Langmuir-Blodgett Film Deposition Research Articles

Photoluminescence of Tetra(benzimidazole)phenylethene Derivatives and Their Carbene Metallacycles in Aggregates and Langmuir-Blodgett Films.

Molecular structure, external stimuli, and environmental factors all have a strong effect on the internal molecular rotation and vibration of aggregate-induced emission (AIE) luminogens. Here, we report the AIE effect for several newly synthesized amphiphilic tetra(benzimidazole)phenylethene (TBiPE) derivatives and their binuclear N-heterocyclic carbene silver (NHC-Ag) metallacycles in solutions, aggregates, and Langmuir-Blodgett (LB) films. Monolayer behaviors and microscopic images indicate that introducing alkyl chains and binuclear NHC-Ag metallacycles can facilitate the formation of a well-defined insoluble monomolecular layer at the air-water interface. Absorption and luminescence spectral features suggest that both the TBiPEs' cyclization structure and binuclear NHC-Ag metallacycles can provide additional driving forces to restrict the internal molecular motion of the tetraphenylethene (TPE) unit, thus enhancing the AIE effects. Further, external stimuli and environmental factors such as poor solvent addition and LB film deposition also play important roles in the photoluminescent intensity, maximum wavelength, and lifetime. These internal and external factors can result in around 30-40 nm blue-shift for the maximum luminescence wavelength and 2-3 times shorter for the luminescent lifetime. These phenomena can be attributed to the reason that the nonradiative energy transfer efficiency is weakened because of the enhanced hydrophobic interaction and metal-carbene coordination as well as the closely packed arrangement of AIEgens in the LB films; consequently, the radiation energy transfer efficiency increased.

Facile preparation and study of supramolecular architecture of an efficient nanocomposite LB film AHSM/SA based on azo-functionalized hockey stick-shaped mesogen at air-water and air-solid interface

Hockey stick-shaped mesogens are fascinating thermotropic liquid crystal systems owing to their exceptional supramolecular assembly properties and shape anisotropy compared to conventional rod-and bent-shaped mesogens. In this article, we present an investigation of the supramolecular organization of a new azo-functionalized hockey stick-shaped mesogen with stearic acid at the air-water interface and air-solid interfaces by applying the Langmuir-Blodgett film deposition method. The incorporation of stearic acid can change the molecular organization of azo-functionalized hockey stick-shaped mesogen at an aqueous interface through hydrophobic-hydrophobic interactions and form a supramolecular nanostructure at the solid interface. The interfacial nature of the Langmuir monolayer was studied by recording the isotherm (surface pressure area, π–A), which was further analyzed by using Brewster angle microscopy. The significant reduction in molecular area, increased surface pressure, and lower isotherm slope of the AHSM/SA composite mixture indicate the hybrid AHSM/SA monolayer's greater stability compared to pure AHSM. BAM images of the AHSM/SA composite signify nanostructure aggregates formed by the interaction of AHSM and SA molecules at the air-water interface. Field emission scanning electron microscopic analysis of composite films revealed the formation of supramolecular domains. The impact of changing the surface pressure and the number of depositions on the morphology of the composite film surface was monitored using field emission scanning electron microscopy. The supramolecular H-type aggregation of azo-functionalized hockey stick-shaped mesogen and stearic acid molecules in the composite LB film was characterized using UV–visible absorption and steady-state fluorescence spectroscopy. The adsorption of stearic acid onto azo-functionalized hockey stick-shaped mesogen via hydrophobic interactions was confirmed by Fourier transform infrared spectroscopy of the composite Langmuir Blodgett film. Further, Raman spectroscopy of the LB films of the AHSM/SA composites is distinct from the pristine film components due to the merging of signals at similar wave numbers for both SA and AHSM with a lack of typical packing pattern further supported by PXRD studies of the films.

Interfacial Interactions of Monoolein Langmuir Monolayers with Aqueous Salt Solutions

Langmuir monolayer is a unique tool to characterize the interface which describes the properties of insoluble monolayer on the sub-phase. Langmuir monolayers have demonstrated the characteristics of many macromolecules as well as amphiphilic molecules at the air-water interface. We evaluated physiochemical characteristics of monoolein lipid Langmuir monolayers on different sub-phases. Interfacial behaviour of monoolein lipid was investigated using Wilhelmy plate pressure sensor technique to generate Langmuir isotherms to explore the effects of interactions with different sub-phases. Various salts alter the surface pressure of the Langmuir monolayer isotherms without the alteration of monolayer phase transitions. The finding of the present work can be effectively used for development of suitable biomedical formulations to offer sufficient strength of coating film with controlled topology and thickness using Langmuir-Blodgett film deposition technique. Addition of the suitable biocompatible ions in to the sub-phase is very crucial for their favourable interfacial interaction with the lipid molecules.

Morphology of Mixed Langmuir and Langmuir-Schaefer Monolayers with Covered CdSe/CdS/ZnS Quantum Dots and Arachidic Acid.

The process of formation of a Langmuir-Schaefer (LS) matrix based on a mixed monolayer of arachidic acid (AA) and 8 nm CdSe/CdS/ZnS quantum dots (QDs) stabilized by molecules of trioctylphosphine oxide (TOPO) was investigated. The change in the morphology, monolayer compressibility, and area per elementary cell of the created mixed monolayers, depending on the ratio of the components, was studied. It is shown that the change in the morphology of Langmuir-Blodgett (LB) monolayers begins to occur at a ratio between the number of QDs and AA molecules of 1:24. Dendrimeric structures with a thickness of the order of 30-40 nm appear in the mixed monolayer when LB film deposition was carried out above the collapse surface pressure of a Langmuir film from only TOPO-covered QDs. Information on the dependence of the morphology of such structures on the molar ratio of the components is necessary for the production of ordered 2D nanostructures containing 0D and 1D objects with quantum bonds. Such nanostructures can be used in nanoelectronic and optoelectronic devices as a sensitive sensor element. The obtained results would be relevant for any type of spherical shape nanoparticles.

Morphological Variation of an LB Film of Giant Amphiphiles Composed of Poly(ethylene oxide) and Hydrophobically Modified POSS.

Hydrophobically modified polyhedral oligomeric silsesquioxanes (XPOSS) are linked to one end of water-soluble poly(ethylene oxide) (PEO) to synthesize giant amphiphiles (XPOSS-PEO). XPOSS-PEO exhibit an interesting surface activation capacity owing to the synergy of the soft PEO segment and hydrophobic XPOSS when they are spread on the water surface and compressed by the barrier. The monolayers of XPOSS-PEO at the air-water interface are transferred onto the silicon substrate at different surface pressures using the Langmuir-Blodgett (LB) film deposition protocol. The modification of the POSS head significantly changes the crystallinity of the PEO tail, which affects the LB film morphologies of the giant amphiphiles. When the POSS are modified with fluorinated agents, the assembled LB films show a fractal growth pattern, but when the POSS are decorated with a pure alkane chain, the fractal growth pattern does not present in the resulting LB film.

Aligned Assembly in a 2-D Gel of a Water-Soluble Peptide.

We demonstrate the assembly of a compact, gel-like Langmuir-Blodgett film of rods formed by self-assembly of a β-sheet-forming water-soluble peptide, Ac-IKHLSVN-NH2, at the surface of aqueous electrolytes. We characterize surface pressure hysteresis and demonstrate shear stiffening of the surface caused by area cycling, which we interpret as due to rearrangement and alignment of the rods. We show strong effects of the electrolyte on the assembly of the elementary rods, which can be related to the Hofmeister series and interpreted by effects on the interaction energies mediated by ions and water. Formation of β-sheet structures and assembly of these into surface-segregated semicrystalline gels was strongly promoted by ammonium sulfate electrolyte. With ammonium sulfate electrolyte as subphase for Langmuir-Blodgett film deposition, shear stiffening by surface area cycling resulted in very compact films on transfer to a substrate.

Fluorinated polyhedral oligomeric silsesquioxanes end-capped poly(ethylene oxide) giant surfactants: precise synthesis and interfacial behaviors

Interfacial behavior of giant surfactants with precisely tethered molecular nanoparticles (MNPs) is an important topic. In this article, by the combination of hydrosilylation, esterification, and CuAAC ‘‘click’’ chemistry, poly(ethylene oxide) (PEO) chains were end-capped with particle-like aryl-trifluorovinyl ether functionalized polyhedral oligomeric silsesquioxane (FVPOSS) to construct “one-head one-tail” and “bola-form” giant surfactants. The giant surfactants are spread at air/water interface, and surface pressure-area (π-A) isotherms reveal their interfacial behaviors under compression. Atomic force microscope (AFM) images indicate that the giant surfactants show fractal growth behavior after transferred to the silicon substrate at different surface pressure through the procedure of Langmuir-Blodgett (LB) film deposition. The results are useful for understanding the assembly of giant surfactants at the interface and developing of nanostructured functional materials.

Effect of Langmuir coating on the localization of excitonic polarization in CdS surface layer

Low temperature (T=2K) optical reflection spectra have been studied for the organic-semiconductor structures prepared by deposition of Langmuir-Blodgett films on CdS surface. The spectra are measured in the resonant spectral range of the An=1 exciton state in CdS. Theoretical analysis of the spectra is carried out with an account of the spatial dispersion effects and the exciton-free surface “dead” layer. The conclusion has been drawn of the interface localization of the Wannier-Mott exciton due to organic film deposition on the crystal surface.

Langmuir-Blodgett Films of C60-end-capped Poly(ethylene oxide)

Buckyballs (C60) are linked to one end and two ends of linear poly(ethylene oxide) (PEO) chains through highly efficient click chemistry to obtain giant amphiphilic molecules C60-PEO and C60-PEO-C60, respectively. C60-PEO and C60-PEO-C60 molecules are spread on water surface and then transferred to solid substrates with Langmuir-Blodgett (LB) film deposition approach. C60-PEO and C60-PEO-C60 exhibit fractal growth behavior on the solid substrate under certain conditions owing to the crystallization ability of PEO segment. PEO chain length and the end capped mode both affect the fractal growth pattern.

Локализация экситона Ванье-Мотта на органополупроводниковом интерфейсе ленгмюровская пленка / CdS"

Low temperature (T=2 K) optical reflection spectra have been studied for the organic-semiconductor structures prepared by deposition of Langmuir-Blodgett films on CdS surface. The spectra are measured in the resonant spectral range of the exciton state in CdS. Theoretical analysis of the spectra is carried out with an account of the spatial dispersion effects and the exciton-free surface “dead” layer. The conclusion has been drawn of the interface localization of the Wannier-Mott exciton due to organic film deposition on the crystal surface.

Surface-modified substrates for the Langmuir-Blodgett deposition of patterned ultra-thin and highly oriented collagen coatings

As a pre-study for highly oriented collagen coatings on implants (with irregular surfaces and shapes), the Langmuir-Blodgett (LB) technology, a low-cost and straightforward approach, was pioneered. The effects of physicochemical (hydrophilic/hydrophobic) patterns and 3D-mechanical barriers present on substrate surfaces are studied in terms of the dynamics of collagen flow during LB film deposition and the formation of highly oriented coatings. Due to the large internal cohesion of collagen films, only large 3D-obstacles deflect the flow of collagen and lead to film rupture, suggesting that objects (screw-threaded dental implants) with small topographic features should be easily and evenly coatable. Moreover, hydrophilic/hydrophobic/collagen patterned substrate surfaces were fabricated, by partly removing coated collagen. These substrates are outstanding for timely studies that need identical conditions but different surface properties side by side. Crystallisation of barium oxalate was carried out as a proof-of-principle.

Surface-modified substrates for the Langmuir-Blodgett deposition of patterned ultra-thin and highly oriented collagen coatings

As a pre-study for highly oriented collagen coatings on implants (with irregular surfaces and shapes), the Langmuir-Blodgett (LB) technology, a low-cost and straightforward approach, was pioneered. The effects of physicochemical (hydrophilic/hydrophobic) patterns and 3D-mechanical barriers present on substrate surfaces are studied in terms of the dynamics of collagen flow during LB film deposition and the formation of highly oriented coatings. Due to the large internal cohesion of collagen films, only large 3D-obstacles deflect the flow of collagen and lead to film rupture, suggesting that objects (screw-threaded dental implants) with small topographic features should be easily and evenly coatable. Moreover, hydrophilic/hydrophobic/collagen patterned substrate surfaces were fabricated, by partly removing coated collagen. These substrates are outstanding for timely studies that need identical conditions but different surface properties side by side. Crystallisation of barium oxalate was carried out as a proof-of-principle.

First observation of 3D aggregates in a single-component Langmuir film below the equilibrium spreading pressure

Single component monolayers from Dipalamitoyl Phosphatidyl Ethanolamine head labelled with the fluorescent chromophore NitroBenzoxaDiazole (DP-NBD-PE) were investigated at the air-water interface as Langmuir films and deposited on silicon wafers or glass plates as Langmuir-Blodgett (LB) films. A step compression and monitoring of the pressure relaxation together with domain formation as observed with Brewster angle microscopy suggests that main transition from liquid expanded to liquid compressed state start at around 6.9 mN/m though on the isotherm it starts around 9 mN/m at 25° C. Brewster angle microscopy also reveals a nonuniform structure in the monolayer. 3D aggregates - cylinders with 50 – 150 nm diameter and bilayer height were observed with Atomic Force Microscopy when deposition was carried at 7 mN/m, above the main phase transition but considerably lower than the equilibrium spreading pressure of 19.6 mN/m for this molecule. When LB film deposition is carried just below the main phase transition a uniform height layer of film in a liquid phase is observed with AFM with no structures. Both compression and deposition were carried at very low speeds with large time to relax in ordered to avoid kinetic effects. These 3D aggregates are not due to the transfer process or interaction with the substrate. These aggregates provide a highly developed area combined with monolayer thick structure which can produce very fast and highly sensitive biosensors.

Two-Dimensional Alignment of Self-Assembled Organic Nanotubes through Langmuir-Blodgett Technique.

A C3-symmetric molecule was found to form organic nanotubes through supramolecular gel formation in organic solvents. These nanotubes can be dispersed in toluene without destroying the tubular nanostructures. Using the dispersions of these organic nanotubes as "spreading solutions", Langmuir-spreading films of these nanotubes were formed. Through repeated compression and expansion cycles, the nanotubes can be aligned to a certain extent. The formed Langmuir films could be subsequently transferred to a solid substrate, and the well-aligned nanotube films were constructed by Langmuir-Blodgett film deposition technique. Interestingly, many guests including polymers, water-soluble or oil-soluble organic molecules can be encapsulated into the nanotubes and further spread on a water subphase. Through elaborate control, large-scale parallel alignment of self-assembled organic nanotubes encapsulated by guests was also realized. This study implies that 2D hierarchical alignment of one-dimensional organic nanostructures can be realized using a simple method.

Factors affecting photocurrent generation performances of Langmuir–Blodgett films of tetraphenylporphyrin-bound acyl celluloses

Various Langmuir–Blodgett (LB) films of tetraphenylporphyrin (TPP)-bound acyl celluloses with different degrees of substitution of the TPP groups (DSTPP) and different acyl groups were prepared. TPP-bound acyl celluloses with DSTPP values less than 0.38 and myristoyl groups as the O-2 and O-3 substituents were suitable for obtaining LB mono-layer films with high quantum yields. The horizontal lifting method was better than the vertical dipping method for the deposition of LB films. The number of layers in LB multi-layer films of TPP-bound myristoyl cellulose with a DSTPP of 0.36 also influenced the quantum yield, and the quantum yield of the LB di-layer film was higher than those of the LB mono- and tri-layer films. This information will be useful in the improvement of the photocurrent generation performances of LB films of TPP-bound acyl celluloses.

Equipment-Free Deposition of Graphene-Based Molybdenum Oxide Nanohybrid Langmuir-Blodgett Films for Flexible Electrochromic Panel Application.

The potential electrochromic application of graphene-based nanohybrids is hampered by the challenges in interfacing the electrochromic nanoparticles with graphene at atomic scale and in fabricating their thin film on the substrate through a scalable method. In an effort to overcome these challenges, we demonstrate a highly dispersible graphene-based molybdenum oxide nanohybrid (mRGO-MoO3-x) for flexible electrochromic application. With only a squeeze pipet, mRGO-MoO3-x could be deposited with a high coverage on various substrates through a scalable equipment-free Langmuir-Blodgett film deposition method. By taking advantage of high transmittance benefited from its remarkable thinness, the mRGO-MoO3-x Langmuir-Blodgett film shows a superior reversible electrochromic property with high coloration efficiency on both hard and flexible substrates.

Characterization of N-cyclohexylmethacrylamide LB thin films for room temperature vapor sensor application

ABSTRACTThis study reports the synthesis, characterization and gas sensing applications of N-cyclohexylmethacrylamide (NCMA) monomer material using FT-IR, 1H and 13C NMR, UV-visible spectroscopy, Quartz Crystal Microbalance (QCM) and Langmuir-Blodgett (LB) thin film deposition techniques. The thin film deposition conditions of NCMA monomer material, which are prepared by LB film technique, are characterized by UV-visible spectroscopy and QCM system. The sensing behaviors of the LB film with respect to volatile organic compounds (VOCs) at room temperature are investigated. Surface pressure change as a function of surface area of NCMA molecule at the water surface shows a well-organized and stable monolayer at 18 mN m−1 surface pressure value for LB film deposition. Transfer ratio values are found to be ≥ 0.94 for quartz glass and ≥ 0.93 for quartz crystal substrate. The typical frequency shift per layer is obtained 20.10 Hz/layer and the deposited mass onto a quartz crystal is calculated as 824.62 ng/layer. The sensing responses of the LB films against chloroform, dichloromethane, acetone, toluene, benzene and ethanol are measured by QCM system. The sensitivities of the NCMA LB film sensor are determined between 0.085 and 0.029 Hz ppm−1. Sensitivities with detection limits are between 35.29 and 100.33 ppm against organic vapors. These results can be concluded that the monomer LB film sample is found to be significantly more sensitive to chloroform and dichloromethane vapors than others organic vapors used in this work. This material may find potential applications in the development of room temperature organic vapor sensing.

Fabrication of ultrathin films containing the metal organic framework Fe-MIL-88B-NH 2 by the Langmuir–Blodgett technique

Abstract In this work, the fabrication of ultrathin films containing the metal organic framework (MOF) Fe-MIL-88B-NH 2 by the Langmuir–Blodgett (LB) technique has been explored. MOF crystals of two different sizes (1.5 ± 0.3 and 0.07 ± 0.01 μm) have been synthesized and assembled at the air–liquid interface by the LB method. The effect of the subphase pH and particle size on the film formation process has been studied. Moreover, for the first time, mixed MOF + polymer (the commercial soluble polyimide Matrimid ® ) LB films containing different MOF loadings have been fabricated. These experiments show that it is possible to obtain ultrathin MOF + polymer films with a controlled MOF density. Furthermore, MOF particles are homogeneously distributed in the polymer matrix, even with very large amounts of MOF (up to 95 wt%). LB films have been incorporated into materials of different nature, including glass and mica substrates and also polymeric membranes based on polysulfone Udel ® and PIM-1 (polymer of intrinsic microporosity), and the modification of water contact angle after LB film deposition has been analyzed.

Effects of POSS nanoparticles on glass transition temperatures of ultrathin poly(t‐butyl acrylate) films and bulk blends

ABSTRACTAs a model system, thin films of trisilanolphenyl‐POSS (TPP) and two different number average molar mass (5 and 23 kg mol−1) poly(t‐butyl acrylate) (PtBA) were prepared as blends by Langmuir–Blodgett film deposition. Films were characterized by ellipsometry. For comparison, bulk blends are prepared by solution casting and the samples are characterized via differential scanning calorimetry. The increase in Tg as a function of TPP content for bulk high and low molar mass samples are in the order of ∼10 °C. Whereas bulk Tg shows comparable increases for both molar masses (∼10 °C), the increase in surface Tg for higher molar mass PtBA is greater than for low molar mass (∼22 °C vs. ∼10 °C). Nonetheless, the total enhancement of Tg is complete by the time 20 wt % TPP is added without further benefit at higher nanofiller loads. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015, 53, 175–182

Optimized Deposition of Graphene Oxide Langmuir-Blodgett Thin Films

Abstract Single sheet graphene (SG) is an innovative transparent material with high electrical and thermal conduction the use of which in transparent electrodes instead of traditional materials improves the performance of optoelectronic devices. In this study, graphene oxide (GO) has been obtained by a modified Hummer`s method followed by an advanced technique of water removal (lyophilisation). The Langmuir-Blodgett (LB) method was applied to transfer GO from suspension to substrate. To optimize the deposition process, as suspending and spreading solvents the benzene and benzene/methanol mixtures were chosen instead of previously studied water suspensions. The number of GO layers in suspension is reduced by exfoliation in order to obtain a single GO monolayer. For this purpose, sonication and centrifugation of GO sheets are carried out. Finally, the effect of variously treated glass substrate surfaces on the deposition efficiency has been studied. In the work, it is shown that ozonization of glass substrate improves the deposition outcome, while ozonization of indium tin oxide (ITO) glass substrate is necessary to perform such deposition. The obtained GO suspensions and LB thin films have been studied using a scanning electron microscope (SEM)