Structure Of Langmuir-Blodgett Films Research Articles

Phase-Separated Structures of Mixed Langmuir−Blodgett Films of Fatty Acid and Hybrid Carboxylic Acid

Phase separation often occurs in mixed Langmuir-Blodgett (LB) films. Usually circular domains at the micrometer length scale form in the LB films. The size and shape of the domains are governed by a compromise between two competing interactions of line tension and dipole-dipole interaction. An attempt was made to control the line tension by varying systematically the hydrophobic moieties of the film-forming molecules. Phase-separated structures of two-component mixed LB films of fatty acid [C(k)H(2k+1)COOH (HkA)] and hybrid carboxylic acid [C(m)F(2m+1)C(n)H(2n)COOH (FmHnA)] were investigated. IR spectra of the mixed LB films of H17A and F8H10A revealed that the alkyl chains were in an all-trans conformation and that the molecular orientation remained unchanged when the two components were mixed. Nanowires formed in the mixed LB films of HkA and F8H10A. The width of the nanowires increased with an increase in k. Domain size and shape in the mixed LB films of H17A and FmHnA depended strongly on the values of m and n. Circular domains at the micrometer length scale formed in the region m + n < 16. In contrast, domains at the nanometer length scale formed in the region m + n > or = 16 except for F6H10A. These results were explained by using a lattice model that considers the effect of the hydrophobic moieties of fatty acid and hybrid carboxylic acid on the line tension.

Redox-controlled multistability of double-decker cerium tetra-(15-crown-5)-phthalocyaninate ultrathin films

The optical and electrochemical properties of novel double-decker cerium bis-tetra-15-crown-5-phthalocyaninate [ Ce ( R 4 Pc 2−)2]0 (R4Pc2− = [4,5,4',5',4",5",4'",5'"-tetrakis-(1,4,7,10,13-pentaoxapentadecamethylene)-phthalocyaninate-anion]) Langmuir-Blodgett and cast films were investigated. The particular feature of cerium ion in complex with tetra-15-crown-5-phthalocyanine is the stability of oxidation state +4 unlike other lanthanide metal centers. Cyclic voltammetry curves exhibited three stable redox states in the Langmuir-Blodgett and cast films. Redox processes in Langmuir-Blodgett films are reversible and reproducible at multiple scan procedures. The mechanisms of redox transformations in Langmuir-Blodgett films are suggested. We demonstrated that the well-defined structure of Langmuir-Blodgett film is essential for fast electron transfer within the planar system, in which the charge is delocalized along the conjugated assembly of uniformly ordered stacks of discotic crown-phthalocyaninate. Fast charge relaxation was observed in highly ordered Langmuir-Blodgett film whereas the electrochemically written redox states remained unchanged in unordered cast film. The combination of electrochemistry with surface plasmon resonance spectroscopy allowed us to demonstrate that stepwise change of potential in the range 200-850 mV induced the respective optical response, which can be observed as the change in resonance angle value. High-speed response and reversibility of the switching process between stable states may be utilized as the basis for switchable optoelectronic devices. Electrochemical multistability of cerium crown-phthalocyaninate provided a basis for developing a simple strategy to fabricate nanoelectromechanical systems with high efficiency and fast response. Our approach relies on the modulation of the distance between decks in a complex stack via redox-controlled change of metal center size that results in change of linear dimensions of the stacks. The reported results are valuable, not only because of their potential applications, for instance, in OFET and MEMS fabrication, but also from a fundamental point of view since they illustrate the interplay between the orientation of stacks bearing discotic aromatic molecules and charge transfer within such a planar assembly.

Polyplatinayne/polyoxometalate composite Langmuir‐Blodgett films: Preparation, structural characterization, and potential optoelectronic applications

AbstractA new family of organometallic/inorganic composite Langmuir‐Blodgett (LB) films consisting of rigid‐rod polyplatinayne polymer ([Pt‐T(OMe‐Fl)T]∞ or [Pt‐T(F‐Fl)T]∞, where the triplet bonds are abbreviated by T, and fluorene ring by Fl) as the π‐conjugated organometallic molecule, polyoxometalate (POM, POM = K3PMo12O40, H3PW12O40, or H6P2W18O62) of the Keggin and Dawson structures as the inorganic component, and dimethyldioctadecylammonium bromide (DODA) or a mixture of octadecanoic acid (OA) and docosanoic acid (DA) as the auxiliary film‐forming agent were prepared and characterized by π–A isotherms, UV–Vis absorption spectra, photoluminescence spectra, atomic force microscopy imaging, scanning tunneling microscopy, and low‐angle X‐ray diffraction. Our experimental results indicate that steady, even, and ordered Langmuir and LB films are formed in pure water and polyoxometalate subphases. It was shown that the POM molecules are probably embedded inside the polyplatinayne molecules in the LB film structure and they can quench the luminescence of the Pt polyyne. These Pt‐polyyne based LB films display interesting electric conductivity behavior. [Pt‐T(OMe‐Fl)T]∞/DODA/HPW12 monolayer film shows a good electrical conductivity, and the tunneling current amounts to ±100 nA when the voltage is set at ±8 V. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3193–3206, 2008

Nanowire Formation in Two-component-mixed Langmuir–Blodgett Films of Fatty Acid and Silane-coupling Agent

Abstract We have found the formation of nanowires in two-component-mixed Langmuir–Blodgett (LB) films of fatty acid and silane-coupling agent for the first time. The phase-separated structures of the mixed LB films were controlled by adjusting intermolecular interactions. The size and shape of the domains were explained by considering two competing interactions of line tension and dipole–dipole interaction.

Structural characterization of Langmuir–Blodgett films of 4,5-bis(dodecyloxy)phthalic acid

In this work, the formation of Langmuir monolayer of 4,5-bis(dodecyloxy)phthalic acid (DPA) molecule at the air–water interface, surface-pressure area ( π– A) isotherm and stability of this monolayer was investigated. The structural characterization of Langmuir–Blodgett (LB) films of DPA deposited on aluminium covered glass substrate was studied using Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction (XRD) measurements. For FTIR measurements, p-polarized grazing angle (GAIR) and horizontal attenuated total reflectance (HATR) techniques have been employed to characterize the LB films. The molecular structure of LB films was investigated by comparing the GAIR and HTAR spectra. The two extra bands that appeared in the FTIR spectra of LB films suggest that the carbonyl groups are bonded to the adjacent carbons of head groups and the carboxylic acids of head groups are capable of forming five-membered cyclic anhydrides in all LB films. The slightly downward shifts of the ν(CH 2) stretching bands are indicative of the increase in conformational order from gauche conformers to highly ordered transconformers in the hydrocarbon chain with increasing number of layers. Changes in intensity between the p-polarized GAIR and HATR spectra may indicate that the alkyl chains are almost perpendicular to the substrate in LB films. The singlet absorption due to the δ(CH 2) and ρ r(CH 2) modes indicated that in LB films of DPA alkyl chains are packed in hexagonal structure. The XRD results show that all the multilayer structure is Y-type and the alkyl chains aligned almost vertically in the LB films.

Circular patterns of calcium oxalate crystals induced by defective Langmuir-Blodgett film

The injury of the renal epithelial cell membrane can promote the nucleation of nascent crystals, as well as adhesion of crystals on it. It thus accelerates the formation of renal calculi. In this paper, the defective Langmuir-Blodgett (LB) films were used as a model system to simulate the injured renal epithelial cell membrane. The microcosmic structure of the defective LB film and the molecular mechanism of the effect of this film on nucleation, growth, deposited patterns and adhesion of calcium oxalate monohydrate (COM) were investigated. The circular defective domains were formed in dipalmitoylphosphatidylcholine (DPPC) LB film after the film was treated by potassium oxalate. These domains could induce ring-shaped patterns of COM crystals. In comparison, the LB film without pretreatment by potassium oxalate only induced random growth of hexagonal COM crystals. As the crystallization time increased, the size of COM crystals in the patterns increased, the crystal patterns changed from empty circles to solid circles, and the number of the circular patterns with small size (5–20 μm) increased. The results would shed light on the molecular mechanism of urolithiasis induced by injury of the renal epithelial membrane at the molecular and supramolecular level.

Self‐Assembly of Amphiphilic Hexapyridinium Cations at the Air/Water Interface and on HOPG Surfaces

Mono- and multilayers of a novel amphiphilic hexapyridinium cation with six eicosyl chains (3) are spread at the air/water interface as well as on highly ordered pyrolytic graphite (HOPG). On water, the monolayer of 3 is investigated by recording surface pressure/area and surface potential/area isotherms, and by Brewster angle microscopy (BAM). Self-organized tubular micelles with an internal edge-on orientation of molecules form at the air/water interface at low surface pressure whereas multilayers are present at high surface pressure, after a phase transition. Packing motifs suggesting a tubular arrangement of the constituting molecules were gleaned from atomic force microscopy (AFM) investigations of Langmuir-Blodgett (LB) monolayers being transferred on HOPG at different surface pressures. These LB film structures are compared to the self-assembled monolayer (SAM) of 3 formed via adsorption from a supersaturated solution, which is studied by scanning tunnelling microscopy (STM). On HOPG the SAM of 3 consists of nanorods with a highly ordered edge-on packing of the aromatic rings and an arrangement of alkyl chains which resembles the packing of molecules at the air/water interface at low surface pressure. Additional details of the molecular packing were gleaned from single-crystal X-ray structure analysis of the hexapyridinium model compound 2b, which possesses methyl instead of eicosyl residues.

Electrical Properties of a Novel 1,3-Bis-(&lt;I&gt;p&lt;/I&gt;-Iminobenzoic Acid) Indane Langmuir-Blodgett Films Containing ZnS Nanoparticles

ZnS nanoparticles have been formed in a newly synthesized 1,3-bis-(p-iminobenzoic acid) indane (IBI) by exposing Zn2+ doped multilayered Langmuir-Blodgett (LB) film to H2S gas after the growth. The formation of ZnS nanoparticles in the LB film structure was verified by measuring UV-Visible absorption spectra. DC electrical measurements were carried out for thin films of IBI prepared in a metal/LB films/metal sandwich structure with and without ZnS nanoparticles. It was observed that ZnS nanoparticles in the LB films cause a blue-shift in the absorption spectra as well as a decrease in both capacitance and conductivity values. By analysing I-V curves and assuming a Schottky conduction mechanism the barrier height was found to be about 1.13 eV and 1.21 eV for IBI LB films without and with ZnS nanoparticles, respectively. It is thought that the presence of ZnS nanoparticles influences the barrier height at the metal-organic film interface and causes a change in electrical conduction properties of LB films.

Fabrication and structural analysis of aromatic polyimide ultra-thin films with different fluorine contents

The structural characterizations of aromatic polyimide (PI) ultra-thin films with different fluorine contents were studied. Three types of polyamic acid (PAA) were produced from polymerization of biphenyl dianhydride (BPDA)/4,4′-oxydianiline (ODA), BPDA/2,2′-bis(trifluromethyl)benzidine (TFDB), and 4,4′-(hexafluoro isopropylidene)-diphthalic anhydride (6FDA)/TFDB in N,N-dimethylacetamide (DMAc). Polyamic acid alkyl salts (PAAS) using O,O′,O″-trihexadecanoyl-triethanolamine were transferred onto a Si-wafer substrate to prepare Langmuir–Blodgett (LB) films. The behaviors of PAAS monolayers at the air/water interface were confirmed with π–A isotherms and Brewster Angle Microscopy (BAM) images. The behaviors of PAAS monolayers at the air/water interface depend on the fluorine contents. As there is more fluorine in the main chain of PAAS, the area per molecule of each monolayer was increased. The structure of PAAS LB films with 10, 20, 30, and 40 layers on a substrate were investigated by UV–vis spectroscopy, X-ray diffraction (XRD), X-ray reflectivity, and IR spectroscopy. The obtained PAAS LB films were imidized with a thermal treatment at 300°C. The imidization of PI ultra-thin film was identified by IR spectrum. Atomic force microscopy (AFM) images showed that the particle size of PI ultra-thin films on a Si-wafer were about 7–25nm.

Stable Langmuir–Blodgett film deposition of polyaniline and arachidic acid

An experimental study was carried out to examine the stable Langmuir–Blodgett (LB) film deposition of mixtures of polyaniline (PA) and arachidic acid (AA) at different concentration ratios, with the aim of developing a systematic methodology for the production of quality PA/AA film at the highest deposition speed. The quality of LB film was examined before, during and after the film deposition process. Images of the PA/AA composite materials at air–liquid interface, based on the Brewster angle microscopy, revealed that a 50/50 concentration ratio of PA/AA composite layer produced the best LB film structure. The feasibility of LB film deposition was determined from dynamic contact angles which were measured by a flow visualization technique. The quality of the deposited film was judged by the transfer ratio and the atomic force microscopy images. The effect of pH was also examined, and it was found that the LB film deposition for the PA/AA system could only be carried out in a narrow range of pH. It was found that the deposited LB film of the PA/AA system had a high transfer ratio and improved surface roughness at the deposition speed 30 mm/min. This deposition speed is much higher than those previously reported.

The dipole interaction model of the molecular aggregation in Y-type Langmuir-Blodgett film

Based on the classical electrostatic theory, the model of dipole-dipole interaction of rod-like amphiphilic molecules in Y-type Langmuir-Blodgett (LB) film is presented in the paper. The relations between the structure and spectral absorption peak of LB films were obtained by using this model. For Y-type films, the relationship of molecular aggregation state and the structure parameters, i.e. molecular separation distance a, separation d between two adjacent layers, molecular tilt angle θ, and layer number g, were studied using our model. Then we compared the similarities and differences of aggregation behavior between Y-type and Z-type films. The theoretical results agree well with experimental data.

An infrared study on Langmuir–Blodgett films of 12,13-bis(hydroxyimino)-11,14-diazatetracosane

Fourier Transform Infrared (FTIR) grazing angle (GAIR) and Horizontal Attenuated Total Reflectance (HATR) techniques were used to characterize Langmuir–Blodgett (LB) films of 12,13-bis(hydroxyimino)-11,14-diazatetracosane (DTC) deposited on an aluminium plated substrate. The LB films of DTC were prepared successfully by transferring onto the solid substrate. The molecular structure of LB films was investigated by comparing the GAIR and HATR spectra. The results suggest that the alkyl chains in DTC are nearly in all- trans conformational state and the alkyl chain tilt, which is the angle between the axis which bisects the C–C bonds and the surface normal, is getting large, when the numbers of monolayer are increased. The splitting of the bands due to the methylene scissoring mode indicates that in LB films of DTC alkyl chains are packed in either an orthorhombic or a monoclinic structure with an orthorhombic subcell containing two mutually orthogonal molecules.

Immobilization of Biomaterials to Nano-Assembled Films (Self-Assembled Monolayers, Langmuir-Blodgett Films, and Layer-by-Layer Assemblies) and Their Related Functions

For utilization of highly sophisticated functions of biomaterials in nano-scale functional systems, immobilization of biomaterials on artificial devices such as electrodes via thin film technology is one of the most powerful strategies. In this review, we focus on three major organic ultrathin films, self-assembled monolayers (SAM), Langmuir-Blodgett (LB) films, and layer-by-layer (LBL) assemblies, and from the viewpoints of biomaterial immobilization, typical examples and recent progresses in these film technologies are described. The SAM method allows facile contact between biomaterials and man-made devices, and well used for bio-related sensors. In addition, recent micro-fabrication techniques such as micro-contact printing and dip-pen nanolithography were successfully applied to preparation of biomaterial patterning. A monolayer at the air-water interface, which is a unit structure of LB films, provides a unique environment for recognition of aqueous biomaterials. Recognition and immobilization of various biomaterials including nucleotides, nucleic acid bases, amino acids, sugars, and peptides were widely investigated. The LB film can be also used for immobilization of enzymes in an ultrathin film on an electrode, resulting in sensor application. The LBL assembling method is available for wide range of biomaterials and provides great freedom in designs of layered structures. These advantages are reflected in preparation of thin-film bio-reactors where multiple kinds of enzymes sequentially operate. LBL assemblies were also utilized for sensors and drug delivery systems. This kind of assembling structures can be prepared on micro-size particle and very useful for preparation of hollow capsules with biological functions.

Electrochemical and coupled XPS studies on Langmuir–Blodgett mixed films of behenic acid and over-grafted platinum nanoparticles: Effect of the behenic acid removal

Abstract We report on the behavior of Pt nanoparticles functionalized with 4-mercaptoaniline over-grafted with 2-thiophenecarbonyl chloride. Stable Langmuir–Blodgett (LB) mixed films were built up from these particles with behenic acid (BHA). Such ultra-thin films were transferred onto gold substrates, which allowed the study of their electrochemical response towards Fe[(CN)6]3− and their XPS chemical analysis before and after the BHA removal. After washing, XPS analysis showed that the signals corresponding to the metal core and the capping agent were almost unchanged. Moreover, the layers became more compact, as shown by the Pt/Au intensity ratio decrease, because of the apparent decrease of length escape of electrons coming from gold, evidencing the removal of the fatty acid in the LB film structure. After BHA removal, the resulting electrochemical activity slightly increased. This result, in agreement with XPS analysis, showed the structural rearrangement within the film that facilitated the percolation between the particle domains.

Enhancement of ferroelectricity in Langmuir–Blodgett multilayer films of weak-polar organic molecules

Ferroelectricity in Langmuir–Blodgett (LB) films (Z-type and alternated Y-type) of nitrogencrown (NC) and arachidic acid (AA) was investigated by electric polarization measurements and small angle X-ray diffraction (SAXD). For Z-type AA LB multilayer and the AA LB films incorporating barium ions, as well as for Z-type NC LB multilayer and the Y-type NC/AA alternating LB films, hysteresis loops of the samples were observed and confirmed existence of the remnant polarizations in the LB films. Their corresponding remnant polarizations were found to be 15, 180, 450 and 9400 μC m −2, respectively. Therefore, the maximum ratios of remnant polarizations up to 620 (9400/15)-folds were obtained from NC/AA alternating LB films. The enhancement of ferroelectricity in NC/AA alternating LB films was observed for the first time. It was demonstrated that the enhancement of ferroelectricity in the LB films could be created by incorporation of barium ions into the LB film structures and strong interaction due to electron clouds redistribution largely originated from the compact insertion configuration of AA between two chains of NC molecules in interleaving films.

The structure of ultrathin Langmuir-Blodgett films of cadmium behenate

Grazing incidence x-ray-diffraction investigations of the structures of Langmuir-Blodgett films of cadmium behenate with 1, 2, 3, 5, and 21 monolayers are reported. The single monolayer film, deposited on a hydrophilic substrate, showed a hexagonal structure, whereas the bilayer film, deposited on a hydrophobic substrate, had a rectangular structure with herringbone orientation of the acyl chains. With multilayer films formed on a hydrophilic substrate, it was possible to detect that the hexagonal structure of the first layer was retained when additional layers were deposited and that the additional layers had the same rectangular structure as the bilayer.

Thermodynamic characteristics and Langmuir–Blodgett deposition behavior of mixed DPPA/DPPC monolayers at air/liquid interfaces

The role of dipalmitoylphosphatic acid (DPPA) as a transfer promoter to enhance the Langmuir–Blodgett (LB) deposition of a dipalmitoylphosphatidylcholine (DPPC) monolayer at air/liquid interfaces was investigated, and the effects of Ca 2+ ions in the subphase were discussed. The miscibility of the two components at air/liquid interfaces was evaluated by surface pressure–area per molecule isotherms, thermodynamic analysis, and by the direct observation of Brewster angle microscopy (BAM). Multilayer LB deposition behavior of the mixed DPPA/DPPC monolayers was then studied by transferring the monolayers onto hydrophilic glass plates at a surface pressure of 30 mN/m. The results showed that the two components, DPPA and DPPC, were miscible in a monolayer on both subphases of pure water and 0.2 mM CaCl 2 solution. However, an exception occurs between X DPPA = 0.2 and 0.5 at air/CaCl 2-solution interface, where a partially miscible monolayer with phase separation may occur. Negative deviations in the excess area analysis were found for the mixed monolayer system, indicating the existence of attractive interactions between DPPA and DPPC molecules in the monolayers. The monolayers were stable at the surface pressure of 30 mN/m for the following LB deposition as evaluated from the area relaxation behavior. It was found that the presence of Ca 2+ ions had a stabilization effect for DPPA-rich monolayers, probably due to the association of negatively charged DPPA molecules with Ca 2+ ions. Moreover, the Ca 2+ ions may enhance the adhesion of DPPA polar groups to a glass surface and the interactions between DPPA polar groups in the multilayer LB film structure. As a result, Y-type multilayer LB films containing DPPC could be fabricated from the mixed DPPA/DPPC monolayers with the presence of Ca 2+ ions.

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.

An infrared study on Langmuir–Blodgett films of 14,15-bis(hydroxyimino)-13-thiaoctacosane

The Langmuir–Blodgett (LB) films of 14,15-bis(hydroxyimino)-13-thiaoctacosane (TOC) on aluminium plated substrates were investigated using Fourier transform infrared (FTIR), grazing angle (GAIR) and horizontal attenuated total reflectance (HATR) techniques. The LB films of TOC can be transferred onto the solid substrate successfully. The molecular structure of LB films was analysis by comparing the GAIR and HTAR spectra. The intense bands at 2848 and 2918 cm −1 are assigned to symmetric ν s(CH 2) and asymmetric ν a(CH 2) stretching vibrations of methylene groups. These peaks suggest that the alkyl chains in TOC are nearly in all-trans conformational state. The presence in the infrared spectra of several bands due to the methylene wagging and twisting modes and of the splitting of the bands due to the methylene scissoring mode at 1467 and 1459 cm −1 and the CH 2 rocking mode at 720 and 731 cm −1 also indicates that in films of TOC alkyl chains are in the all-trans conformation and packed in either an orthorhombic or a monoclinic structure with an orthorhombic subcell containing two mutually orthogonal molecules. Another conclusion presented in this paper that the alkyl chain tilt, which is the angle between the axis, which bisects the C–C bonds and the surface normal, was quite large by comparing the GAIR and HATR spectra.

Infrared Spectroscopy Analysis of the Structure of Multilayer Langmuir−Blodgett Films: Effect of Deposition Velocity and pH

Multiple Langmuir-Blodgett (LB) films of arachidic acid were deposited on germanium (Ge) substrates from subphase solutions of 10(-4) M CdCl2 at different pH values and at different deposition speeds. Attenuated total reflectance infrared (ATR-IR) spectroscopy was used to obtain information on the molecular order and structure of these multilayer LB films. At pHs higher than the pKa of the fatty acid/cation system, transfers took place only during the downstroke, indicating X-type deposition. At pH = pKa and large deposition speeds, deposition partially failed during the downstroke, resulting in Z-type depositions. Analysis of the infrared spectra indicates that multiple LB films deposited only during the upstroke (Z-type) or during downstrokes (X-type) have a centrosymmetric structure typical of films deposited during the upstroke and downstroke, except for a slight decrease in molecular order and tilt angle as the pH increases (X-type). The centrosymmetric structure indicates that rearrangement of layers takes place between cycles. Experimental evidence of such rearrangement occurring in a fatty acid/divalent cation salt subphase is shown here, and rearrangement alternatives are discussed.