Molecular orientation analysis of a single-monolayer Langmuir-Blodgett film on a thin glass plate by infrared multiple-angle incidence resolution spectrometry

Molecular orientation analysis in a single monolayer deposited on a glass substrate has been a difficult matter, since the glass substrate absorbs infrared rays so strongly that the measurements of infrared spectra are difficult to perform, and the single monolayer is not suitable for X-ray diffraction analysis because no periodical structure is available. When a thin glass is used as the substrate, in particular, the infrared analysis becomes more difficult, since optical fringes appear strongly on the absorption spectra due to the multiple reflections in the glass. In the present study, infrared multiple-angle incidence resolution spectrometry (MAIRS) has been employed to remove the fringes from the spectra of single- and five-monolayer Langmuir-Blodgett (LB) films of cadmium stearate deposited on a thin glass plate. The MAIRS in-plane spectra gave quantitatively reliable infrared transmission spectra for both films with little fringes, which made it possible for the first time to analyze the molecular orientation in the single-monolayer LB film on glass. As a result, it has been revealed that the molecule in the single-monolayer LB film on thin glass exhibits a significantly larger molecular tilt angle than those prepared on other substrates such as gold and germanium.     

Advanced multiple-angle incidence resolution spectrometry for thin-layer analysis on a low-refractive-index substrate

A long-time issue that thin films supported on a substrate with low refractive index cannot be subjected to multiple-angle incidence resolution spectrometry (MAIRS) has been resolved, and an advanced MAIRS technique has been developed. Infrared multiple-angle incidence resolution spectroscopy (IR MAIRS) is being recognized as a powerful spectroscopic tool for revealing molecular orientation in thin films or molecular adsorbates. MAIRS has been, however, employed with only IR spectroscopy thus far, since MAIRS requires high refractive index substrates such as germanium and silicon, and shorter wavelength regions have no appropriate substrates. Although one of the most commonly useful substrates for IR spectroscopy is CaF2, unfortunately it cannot be employed for IR MAIRS because of the low refractive index. To overcome this experimental limitation, the principle of MAIRS has been studied theoretically, and it has been found that polarization effects on transmission intensity is the main cause that disturbs a proper MAIRS analysis. As a result, now it is possible to employ IR MAIRS for analysis of thin films on CaF2 by removing the s-polarization and by use of the advanced MAIRS algorithm.     

Semifluorinated TTF derivatives in Langmuir-Blodgett films

New semifluorinated tetrathiafulvalene (TTF) derivatives were prepared and used in Langmuir and Langmuir-Blodgett (LB) films. Transfer onto a solid substrate of such pure monolayers can be easily achieved leading to organized LB films in which the fluorinated chains are tilted with respect to the normal of the substrate as demonstrated by infrared and X-ray experiments. Doping of such films by iodine does not induce change in the layer spacing on the contrary to already published studies concerning alkyl derivatives of TTF. Such structural stability and values of the layer thickness suggest some interdigitation between TTF groups within the LB film. Depending on the exact chemical structure of the TTF moiety, the iodination is stabilized or not. When the doped film is stabilized in a mixed valency state, conductivity of approx. 10⁻² S cm⁻¹ was measured at room temperature.     

Preparation of poly(3-hexylthiophene)/[6,6]-phenyl-C61-butyric acid methyl ester Langmuir-Blodgett bulk hetero junctions on indium tin oxide

Mono-layers of aggregated Poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) molecules were obtained by using solutions of P3HT, PCBM and P3HT-PCBM mixture without stabilizers such as stearates in chloroform at an air-water interface. 1 to 10 cycle-lifted LB films of P3HT and PCBM were successfully transferred to cleaned bare indium-tin-oxide coated glass substrate by vertical lifting method excluding the first 1 to 2 cycle layer. The dependence of P3HT and PCBM film thickness on the transfer cycles has been explained by the molecular sizes, where four edge-on P3HT molecular and six PCBM molecular stacking which result in thickness was taken into account. Work functions of deposited LB-layers were consistent with those of the ordinary casted films. P3HT and PCBM LB-layers showed optical activity in both infra-red (IR) and visible absorption regions of the spectrum. P-polarized IR absorption owing to C=C and C=O stretching vibrations observed in LB-layered films clearly indicate the enhancement of the orientation of these bonds perpendicular to the substrate surface in contrast to the spin-coated one. Visible optical absorption intensity was increased well in proportion with the lift cycle-numbers of both P3HT and PCBM LB films. The photovoltaic characteristics have been observed in the devices fabricated with P3HT (5 cycles-layer)/PCBM (5 cycles-layer) LB hetero structure as an active layer of the solar cells. The surface pressure of LB compression for the mixture of P3HT and PCBM, that is, bulk hetero mixtures, has also been well built up to 30 mN/m.     

Layer by layer composite film of dimyristoyl-phosphatidylcoline and bacteriorhodopsin fabricated by multilayer molecular thin film method using fatty acid and lipid

A composite film of dimyristoyl-phosphatidylcoline (DMPC) and bacteriorhodopsin (BR) was fabricated by multilayer molecular thin film method using fatty acid and lipid on a quartz substrate or a hydrogenated amorphous silicon thin film. FTIR reflection absorption spectrums and UV absorption spectrums of the films were characterized on the detail of surface structure of the films. The spectroscopic data exhibited a specific layer by layer interaction of BR and environmental molecule DMPC above fatty acid. Especially, 4 layer composite LB films DMPC and BR exhibited an entirely different feature of IR reflection absorption spectrum depend on fatty acid species.     

Cartesian-structure analysis in cast films by advanced infrared multiple-angle incidence resolution spectroscopy

Multiple-angle incidence resolution spectroscopy (MAIRS) has been improved to be an advanced algorithm so that the Cartesian structure in organic thin films can be analyzed. The infrared MAIRS technique was originally proposed as a totally new spectroscopic technique to reveal structural anisotropy in thin films on an infrared-transparent substrate, which yields both in-plane- (IP; X and Y) and out-of-plane (OP; Z)-mode spectra from an identical sample. Since this technique employs an analytical concept based on a signal decomposition of light intensity (not absorbance spectra), the algorithm intrinsically has high potential for further development. In the present study, the theoretically deduced matrix that correlates the light intensity to the angle of incidence has been modified to further decompose the IP-mode spectrum into X and Y components. As a result, anisotropic measurements of infrared spectra of thin film have become possible for the X, Y, and Z directions (Cartesian coordinate) simultaneously. With this advanced algorithm, the Cartesian structural changes in a cast film prepared on a germanium substrate have readily been analyzed, and a change from the biaxial to the uniaxial film structure with aging has spectroscopically been revealed.     

Pyroelectric figure of merit for a calix [4] acid/amine alternate layer Langmuir–Blodgett film

In this work calix [4] acid (A) has been deposited alternately with calix [4] amine (B) using the LB film deposition technique to form a non-centrosymmetric ABABA… molecular architecture. Pyroelectric and dielectric electric measurements have been performed for a 31 layer calix [4] acid/amine alternate layer LB film. Pyroelectric coefficients for this LB film system have been obtained using a quasi-static measurement system. Dielectric measurements have been used to determine the dielectric constant and the dielectric loss tangent. The data obtained from pyroelectric and dielectric measurements have been used to calculate the figure of merit for these LB film systems which has a value of 2.56 μC m⁻² K⁻¹.     

聚苯乙炔单分子膜成膜特性研究

研究了聚苯乙炔单分子膜的成膜特性及其结构，结果表明，聚苯乙炔能在较大的表面压范围内形成稳定的单分子膜，并具有不可重复压缩性，表面压力的各向异性和松弛特性，ＴＥＭ照片显示，聚苯乙炔分子链在单分子膜中是有序排列的，转移比和ＸＰＳ研究证明，单分子膜向铝片的沉积是成功的。     

Molecular film technology for biosensors

Two different molecular film technologies have been developed for fabricating biosensors. Firstly, bovine serum albumin spread on the air-water interface was cross-linked and transferred onto the glass surface, on which various molecular assemblies were formed by the bioaffinity technique. Secondly, a protein monolayer was adsorbed from an aqueous phase on the potential-controlled electrode surface, which was followed by electrochemical polymerization and deposition of pyrrole between the protein molecules to make the adsorbed protein film conductive.

A unique optical biosensor for taste has been fabricated by depositing fluorophore-containing Langmuir-Blodgett (LB) films on the glass surface. Each layer of the LB films exhibits its characteristic fluorescence peak which is quenched or enhanced in contact with taste substances. The sensor consisted of three different LB films containing pyrene and anthracene and deposited on a glass plate. Novel performance was demonstrated with the response of the sensor to glutamate and nucleotide umami substances.     

The structure of multilayer films of DNA-aliphatic amine is preparation technique dependent

The structures of DNA-hexadecylamine and DNA-hexadecyltrimethylammonium bromide multilayer films obtained by two different approaches: layer-by-layer (LbL) adsorption and Langmuir–Blodgett (LB) technique were compared. Interlayer distance and DNA conformation in these films were determined by small-angle X-ray scattering, infrared and ultraviolet spectroscopy. The following results were obtained: (1) X-ray diffractrograms of the films indicated a distinct layer structure; (2) the interlayer distances for LbL films were less than for LB-films, made from the same components and (3) the double stranded DNA was included into the DNA-hexadecylamine film as a single-stranded formation, whereas DNA in the DNA-hexadecyltrimethylammonium film retained its double-stranded form. Structural models of LbL and LB films were created.     

25th Anniversary Article: What Can Be Done with the Langmuir‐Blodgett Method? Recent Developments and its Critical Role in Materials Science

The Langmuir‐Blodgett (LB) technique is known as an elegant method for fabrication of well‐defined layered structures with molecular level precision. Since its discovery the LB method has made an indispensable contribution to surface science, physical chemistry, materials chemistry and nanotechnology. However, recent trends in research might suggest the decline of the LB method as alternate methods for film fabrication such as layer‐by‐layer (LbL) assembly have emerged. Is LB film technology obsolete? This review is presented in order to challenge this preposterous question. In this review, we summarize recent research on LB and related methods including (i) advanced design for LB films, (ii) LB film as a medium for supramolecular chemistry, (iii) LB technique for nanofabrication and (iv) LB involving advanced nanomaterials. Finally, a comparison between LB and LbL techniques is made. The latter reveals the crucial role played by LB techniques in basic surface science, current advanced material sciences and nanotechnologies.     

Optical and electrical properties of merocyanine dye LB films by various time of UV irradiation and heat treatment

The Langmuir-Blodgett (LB) technique provides many possibilities for the control of film thickness, dimensions, and molecular structures on the nanometer scale. Various kinds of dye molecules have been found to form the J-aggregation which has been used as sensitizers of silver halide photography for long time. In recent years, they attract attention as model systems for investigating the ultra-fast exciton dynamics, materials for ultra-fast nonlinear optical devices, fluorescence probes for mitochondrial membranes. We fabricated the merocyanine dye LB films with arachidic acid (AA). In order to observe the J-aggregation of the merocyanine dye LB films, CdCl2 and KHCO3 solutions were added in subphase. From the optical absorption spectra of the mixed dye LB films (6Me-Ds:AA = 1:2) at different layers, the optical absorption peak was about 520 nm. However, the optical absorption peak of the LB films was shifted to 600 nm, when CdCl2 and KHCO3 solutions were added. This is the consequence result to the J-aggregation of the merocyanine dye. We also investigated the optical absorption peak of the LB films according to various time at 60 degrees C and 275 nm UV. We measured the STM morphology of the merocyanine dye LB film (1 layer) before UV irradiation and heat treatment. The morphology size of the LB film on HOPG was 5 nm. The roughness and molecular size were about 66.163 pm and 0.176 nm, respectively. The J-aggregation of this type was also accompanied by large morphological changes. We analyze the morphology and electrical properties of the LB films by the scanning tunneling microscopy (STM).     

Development of UV-visible multiple-angle incidence resolution spectrometry and application study of anisotropic surface plasmon excitation in a silver thin film on a glass substrate

Multiple-angle incidence resolution spectrometry (MAIRS) that was originally developed in an infrared region for analysis of molecular orientation in a thin film on a substrate has been extended to develop a novel UV-visible spectrometry. The new technique, named Vis-MAIRS, has been employed for analysis of anisotropic surface plasmon excitation in a silver thin film with a thickness of 5 nm deposited on a glass slide. The Vis-MAIRS spectra yield two spectra at a time, which correspond to absorption spectra whose transition moments are parallel and perpendicular to the film surface. The two spectra of the silver thin film were largely different from each other in shape, which strongly suggested that the silver nanoparticles in the thin film were in an ellipsoidal shape. In addition, absorption due to long-range surface plasmon propagation across the nanoparticles aligned parallel to the film surface, which is a result of the dipole or quadruple couplings of plasmon in each particle, was clearly monitored for the first time in the Vis-MAIRS spectra. In this manner, Vis-MAIRS is expected to be a useful tool to study aggregates of metal nanoparticles in a film.     

Photosensitive polyimide Langmuir-Blodgett films derived from 4-(17-octadecenyl)pyridine and polyamic acid

Thermally stable and photosensitive Langmuir-Blodgett (LB) films have been developed from polyamic acid (PA) and 4-(17-octadecenyl)pyridine (ODP). Fine patterns are easily fabricated with these LB films. From experiments using model compounds it has been found that the double bond in ODP is necessary for a cross- linking reaction to occur. The normalized thickness saturates around 40% for LB films irradiated in air or under flowing nitrogen conditions. It also saturates around 40% for LB films with higher molecular weight PA. By Fourier transform IR spectroscopy and gel permeation chromatography (GPC) measurements it has been found that this saturation is not due to a side reaction of the photosensitive agent nor is it due to main chain polymer degradation. It may be due to a scission between the main chain and the side-chain which contains the photosensitive group. Although the sensitivity has not been improved by using a high molecular weight polymer, it has been found that higher molecular weight polymers have the advantage of uniformity of the film after imidization.     

聚3,4-乙烯二氧噻吩/聚苯乙烯磺酸复合LB膜在OLED器件上的应用

采用Langmuir-Blodgett(LB)膜静电诱导沉积法制备聚3,4-乙烯二氧噻吩(PEDOT)高度有序导电聚合物复合薄膜,研究了薄膜的导电性能并进一步研究薄膜在改善器件性能方面的作用.并将其应用于有机电致发光二极管(OLED)器件的空穴缓冲层,将聚3,4-乙烯二氧噻吩/聚苯乙烯磺酸(PEDOT/PSS)复合LB沉积于纳米铟锡金属氧化物(ITO)电极上,制备了以复合LB膜为空穴缓冲层的OLED器件.发现复合LB膜改善了器件性能(启动电压降低,最大亮度增加),但进一步的研究表明LB膜器件在一定时间后出现性能劣化.I-V特性和X射线反射率(XRR)分析表明,薄膜的结构发生一定程度的改变是导致器件性能变差的可能原因.     

First‐Layer Effect in Graphene‐Enhanced Raman Scattering

Graphene as a substrate for enhancing Raman scattering, called graphene‐enhanced Raman scattering (GERS), has been reported in previous work. Herein, it is found that the “first‐layer effect”, which is widely used to explain the chemical‐enhanced mechanism in surface‐enhanced Raman scattering (SERS), exists in the GERS system. The Langmuir–Blodgett (LB) technique is used to construct mono‐ and multilayer ordered aggregates of protoporphyrin IX (PPP). Raman spectra of PPP with different layer numbers of the LB film on graphene are collected. The Raman signal from the first monolayer LB film of PPP has a larger contribution to the Raman enhancement than that from subsequent monolayers. Meanwhile, the Raman enhancement is dependent on the molecular configuration in contact with graphene, in which the functional group of PPP in direct contact with graphene has a stronger enhancement than other groups. These results reveal that GERS is strongly dependent on the distance between graphene and the molecule, which is convincing evidence that the Raman enhancement effect based on graphene belongs to the chemical‐enhanced mechanism. This discovery provides a convenient system for the study of the chemical‐enhanced mechanism and will benefit further understanding of SERS.     

Luminescence properties of the Langmuir-Blodgett film of terbium(III) stearoylanthranilate

Terbium(III) stearoylanthranilate has been prepared as a high property Z-type Langmuir-Blodgett (LB) film on various substrates by a vertical transfer process. The UV-visible absorption spectra and the low angle X-ray diffraction peaks have been collected in order to investigate the molecular arrangement and aggregation in the LB films. The average molecular orientation in multilayer stacking was determined by Attenuated Total Reflection Spectroscopy. The influence of the chemical environment of terbium within the LB films on the luminescence properties has been discussed.     

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.     

Langmuir-Blodgett films of ethylenedithiotetrathiafulvalene derivative containing hydroxyl groups

Langmuir-Blodgett (LB) films of an ethylenedithiotetrathiafulvalene (EDT-TTF) derivative containing hydroxyl groups, 4, 5-bis(11-hydroxyundecylthio)-4′, 5′-ethylenedithiotetrathiafulvalene were deposited without using stabilizer molecules. Doping of the film with iodine leads to oxidation of EDT-TTF moiety as evidenced by UV-vis and IR spectroscopy. X-ray diffraction studies reveal the presence of layered arrangement of the EDT-TTF derivative molecules in the LB film. Cyclic voltammetry studies indicate that the electrochemical oxidation of the EDT-TTF derivative in its LB film is irreversible. Due to the insulating nature of the alkyl chains, only the first layer of the LB film was found to be redox-active. The electrical conductivity of the 25 layer LB film was found to increase by two orders of magnitude on doping with iodine. On equilibrating the doped film in air, the conductivity gradually reduced with time and finally reached the conductivity of undoped film. This reversibility could be because of the steric hindrance induced by the two long alkyl groups. The alkyl chains help in rendering the EDT-TTF molecule amiable to LB film formation but are found to reduce the electrical conductivity of the films and also cause instability of the doped state. The hydroxyl groups at the end of the alky chain impart amphiphilic nature to the molecules and help in stabilizing the film at the air-water interface.     

Optimum condition of Fourier transform infrared multiple-angle incidence resolution spectrometry for surface analysis

A novel measurement technique of pure out-of-plane vibrational modes of thin films on a nonmetallic substrate has recently been proposed, which is named multiple-angle incidence resolution spectrometry (MAIRS). Since this technique could not be replaced by other conventional techniques, MAIRS was expected to be a promising tool for analysis of thin soft materials and surface adsorbates. Nevertheless, some experimental conditions have been found to be inappropriate for MAIRS, which yields incorrect results. In the present study, therefore, the problems in the technique have been investigated in terms of optics to improve the accomplishments of MAIRS. The problems have been found to have a strong relationship with optics in FT-IR, which is influenced by refractive index of the sample material and angle of incidence. In particular, optimization of the size matching of the detector surface and the infrared spot at the detector was a key to having MAIRS perform properly. It has been concluded that reliable MAIRS measurements require overfilling of the detector and a substrate with a high-refractive index.