Mixed 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.

Thermal Behavior of H-Aggregate in a Mixed Langmuir−Blodgett Film of Merocyanine Dye, Arachidic Acid, and n-octadecane Ternary System Investigated by UV−visible and IR Absorption Spectroscopy

We have investigated the thermal behavior of H-aggregate in a mixed Langmuir-Blodgett (LB) film of the merocyanine dye (MS18)-arachidic acid (C20)- n-octadecane (AL18) ternary system by means of UV-visible and IR absorption spectroscopy in the range from 25 to 250 degrees C with a continuous scan. The results of both UV-visible and IR spectra indicate that the temperature-dependent variation in MS 18 aggregation state is linked not only with the degree of intramolecular charge transfer and the behavior of packing, orientation, conformation, and thermal mobility of the MS18 hydrocarbon chain but also with the presence and absence of AL18. The H-aggregate dissociates from 25 up to 50 degrees C, which is caused by the AL18 evaporation from the mixed LB film and the increment of thermal mobility of the MS18 hydrocarbon chain. From 110 to 160 degrees C, blue-shifted bands, attributed to the oligomeric MS18 aggregation, appear near 515 nm in the MS18-C 20-AL18 ternary system as well. The temperature at which the 515 nm band occurs is identical for both present ternary system and previously investigated MS18-deuterated arachidic acid (C20- d) binary system, and it is in good agreement with the melting point (110 degrees C) of cadmium arachidate (CdC20). Therefore, it is indicated that the driving force which induces the 515 nm band comes from the melting phenomenon of CdC20 molecules which are phase-separated from MS 18 molecules in as-deposited LB films.

Micro- and Nanopatterned Copper Structures Using Directed Self-Assembly on Templates Fabricated from Phase-Separated Mixed Langmuir−Blodgett Films

We report a versatile method to confine metal thin films in micro- and nanopatterns using directed self-assembly on the templates fabricated from phase-separated mixed Langmuir-Blodgett (LB) films. The pattern of the mixed LB films can be tuned by adjusting intermolecular interaction between the film-forming molecules in the LB films and by varying the fabrication conditions of the films such as the mixing ratio, subphase temperature, and surface pressure. We use the patterned LB films for templates to confine metal in patterned regions, taking advantage of the difference between the surface free energy of the patterned regions and that of the self-assembled monolayer of the silane coupling agent. Au nanoparticles are confined onto the patterned films as a catalyst for the succeeding Cu electroless deposition. The atomic force microscopic images, Auger electron spectra, and scanning Auger electron maps of a Cu-deposited film show that Cu is selectively deposited on the patterns of phase separation of the original mixed LB films.

Aggregation Behavior of Homo‐PS/PS‐b‐P2VP Blends at the Air/Water Interface

AbstractThe mixed Langmuir monolayers and Langmuir–Blodgett (LB) films of homo‐polystyrene (h‐PS) and the diblock copolymer polystyrene‐block‐poly(2‐vinylpyridine) (PS‐b‐P2VP) have been characterized by the Langmuir monolayer technique and tapping mode atomic force microscopy (AFM), respectively. When the content of h‐PS is below 80 wt.‐%, the mixed LB films of h‐PS/PS‐b‐P2VP mainly exhibit isolated circular nanoaggregates. With a further increase of the h‐PS content (80–95%), however, highly uniform and stable necklace‐network structures are observed in the mixed LB films.magnified image

Fabrication, Structural Characterization, and Applications of Langmuir and Langmuir−Blodgett Films of a Poly(azo)urethane

The synthesis of a poly(azo)urethane by fixing CO(2) in bis-epoxide followed by a polymerization reaction with an azodiamine is presented. Since isocyanate is not used in the process, it is termed "clean method" and the polymers obtained are named "NIPUs" (non-isocyanate polyurethanes). Langmuir films were formed at the air-water interface and were characterized by surface pressure vs mean molecular area per mer unit (Pi-A) isotherms. The Langmuir monolayers were further studied by running stability tests and cycles of compression/expansion (possible hysteresis) and by varying the compression speed of the monolayer formation, the subphase temperature, and the solvents used to prepare the spreading polymer solutions. The Langmuir-Blodgett (LB) technique was used to fabricate ultrathin films of a particular polymer (PAzoU). It is possible to grow homogeneous LB films of up to 15 layers as monitored using UV-vis absorption spectroscopy. Higher number of layers can be deposited when PAzoU is mixed with stearic acid, producing mixed LB films. Fourier transform infrared (FTIR) absorption spectroscopy and Raman scattering showed that the materials do not interact chemically in the mixed LB films. The atomic force microscopy (AFM) and micro-Raman technique (optical microscopy coupled to Raman spectrograph) revealed that mixed LB films present a phase separation distinguishable at micrometer or nanometer scale. Finally, mixed and neat LB films were successfully characterized using impedance spectroscopy at different temperatures, a property that may lead to future application as temperature sensors. Principal component analysis (PCA) was used to correlate the data.

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.

Oxygen reduction of pre-synthesized organically capped platinum nanoparticles assembled in mixed Langmuir–Blodgett films: Evolutions with the platinum amount and leveling after fatty acid removal

Mixed Langmuir–Blodgett (LB) films based on crown derivatized platinum nanoparticles (NPs) and fatty acid showed a direct electrochemical activity toward oxygen reduction reaction (ORR) in acidic medium. This paper reports on the original and strong effects observed in the electrochemical response of these two-phase systems towards oxygen reduction by varying the Pt amount in the mixed LB films. The easy manipulation of pre-synthesized organically capped nanoparticles, combined with the features of the Langmuir–Blodgett technique allows good control of the platinum loading in the films. Pt loadings are set by changing the number of deposited monolayers and/or their nanoparticle density. Loading variations induce strong modifications in the voltammograms and are considered in terms of the relative weight of the two phases: platinum nanoparticles and fatty acids. We point out the strong influence of the environment of platinum nanoparticles towards their electrocatalytical behaviour. Various effects, such as electrical resistance of the nanostructures are considered. Evolution of the peak current density ratios from O 2 and [Fe(CN) 6] 3−/4− probes as a function of platinum loading in mixed films could suggest a possible change in the dominating number of electrons exchanged in the ORR. The effect of the fatty acid phase is definitely demonstrated by the leveling of the electrochemical responses after its elimination from the thin film structures. The electrochemical response is then likely governed by only the organic crown of the particles, which controls the ultimate local environment of the platinum particles. In such a situation, the optimized platinum loading is found to be 2.4 μg cm −2.

Conversion of the Aggregation State of Merocyanine Dye, Modification of the Subcell Packing of Arachidic Acid, and Removal of the Majority of n-Octadecane by Hydrothermal Treatment in the Liquid Phase in a Mixed Langmuir−Blodgett Film of the Ternary System

We have investigated the influence of heat treatment in an air atmosphere (HT) and hydrothermal treatment in the liquid phase (HTTL) on the H-aggregate in a mixed Langmuir-Blodgett (LB) film of merocyanine dye with an octadecyl group (MS(18))-arachidic acid (C(20))-n-octadecane (AL(18)) ternary system by means of polarized visible and IR absorption spectroscopy. HT causes the variation from the H-aggregate to the monomer, the increment in the number of gauche conformers in the MS(18) hydrocarbon chain, the slight orientation change in the C(20) hydrocarbon chain, and the complete evaporation of AL(18). The dissociation of MS(18) is probably ascribed to the complete evaporation of AL(18) from the mixed LB film and the increase in thermal mobility of the long axis of the MS(18) hydrocarbon chain during HT. However, HTTL can easily and rapidly induce the conversion of the MS(18) aggregation state from H- to J-aggregates, the modification of the C(20) subcell packing from hexagonal to orthorhombic, and the removal of most of the AL(18) molecules. The conversion of the MS(18) aggregation state can be interpreted to consist of two processes from the H-aggregate to the monomer and from the monomer to the J-aggregate. In the initial stage of HTTL, the MS(18) aggregation state changes from the H-aggregate to the monomer, which is caused by the removal of almost all of the AL(18) molecules from the mixed LB film to warm water via the thermal energy of warm water. Then, the large relative permittivity of warm water is expected to relate strongly to the subsequent variation from the monomer to the J-aggregate. This transformation results in the decrease in the total value of the electrostatic energy based on the MS(18) permanent dipole interaction. Moreover, the modification of the C(20) subcell packing is possibly due to the hydrophobic effect, where the C(20) hydrocarbon chains cohere again in the warm water during HTTL. Consequently, it has been found that HTTL is quite effective to reorganize the chromophore alignment of MS(18), to modify the subcell packing of C(20) and to erase the majority of AL(18) molecules in the mixed LB film of the MS(18)-C(20)-AL(18) ternary system in a short time.

Direct Sol-Gel Synthesis of Patterned Zirconia Thin Films Using Self-Assembly in Phase-Separated Mixed Langmuir-Blodgett Films

We demonstrated a new method for directed self-assembly of zirconia thin films, reflecting the phase-separated structures of mixed Langmuir-Blodgett (LB) films, through a sol-gel route. Templates were fabricated by heat treatment of mixed LB films of fatty acid and silane-coupling agent, followed by selective removal of the fatty acid. Templates functionalized with amino groups were immersed into zirconia precursor solution. Atomic force microscopy and Kelvin probe force microscopy images showed that the films prepared under optimal conditions had products with the same surface potential within the ex-domain region. Energy dispersive X-ray (EDX) spectra of the products in the ex-domain region clearly showed a peak assigned to Zr. These results confirmed that the patterned zirconia films were prepared on the templates fabricated from phase-separated LB films.

Dis-aggregation of an insoluble porphyrin in a calixarene matrix: characterization of aggregate modes by extended dipole model

In this paper, the different aggregation modes of a water-insoluble porphyrin (EHO) mixed with an amphiphilic calix[8]arene (C8A), at the air-water interface and in Langmuir-Blodgett (LB) film form, are analyzed as a function of the mixed composition. The strategy used to control the EHO aggregation has consisted of preparing mixed thin films containing EHO and C8A, in different ratios, at the air-water interface. Therefore, the increase of the C8A molar ratio in the mixed film diminishes the aggregation of the EHO molecules, although such an effect must be exclusively related to the dilution of the porphyrin. The reflection spectra of the mixed C8A-EHO films registered at the air-water interface, show a complex Soret band exhibiting splitting, hypochromicity and broadening features. Also, during the transfer process at high surface pressure, it has been shown that the EHO molecules are ejected from the C8A monolayer and only a fraction of porphyrin is transferred to the solid support, in spite of a complete transfer for the C8A matrix. The complex structure of the reflection spectra at the air-water interface, as well as the polarization dependence of the absorption spectra for the mixed LB films, indicate the existence of four different arrangements for the EHO hosted in the C8A matrix. The aggregate formation is governed by two factors: the attraction between the porphyrin rings which minimizes their separation, and the alkyl chain interactions, that is, hydrophobic effect and/or steric hindrance which determine and restrict the possible aggregation structures. By using the extended dipole model, the assignment of the spectral peaks observed to different EHO aggregates is shown.

Using phospholipid Langmuir and Langmuir–Blodgett films as matrix for urease immobilization

The immobilization of enzymes in organized two-dimensional matrices is a key requirement for many biotechnological applications. In this paper, we used the Langmuir–Blodgett (LB) technique to obtain controlled architectures of urease immobilized in solid supports, whose physicochemical properties were investigated in detail. Urease molecules were adsorbed at the air–water interface and incorporated into Langmuir monolayers of the phospholipid dipalmitoyl phosphatidyl glycerol (DPPG). Incorporation of urease made DPPG monolayers more flexible and caused the reduction of the equilibrium and dynamic elasticity of the film. Urease and DPPG–urease mixed monolayers could be transferred onto solid substrates, forming LB films. A close packing arrangement of urease was obtained, especially in the mixed LB films, which was inferred with nanogravimetry and electrochemistry measurements. From the blocking effect of the LB films deposited onto indium tin oxide (ITO) substrates, the electrochemical properties of the LB films pointed to a charge transport controlled by the lipid architecture.

Direct Sol–Gel Fabrication of Patterned Zirconia Thin Films Using Self-assembly in Phase-separated Mixed Langmuir–Blodgett Films

Abstract We demonstrate a new method through sol–gel processes for the preparation of patterned zirconia thin films by using directed self-assembly into patterns reflecting the phase-separated structures of mixed Langmuir–Blodgett films. Atomic force microscopy and Kelvin probe force microscopy images confirmed the formation of patterned zirconia thin films.

Formation of Metal-free J-aggregates in Merocyanine/Spiropyran Mixed Langmuir-Blodgett Film

In order to fabricate metal-free J-aggregate, merocyanine(MD)/spiropyran(SP) mixed LB film was transferred on a glass plate from a pure aqueous solution. Upon UV-light illumination, SP molecules isomerized from SP-form to photomerocyanine (PMC)-form and PMC-form molecules formed J-aggregate with self-assembly. Subsequent vapor-treatment of dimethylamine (DMA) aqueous solution after UV-light illumination induced J-aggregate formation of MD molecules. Metal-free J-aggregate of MD dye was formed by the stepwise treatment of UV illumination and the DMA vapor treatment. The formation mechanism of J-aggregate was discussed.

Spectroscopic properties of mixed Langmuir–Blodgett films of rhodamine dyes and poly( N, N-diallyl- N-octadecylamine- alt-maleic acid)

Langmuir–Blodgett (LB) films of poly( N, N-diallyl- N-octadecylamine- alt-maleic acid) as well as mixed films consisting of polyampholyte and two amphiphilic fluorophores – alkyl substituted rhodamine dyes – were prepared and investigated. The π– A isotherm of the polyampholyte at air–water interface is typical for monolayer in the liquid state. Mixed monolayers of polyampholyte and rhodamine amphiphiles show improved packing of the hydrophobic chains. Absorption and fluorescence spectroscopic studies of the mixed LB films reveal the aggregation of dyes in the densely packed multilayer films.

Thermal Behavior of J-Aggregates in Mixed Langmuir−Blodgett Films Composed of Merocyanine Dye and Deuterated Arachidic Acid Investigated by UV−visible and Infrared Absorption Spectroscopy

We have investigated the thermal behavior of J-aggregates in the mixed Langmuir-Blodgett (LB) films composed of the merocyanine dye (MS18)-deuterated arachidic acid (C20-d) binary system in the temperature range from 25 to 250 degrees C by means of UV-visible and IR transmission absorption spectroscopy. The temperature-dependent variations in both UV-visible and IR absorption spectra indicate that the MS18 aggregation states are linked with the MS18 intramolecular charge transfer and the behavior of the packing, orientation, conformation, and thermal mobility of the MS18 hydrocarbon chain. The J-aggregate formed at 25 degrees C in the mixed LB films dissociates in the temperature range from 25 to 110 degrees C, which is mainly ascribed to the increase in the thermal mobility of MS18 hydrocarbon chain and the dissociation of the chelation by a cadmium ion to the MS18 keto group. A thermally induced blue-shifted band appears at around 515 nm from 110 to 160 degrees C. This band is attributed to oligomeric aggregation with side-by-side alignment of the MS18 transition dipole moments on the basis of the shift to a higher-energy side, broadening, and temporary increment of the MS18 intramolecular charge transfer of the band. Consequently, the appearance of the thermally induced blue-shifted band indicates the possibility that the MS18 aggregation states can be controlled from the red shift to the blue shift by the annealing method adopted in the present study.

Microdomains in mixed monolayers of oleanolic and stearic acids: thermodynamic study and BAM observation at the air–water interface and AFM and FTIR analysis of LB monolayers

Monolayers of oleanolic acid (OLA) mixed with stearic acid (SA) were studied at the air–water interface. The surface pressure–area ( π– A) isotherms, measured over the whole composition range, and BAM observations were used to investigate the phase behaviour and self-organization of these components in a two-dimensional structure. Pure OLA forms a very compressible monolayer, and BAM observation revealed the coexistence of large and irregular solid domains of different thickness dispersed in a gas matrix, compatible with the two most probable orientations of the OLA molecule at the interface. Mixtures of OLA/SA form condensed monolayers from low surface pressures and the thermodynamic analysis indicates that OLA molecules, in the presence of the long-chain SA, orient with the major axis almost perpendicular to the interface. Langmuir–Blodgett (LB) monolayers of pure SA and mixtures were further characterized by atomic force microscopy (AFM) and Fourier transform infrared spectroscopy (FTIR). AFM images of LB mixed monolayers evidenced microphase separation, not observable by BAM. The SA rich domains are 4–6 Å thicker than those rich in OLA. The FTIR spectra of mixed LB films on CaF 2 substrates showed that OLA does not perturb the all- trans conformation of the SA long alkyl chains, up to a mole fraction of 0.4. The carbonyl-stretching band of OLA suggests that the carboxylic groups of neighbour OLA molecules are involved in hydrogen bonds, forming dimers, as in pure solid phase OLA. These interactions seem to prevail over the OLA–water hydrogen bonds.

Photophysical characterizations of 2-(4-biphenylyl)-5 phenyl-1,3,4-oxadiazole in restricted geometry

Langmuir and Langmuir–Blodgett (LB) films of non-amphiphilic 2-(4-Biphenylyl)-5-phenyl-1,3,4-oxadiazole (abbreviated as PBD) mixed with stearic acid (SA) as well as with the inert polymer matrix poly(methyl methacrylate) (PMMA) have been studied. Surface pressure versus area per molecule ( π– A) isotherm studies suggest that PBD molecules very likely stand vertically on the air–water interface and this arrangement allows the PBD molecules to form stacks and remain sandwiched between SA/PMMA molecules. At lower surface pressure, phase separation between PBD and matrix molecules occurs due to repulsive interaction. However, at higher surface pressure, PBD molecules form aggregates. The UV–vis absorption and steady-state fluorescence spectroscopic studies of the mixed LB films of PBD reveal the nature of the aggregates. H-type aggregate predominates in the mixed LB films, whereas I-type aggregate predominates in the PBD-PMMA spin-coated films. The degree of deformation produced in the electronic levels are largely affected by the film thickness and the surface pressure of lifting.

Microstructure of Mixed Cadmium Stearate and Behenate Langmuir-Blodgett Films

X-ray diffraction (XRD) was used to investigate the microstructure and phase separation of mixed multilayers of cadmium stearate (SA) and behenate (BA) deposited onto hydrophilic glass by the Langmuir-Blodgett technique. No unitary fatty acid diffraction peaks in the XRD spectra of the mixed LB films, which reveals that domains in these samples are small and uniform. The interplanar spacing of the mixed LB films changes with the ratio of BA to SA in a step-shaped curve, which suggests that with the changing of the ratio between BA and SA, only three kinds of ordered structure form in the mixed system, and each microstructure, in particular, the short chains against long chains meshed microstructure can be maintained in a certain ratio range. In addition, for the meshed microstructure, the alkyl chains of both SA and BA stand straight or may have exactly the same small tilted angle from the substrate normal, as is indicated by the symmetric and asymmetric stretching vibration of methylene (CH2) peaks which are at 2847.80 and 2914.37 cm1 respectively in the Fourier transform infrared (FT-IR) transmission spectra. The mixed system always goes through a longitudinal regularity decreasing process when BA/SA is out of the intermediate ratio range (BA/SA: 1/5-1/1), which is illustrated by the relative XRD intensity changing with the ratio of BA/SA in a ``W'' shape. These results for the mixed LB films of BA/SA provide meaningful data for choosing the mixture ratio when fabricating composite films with special structure.

Photoluminescence of a mixed Langmuir–Blodgett film of C 60 and stearic acid at room temperature

π– A isotherms, transmission electron microscope (TEM), atomic force microscope (AFM) images and photoluminescence spectra of a mixed Langmuir–Blodgett (LB) film of C 60 and stearic acid (SA) deposited on silicon substrate have been measured at room temperature. C 60/SA nanoparticles aggregated and formed an ordered net-like structure when deposited on silicon substrate. Two PL intense bands centered at 731 and 806 nm, respectively, which are rare at room temperature, were obtained. It is supposed that the particular ordered net-like construction of the LB film plays a crucial role in the enhancement of the photoluminescence. The 731 nm PL band is related with the aggregation state of the particles and the 806 nm PL band is referred as the intrinsic PL spectrum of the C 60.

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.