A gas and several condensed phases of single, double, and triple layers of lying-down molecules are found, depending on n and T. At high coverages, the alkanes studied here show transitions from a triple to a double to a single layer with increasing temperature. The transition temperature from a double to a single layer is found to be approximately 5 degrees C, lower than the bulk rotator-to-liquid melting temperature, while the transition from a triple to a double layer is about as much below the double-to-single layer transition. Both monolayer and bulk transition temperatures show a linear increase with n with identical slopes of approximately 4.5 degrees C/CH2 within the range of n values addressed here. It is suggested that the film and bulk transitions are both driven by a common cause: the proliferation of gauche defects in the chain with increasing temperature.     

Ultrathin films of functionalised single-walled carbon nanotubes: a potential bio-sensing platform

ABSTRACT

The Langmuir monolayer is a special class of lyotropic liquid crystalline system wherein phase transition essentially depends on surface density, temperature and ion-content in the aqueous medium. The variety of surface phases can be transferred onto devices by the Langmuir–Blodgett (LB) technique. The Langmuir monolayer of pristine single-walled carbon nanotubes (SWCNTs) exhibited gas and liquid-like phases. The LB film of SWCNTs shows target surface pressure dependent interesting morphologies. The methane gas sensing using parallel alignment of SWCNTs was found to be better than that of randomly oriented SWCNTs. The SWCNTs can be functionalised chemically to enhance the ease of film processability and affinity towards analytes. These are essential parameters for the development of a sensor. In this article, we present our work on Langmuir monolayer and LB films of octadecylamine functionalised SWCNTs (ODACNTs) and its sensing application towards bio-analytes, e.g. L-aspartic acid and bovine serum albumin. The sensing performance of LB film of ODACNTs was compared with that of spin-coated films of ODACNTs. The sensing performance of LB films of ODACNTs indicated a potential platform for bio-sensing application.     

Preparation of ordered films containing a phenylene ethynylene oligomer by the Langmuir-Blodgett technique

This paper reports the fabrication and characterization of Langmuir and Langmuir-Blodgett (LB) films incorporating an oligo(phenylene-ethynylene) (OPE) derivative, namely, 4-[4-(4-hexyloxyphenylethynyl)-phenylethynyl]-benzoic acid (HBPEB). Conditions appropriate for deposition of monolayers of HBPEB at the air-water interface have been established and the resulting Langmuir films characterized by a combination of surface pressure and surface potential versus area per molecule isotherms, Brewster angle microscopy, and ultraviolet reflection spectroscopy. The Langmuir films are readily transferred onto solid substrates, and one-layer LB films transferred at several surface pressures onto mica substrates have been analyzed by means of atomic force microscopy, from which it can be concluded that 14 mN/m is an optimum surface pressure of transference, giving well-ordered homogeneous films without three-dimensional defects and a low surface roughness. The optical and emissive properties of the LB films have been determined with significant blue-shifted absorption spectra indicating formation of two-dimensional H aggregates and a Stokes shift illustrating the effects of the solid-like environment on the molecular chromophore.     

Blends of poly(epsilon-caprolactone) and intermediate molar mass polystyrene as Langmuir films at the air/water interface

Poly(epsilon-caprolactone)/polystyrene (PCL/PS) blends, where nonamphiphilic PS is glassy in the bulk state at the experimental temperature of 22.5 degrees C, are immiscible as Langmuir films at the air/water (A/W) interface. Surface pressure-area per monomer isotherm analyses indicate that the surface concentration of amphiphilic PCL is the only factor influencing the surface pressure below the collapse transition. For PS-rich blends, Brewster angle microscopy (BAM) studies at the A/W interface and atomic force microscopy studies on Langmuir-Schaefer films reveal that PS nanoparticle aggregates formed at very low surface pressures can form networks upon further compression. The morphologies seen in PS-rich blends (networklike rings) are consistent with a recent study of a nonamphiphilic polyhedral oligomeric silsesquioxane (POSS), octaisobutyl-POSS, blended with amphiphilic poly(dimethylsiloxane), suggesting that the nonamphiphilic PS aggregates at the A/W interface produce domains with dipole densities that differ from that of pure PCL. In all composition regimes, the amphiphilic PCL phase tends to spread and form a continuous surface layer at the A/W interface, while simultaneously improving the dispersion of nonamphiphilic PS domains. During film expansion, BAM images show a gradual change in the surface morphology from highly continuous networklike structures (PS-rich blends) to broken ringlike structures (intermediate composition) to small discontinuous aggregates (PCL-rich blends). This study provides valuable information on the morphological evolution of semicrystalline PCL-based polymer blends confined in a "two-dimensional" geometry at the A/W interface and fundamental insight into the influence of microstructure (domain size, phase-separated structures, crystalline morphology, etc.) on the interfacial properties of blends as Langmuir films.     

Pure and mixed films of a nitrostilbene derivative at the air-water interface, Langmuir-Blodgett multilayer fabrication, and optical characterization

This paper reports the preparation and characterization of pure Langmuir and Langmuir-Blodgett (LB) films of a stilbene derivative containing two alkyl chains, namely 4-dioctadecylamino-4'-nitrostilbene. Mixed films incorporating docosanoic acid and the stilbene derivative are also studied. Brewster angle microscopy (BAM) analysis has revealed the existence of randomly oriented three-dimensional (3D) aggregates, spontaneously formed immediately after the spreading process of the stilbene derivative onto the water surface. These 3D aggregates coexist with a Langmuir film that shows the typical gas, liquid, and solid-like phases in the surface pressure and surface potential vs area per molecule isotherms, indicative of an average preferential orientation of the stilbene compound at the air-water interface, and a gradual molecular arrangement into a defined structure upon compression. A blue shift of 55 nm of the reflection spectrum of the Langmuir film with respect to the spectrum of a chloroform solution of the nitrostilbene indicates that two-dimensional (2D) H-aggregates are formed at the air-water interface. The monolayers are transferred undisturbed onto solid substrates with atomic force microscopy (AFM) revealing that the one layer LB films are constituted by a monolayer of the stilbene derivative together with some 3D aggregates. When the nitrostilbene compound is blended with docosanoic acid, the 3D aggregation is avoided in the Langmuir and Langmuir-Blodgett films, but does not limit the formation of 2D H-aggregates, desirable for second-order nonlinear optical response in the blue domain. The AFM images of the mixed LB films show that they are formed by a docosanoic acid monolayer and, on the top of it, a bilayer of the stilbene derivative.     

Effect of temperature on the interfacial behavior of a polystyrene-b-poly(methyl methacrylate) diblock copolymer at the air/water interface

Monolayers of a polystyrene-poly(methyl methacrylate) (PS-PMMA) diblock copolymer at the air-water interface were studied by measuring the surface pressure-area isotherms at several temperatures. Langmuir film balance experiments and atomic force microscopy showed that the diblock copolymer molecules formed surface micelles. In the plot of the surface pressure versus surface area per repeating unit, the monolayer changed from the gas phase to the liquid expanded phase at lower surface pressure for systems at low temperature compared to those at high temperature. In addition, a plateau, corresponding to the transition from the liquid expanded to liquid condensed phase, appeared in that plot at lower surface pressure for systems with a higher subphase (water) temperature. Hysteresis was observed in the compression-expansion cycle process. Increasing the subphase temperature alleviated this hyteresis gap, especially at low surface pressures. The minimum in the plot of the surface pressure versus surface area per repeating unit in the expansion process (which arises from the transition) and the transition plateau appeared more vividly at higher water temperature. These dynamic experimental results show that PS-PMMA diblock copolymers, in which both blocks are insoluble in water, do not form complicated entanglements in two-dimensional space. Although higher water temperature provided more entropy to the chains, and thus more conformational freedom, it did not change the surface morphology of the condensed film because both blocks of PS-PMMA are insoluble in water.     

Surface chemistry studies of (CdSe)ZnS quantum dots at the air-water interface

Trioctylphosphine oxide- (TOPO-) capped (CdSe)ZnS quantum dots (QDs) were prepared through a stepwise synthesis. The surface chemistry behavior of the QDs at the air-water interface was carefully examined by various physical measurements. The surface pressure-area isotherm of the Langmuir film of the QDs gave an average diameter of 4.4 nm, which matched very well with the value determined by transmission electron microscopy (TEM) measurements if the thickness of the TOPO cap was counted. The stability of the Langmuir film of the QDs was tested by two different methods, compression/decompression cycling and kinetic measurements, both of which indicated that TOPO-capped (CdSe)ZnS QDs can form stable Langmuir films at the air-water interface. Epifluorescence microscopy revealed the two-dimensional aggregation of the QDs in Langmuir films during the early stage of the compression process. However, at high surface pressures, the Langmuir film of QDs was more homogeneous and was capable of being deposited on a hydrophobic quartz slide by the Langmuir-Blodgett (LB) film technique. Photoluminescence (PL) spectroscopy was utilized to characterize the LB films. The PL intensity of the LB film of QDs at the first emission maximum was found to increase linearly with increasing number of layers deposited onto the hydrophobic quartz slide, which implied a homogeneous deposition of the Langmuir film of QDs at surface pressures greater than 20 mN.m(-1).     

Thin films of discotic liquid crystals and their applications

ABSTRACT

Discotic liquid crystals (DLCs) are considered as fascinating systems due to their unique property of self-assembly to yield different columnar structures. DLCs are organic semiconductors and create pathways for the development of numerous optical and electrical devices. The thin films of DLCs can be considered as low dimensional system which can exhibit remarkable optical and physical properties. In this article, we present a review on ultrathin films of some interesting DLC molecules at air–water and air–solid interfaces. The Langmuir monolayer and Langmuir–Blodgett films of DLC molecules are extensively studied. The ultrathin films of DLC molecules can yield highly anisotropic layer wherein the molecular orientation and aggregation can have large impact on the physicochemical properties of the film. Different surface phases with different molecular orientations as function of surface density and temperature can be obtained by forming the Langmuir monolayer of the DLC molecules at the air–water interface. The Langmuir monolayer in a particular phase can be deposited onto the active area of a device layer-by-layer by employing a highly controlled Langmuir–Blodgett technique. Here, we report some interesting results related on molecular orientation of the DLC molecules at different interfaces. Such aggregation of DLC molecules in ultrathin films may find applications in thin film-based electro-optical devices.     

硬脂酸单分子膜上电沉积Ag膜的研究

通过电沉积方法,以气/液界面上形成的硬脂酸单分子膜为模板诱导沉积金属银膜.考察了镀液pH值、单分子膜表面压及沉积电位对银膜形貌及结构的影响.实验发现,酸性镀液的气/液界面上形成的单分子膜不能诱导沉积银,而在中性和碱性镀液的气/液界面上可以诱导银膜的生长.当单分子膜处于液态或固态时,气/液界面有银膜形成;液态单分子膜上的银膜生长速度较快,且银膜的结构一致.随着电极电位的升高,银膜沉积的速度加快,呈环状向外生长的圆形银膜逐渐变得不规则.将不同实验条件下的银膜转移出来,采用扫描电镜(SEM)、透射电镜(TEM)对银膜的结构与形貌进行了表征.研究表明,银首先在单分子膜上异相成核,由八面体构型逐渐发展成星型,最终在气/液界面形成具有松枝状微观结构的光亮银膜.     

Thermal decomposition of commercial silicone oil to produce high yield high surface area SiC nanorods

This article reports on the synthesis of high surface area (563m2/g) beta-SiC nanorods by thermal decomposition of commercial silicone oil at a relatively low reaction temperature (800 degrees C) in a closed Swagelok cell. High yield (75%) of SiC nanorods are obtained in this one-stage, solvent-, catalyst-, and template-free synthesis technique that runs at a relative low temperature and employs cheap single-precursor. The morphological (TEM, HR-SEM), compositional (CHNS, EDX, SAEDX]), structural (XRD, HR-TEM, and ED), thermal (TGA) characterizations and surface area analysis are carried out for the obtained SiC nanorods. The possibility of hydrogen storage in this high surface area nano-SiC rods are also tested and reported for the first time.     

Surface Dynamic Elasticity of Poly(ethylene oxide) Monolayers on a Water Surface

The methods of transverse and longitudinal surface waves and of oscillating barrier were used to measure a surface dynamic elasticity of poly(ethylene oxide) films spread on aqueous substrate within the frequency range of 0.001–520 Hz. Unlike the adsorption films, the main relaxation processes in the spread poly(ethylene oxide) films are observed at higher frequencies. A comparison of static and dynamic values of the surface elasticity shows that the surface film at surface polymer concentrations higher than 0.4 mg/m² cannot be considered already as purely two-dimensional film. It was found that the surface tension (surface pressure) can be insufficiently sensitive to conformational transformations in the surface polymer films.     

Kinetics of DC Discharge Plasma Polymerization of Hexamethyldisiloxane and Pyrrole

This paper investigates DC plasma polymerization kinetics by combining plasma parameters with film deposition rate in different conditions. The monomers hexamethyldisiloxane (HMDSO) and pyrrole were used. Both single and double Langmuir probes were used to measure the plasma parameters in pulsed power and continuous discharges. In order to avoid probe tip contamination, the probe was heated. Plasma density and electron temperature are reported. The electron current wave form is obtained in pulse power conditions. From the data, a plasma polymerization model is proposed. The conclusion is that the monomer molecules and free radicals adsorbed on the substrate surface react with activated sites produced by high energy ions bombarding the film, resulting in polymerization at the film surface.     

Interaction between organophosphorous hydrolase and paraoxon studied by surface chemistry in situ at air-water interface

Subphase conditions have been optimized to obtain stable organophosphorous hydrolase (OPH-EC 3.1.8.1) as Langmuir films. The Langmuir film was characterized by surface pressure and surface potential-area isotherms and UV-Vis spectroscopy in situ. The interaction of an organophosphorous compound, namely Paraoxon, with the OPH film was investigated for various surface pressures. The stability of the monolayer and the evidence of the enzyme activity at air-water interface support the use of enzyme LB films as biosensor.     

剪切场下两亲性棒状粒子对聚异丁烯/聚二甲基硅氧烷共混物相形态的影响

合成了具有两亲表面性质的棒状SiO₂粒子,借助共聚焦激光扫描显微镜研究了两亲性棒状SiO₂粒子在共混物中的选择性分布,并通过在线剪切-显微技术和流变技术研究了其对聚异丁烯/聚二甲基硅氧烷（PIB/PDMS）不相容共混物形态结构的影响.研究表明,两亲性棒状SiO₂粒子倾向于分布在两相界面处及PIB相中.分散相的剪切诱导凝聚行为强烈依赖于粒子的含量和共混物的组成比.少量两亲性SiO₂粒子会促进分散相的凝聚,而加入足够量的粒子则能抑制分散相凝聚.     

Surface tension and fluid flow driven self-assembly of ordered ZnO nanorod films for high-performance field effect transistors

Colloidal nanorods of inorganic semiconductors are of interest for a range of optoelectronic devices. The ability to self-assemble these materials into ordered arrays by solution-processing techniques is crucial for achieving adequate device performance. Here we show that uniform ZnO nanorod films with defined nanorod alignment can be solution-deposited over large areas by controlling the surface energy of the nanorods through the choice of suitable ligands and by the fluid flow direction during growth. ZnO nanorods with long carbon chain ligands exhibit a smaller surface free energy than those with short carbon chain ligands resulting in better in-plane alignment and large domain sizes up to dozens of micrometers in spin-coated films. A model is presented to rationalize the observed self-assembly behavior. It is based on the formation of a lyotropic liquid crystalline phase on the surface of the liquid film which is facilitated by enhanced segregation of nanorods with low surface tension to the surface. Alignment of the nanorods is controlled by radial and vertical liquid flows in the drying solution. The ability to control the orientation of the nanorods and to achieve large domain size results in significant device performance improvement. Field-effect transistors with mobilities of up to 1.2-1.4 cm2/V.s are demonstrated in spin-coated, in-plane aligned ZnO nanorod films subject to postdeposition hydrothermal growth.     

Formation of 2D spherulites in Langmuir films of amphiphilic T-shaped liquid crystals

Langmuir films of facial T-shaped amphiphilic liquid crystals were studied at the air-water interface. The liquid crystals were composed of three incompatible segments: a central rigid rodlike p-terphenyl (TP) group, two flexible hydrophobic n-alkyl terminal chains of identical length linked through ether bonds, and one hydrophilic lateral chain of three ethylene oxide units with a carboxyl end group. In order to determine the influence of the alkyl chain length on the characteristics of condensed films three TPs having n-alkyl chains with eight (TP8/3), ten (TP10/3) or 16 (TP16/3) carbon atoms were investigated. Surface pressure - mean molecular area isotherms revealed clear differences. TP8/3 and TP10/3 exhibit an extended plateau region where a phase transition from monolayer to multilayer takes place. On the other hand, the TP16/3 isotherm showed a distinct maximum ('spike') corresponding to a surprising surface crystallization process which is reported for the first time for a Langmuir film of a liquid crystal. Brewster angle microscopy clearly confirmed these differences: TP8/3 and TP10/3 formed circular domains with liquid crystalline order, while TP16/3 formed well-defined two-dimensional polycrystalline spherulites which are fractured after further compression. The film thickness determined by X-ray reflectivity measurements correlated with a multilayer formation for TP10/3. The morphology of Langmuir-Blodgett (LB) films transferred onto silicon wafers and studied by atomic force microscopy also confirmed the striking different behavior (multilayer formation vs. 2D crystallization) of the TPs under investigation.     

The structures of Langmuir-Blodgett films of fatty acids and their salts

Recent advances in several experimental techniques have enabled detailed structural information to be obtained for floating (Langmuir) monolayers and Langmuir-Blodgett films. These techniques are described briefly and their application to the study of films of fatty acids and their salts is discussed. Floating monolayers on aqueous subphases have been shown to possess a complex polymorphism with phases whose structures may be compared to those of smectic mesophases. However, only those phases that exist at high surface pressures are normally used in Langmuir-Blodgett (LB) deposition. In single LB monolayers of fatty acids and fatty acid salts the acyl chains are in the all-trans conformation with their long axes normal to the substrate. The in-plane molecular packing is hexagonal with long-range bond orientational order and short-range positional order: known as the hexatic-B structure. This structure is found irrespective of the phase of the parent floating monolayer. The structures of multilayer LB films are similar to the structures of their bulk crystals, consisting of stacked bilayer lamellae. Each lamella is formed from two monolayers of fatty acid molecules or ions arranged head to head and held together by hydrogen bonding between pairs of acids or ionic bonding through the divalent cations. With acids the acyl chains are tilted with respect to the substrate normal and have a monoclinic structure, whereas the salts with divalent cations may have the chains normal to the substrate or tilted. The in-plane structures are usually centred rectangular with the chains in the trans conformation and packed in a herringbone pattern. Multilayer films of the acids show only a single-step order-disorder transition at the melting point. This temperature tends to rise as the number of layers increases. Complex changes occur when multilayer films of the salts are heated. Disorder of the chains begins at low temperatures but the arrangement of the head groups does not alter until the melting temperature is reached. Slow heating to a temperature just below the melting temperature gives, with some salts, a radical change in phase. The lamellar structure disappears and a new phase consisting of cylindrical rods lying parallel to the substrate surface and stacked in a hexagonal pattern is formed. In each rod the cations are aligned along the central axis surrounded by the disordered acyl chains.     

DNA分子在气液界面的组装相变特性及其LB膜结构研究

对十八胺与DNA在气液界面上组装及其相变过程进行了研究，利用AFM观察了不 同压力下转移的DNA复合LB膜结构。发现在低表面压时，DNA复合单分子膜表现为技 术发散的分形结构；随着压力的升高，DNA复合膜逐渐由紧密的网状排布结构变为 团聚的块状和团簇结构。表明通过调节膜压，可使膜内DNA分子的构象发生大的变 化，从而生成具有特定形态的二维纳米图案。这种具有特殊形态和结构的DNA LB膜 可望为合成新型生物纳米结构有序功能体系提供模板。