Large organized surface domains self-assembled from nonpolar amphiphiles

For years, researchers had presumed that Langmuir monolayers of small C(n)F(2n+1)C(m)H(2m+1) (FnHm) diblock molecules (such as F8H16) consisted of continuous, featureless films. Recently we have discovered that they instead form ordered arrays of unusually large (~30-60 nm), discrete self-assembled surface domains or hemimicelles both at the surface of water and on solid substrates. These surface micelles differ in several essential ways from all previously reported or predicted molecular surface aggregates. They self-assemble spontaneously, even at zero surface pressure, depending solely on a critical surface concentration. They are very large (~100 times the length of the diblock) and involve thousands of molecules (orders of magnitude more than classical micelles). At the same time, the surface micelles are highly monodisperse and self-organize in close-packed hexagonal patterns (two-dimensional crystals). Their size is essentially independent from pressure, and they do not coalesce and are unexpectedly sturdy for soft matter (persisting even beyond surface film collapse). We and other researchers have observed large surface micelles for numerous diblocks, using Langmuir-Blodgett (LB) transfer, spin-coating and dip-coating techniques, or expulsion from mixed monolayers, and on diverse supports, establishing that hemimicelle formation and ordering are intrinsic properties of (perfluoroalkyl)alkanes. Notably, they involve "incomplete" surfactants with limited amphiphilic character, which further illustrates the outstanding capacity for perfluoroalkyl chains to promote self-assembly and interfacial film structuring. Using X-ray reflectivity, we determined a perfluoroalkyl-chain-up orientation. Theoretical investigations assigned self-assembly and hemimicelle stability to electrostatic dipole-dipole interactions at the interface between Fn- and Hm-sublayers. Grazing-incidence small-angle X-ray scattering (GISAXS) data collected directly on the surface of water unambiguously demonstrated the presence of surface micelles in monolayers of diblocks prior to LB transfer for atomic force microscopy imaging. We characterized an almost perfect two-dimensional crystal, with 12 assignable diffraction peaks, which established that self-assembly and regular nanopatterning were not caused by transfer or induced by the solid support. These experiments also provide the first direct identification of surface micelles on water, and the first identification of such large-size domains using GISAXS. Revisiting Langmuir film compression behavior after we realized that it actually was a compression of nanometric objects led to further unanticipated observations. These films could be compressed far beyond the documented film "collapse", eventually leading to the buildup of two superimposed, less-organized bilayers of diblocks on top of the initially formed monolayer of hemimicelles. Remarkably, the latter withstood the final, irreversible collapse of the composite films. "Gemini" tetrablocks, di(FnHm), with two Fn-chains and two Hm-chains, provided two superposed layers of discrete micelles, apparently the first example of thin films made of stacked discrete self-assembled nanoobjects. Decoration of solid surfaces with domains of predetermined size of these small "nonpolar" molecules is straightforward. Initial examples of applications include deposition of metal dots and catalytic oxidation of CO, and nanopatterning of SiO(2) films.     

Electrochemical and photoelectrochemical response of electrodes coated with LB films of an azopolymer

This paper describes the electrochemical and photoelectrochemical behaviour of electrodes coated with Langmuir-Blodgett (LB) films of an azopolymer. The coating material used is a pyridine azopolymer (PAzPy) obtained by free radical polymerization of 6-[2-(4-pyridyazo)phenoxy]hexyl methacrylate (AzPy). Cyclic voltammetry experiments of LB films deposited at several transference surface pressures were performed to analyze the effect of the molecular packing on the electrochemical response. The influence of the pH of the electrolytic solution was also considered. AFM images have helped in the interpretation of the molecular architecture influence on the redox activity of the films. From the experimental results it was concluded that PAzPy is situated with the nitrogen from the pyridine group close to the ITO electrode surface in the LB films, which allows a direct electron transfer between the electrode surface and the azobenzene group leading to a quick electrochemical response of the films. The azobenzene electrochemical activity and the kinetics of the process are also highly dependent on the proton transfer process between the electrolytic solution and the azobenzene unit. The efficiency of the proton transfer process is determined by the pH of the electrolytic solution as well as by the molecular architecture of the film. The results presented in this paper show that, under optimal conditions, both the percentage of electroactive azobenzene chromophores and the standard heterogeneous rate constant of electron transfer are higher for PAzPy arranged in LB films compared with the values so far reported for azobenzenes of lower molecular weight.     

Structure and imidization of polyamic acid salt Langmuir–Blodgett films

Polyimide Langmuir‐Blodgett (LB) films were prepared with a Pyromellitic dianhydride‐4, 4′ oxydianiline precursor, and the properties of the polyamic acid salt monolayer characterized by different methods. The π‐A relationship revealed that the precursor monolayer exhibits anisotropy on the water surface, the Wilhelmy plate being more sensitive to pressure when it is perpendicular to the compression direction. FTIR results showed that polyamic acid salt LB films have lower imidization energy than the corresponding painting films and can be imidized at lower temperature. The molecular arrangement in the LB films was studied by X‐ray diffraction and polarized FTIR, showing that the polyamic acid salt LB film is of Y‐type, in which the molecules are highly oriented, with the main chain lying parallel to the substrate and the long fatty acid chains stretching out at a certain angle. © 2002 Society of Chemical Industry     

Control of polymerization processes of 10,12-pentacosadiynoic acid LB films

Studies have been carried out on KrF excimer laser light (EX), X-ray or electron beam (EB) induced polymerization of 10,12-pentacosadiynoic acid (PDA) Langmuir-Blodgett (LB) films in relation to molecular density or molecular arrangement of the films using X-ray diffraction analysis, infrared (IR) spectroscopy and Raman spectroscopy. The molecular arrangement or density of the PDA LB films was controlled by subphase conditions when the films were built up, such as pH, temperature of a subphase or salt concentration in the subphase. Polymerization sensitivity of the PDA LB film was affected by the arrangement or molecular density. On low density (A type) films the polymerization occurred by irradiation with EX, X-ray or EB, but on high density (B type) films the polymerization occurred only when the irradiation was carried out by high energy beams such as X-ray or EB. Decomposition of polymerized films was observed further by excessive irradiation of EX or X-ray, but not on the B type films. It was revealed by X-ray diffraction analysis that in the A type film, the PDA molecules bent to a larger extent than those in the B type film and the polymerization proceeded topochemically, that is, the thickness decreased little after EB irradiation in a helium atmosphere. On the other hand, in the B type film, the thickness decreased by about 10% as a result of EB irradiation. By IR reflection-absorption (RA) and Raman measurements, it was confirmed that conjugated diacetylenic bonds disappeared and conjugated double and new conjugated triple bonds appeared after high energy beam irradiations. These results support the supposition that 1,4-polymerization, i.e. polydiacetylene type polymerization, occurs easily in the A type film and 1,2- or 3,4-polymerization, i.e. polyacetylene type polymerization, occurs in the B type film, and that the polymerized A type film was decomposed at the polydiacetylenic bond when the irradiation continued further. It was also shown that the polyacetylene type polymer was obtained only when the B type film was irradiated with the high energy beam.     

Effect of spreading solvents on Langmuir monolayers and Langmuir–Blodgett films of PS-b-P2VP

Langmuir monolayers of polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) diblock copolymers (with the same PS block length and different P2VP block lengths) formed at the air/water interface were characterized with the Langmuir film balance technique. Nonselective and selective solvents were used to spread the samples on the water surface and the spreading solvents showed large effect on the surface pressure–molecular area isotherms. The corresponding Langmuir–Blodgett (LB) films of the samples were characterized with atomic force microscopy. The LB films transferred from the Langmuir monolayers spread with a nonselective solvent only exhibited isolated circular micelles, while those with a selective solvent exhibited quite different morphologies including planar structure, rodlike structure, circular micelles, and labyrinth pattern. As far as we know, the labyrinth pattern appears in the LB films for the first time.     

Electrical and electroluminescent properties of poly(p-phenylene vinylene) LB films based LEDs using aluminum metal as the electrode

The electrical properties of poly(p-phenylene vinylene) (PPV) Langmuir-Blodgett (LB) films were investigated, wherein transparent indium-tin oxide (ITO) and aluminum (Al) were used as the electrodes. Their I–V characteristics depended strongly on the thickness of PPV LB film, and the electric conductivity of the PPV LB film was in the range of 10⁻²–10⁻¹⁵ (S/cm). Their C–V characteristics showed that the capacitance was reversibly proportional to the thickness of PPV LB film and was kept constant when the applied voltage changed from −1.0 V to +1.0 V. These results indicated that PPV LB film was an insulator in this range of applied voltage without doping. Under forward bias, yellow-green light emission was observed in PPV LB film based light emitting diodes (LEDs), the highest light emission reached more than 100 cd/m² in the case that PPV LB film was deposited for 80 layers, i.e. a ITO/PPV(80L)/Al device.     

Formation and structure of organized molecular films for organo‐modified montmorillonite and mixed monolayer behavior with poly(L‐lactide)

We investigated the molecular orientation and surface morphology of organized molecular films with regard to solid‐state structures for organo‐modified montmorillonites by surface pressure‐area (π ? A) isotherm, in‐plane and out‐of plane X‐ray diffraction (XRD), and atomic force microscopy (AFM). From the results of out‐of plane XRD, formation of highly ordered layer structure was confirmed in these clay Langmuir‐Blodgett (LB) film. Further, two‐dimensional lattice of long alkyl chain of organo‐modified parts packed hexagonally or orthorhombically in the films. Surface morphology of Z‐type monolayers on solid of organo‐modified montmorillonites indicates heterogeneous modification ratio in montmorillonite surface by AFM observation. In addition, monolayer behavior on the water surface and mesoscopic morphological formation on solid of mixed films of organo‐modified montmorillonite and poly‐(L ‐lactide) (PLLA) were investigated by π ? A isotherm and AFM. Collapsed surface pressures are independent on the mixed ratio, and indicate almost constant value in their isotherms. This tendency is a peculiarity of immiscible system. From the result of AFM observation, phase separated structure was confirmed in mesoscopic scales. This phase separated morphology remarkably varied with mixed ratio. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Long-Range Interactions in Thin Smectic Films on Substrates: X-Ray Reflectivity Studies

Long-range forces between interfaces of thin and ultrathin smectic films are responsible for their thickness and stability. We present here X-ray reflectivity studies of the forces in spin-coated thin films of three different commercial liquid crystal (LC) mixtures as well as in main-chain LC polymers based on polysiloxane. All these LC materials possess a smectic C* phase at room temperature. We demonstrate spontaneous molecular self-assembly after spin coating into a nearly perfect smectic layer structure on various substrates. However, annealing at room temperature is essential to achieve an equilibrium state. Measurements on ultrathin annealed films of the LC mixtures show dramatic variation of the smectic layer spacing, L, as a function of the number of smectic layers, n (or film thickness, d). The functional dependence of L(n) for all three different liquid crystal mixtures suggests a long-range interaction between the interfaces that decays algebraically as 1/n^κ where κ = 2 ± 0.3. This decay is consistent with a van der Waals type of interaction, although its magnitude cannot be explained by the existing mechanisms. X-ray studies of thick and thin annealed polysiloxane films allow determination of the phases, the phase transition temperatures, and the temperature dependence of the tilt angle in the smectic C* phase. Thin (300 Å to 600 Å) polysiloxane films far above the bulk smectic–isotropic phase transition temperature show the formation of smectic film at the film–substrate interface due to surface freezing phenomena. Preliminary investigations of the temperature dependence of the smectic film thickness indicate that the interaction between the interfaces decays algebraically, with an exponent κ = 1.5 ± 0.5.     

Wettability of fibrous quartz with Langmuir-Blodgett films of arachidic acid and/or cellulose didecanoate

The wettability of quartz with Langmuir-Blodgett (LB) films of arachidic acid (AA) and/or cellulose didecanoate (CDD) was investigated by contact angle measurements, employing the Wilhelmy method. The advancing angles increased considerably with the film deposition, especially for the AA films, whereas the receding angles increased only slightly. A further increase in the advancing angles with time was found after the film deposition. The experimental results are discussed considering the quartz with the LB films to have a heterogeneous surface, i.e. predominantly high-energy surface with fractional low-energy regions. The increment in the advancing contact angle due to film deposition is explained by the increase in the percentage of the low-energy region. The time dependence of the advancing angle after the film deposition is considered to be caused by the increase in the difference in the intrinsic wettability between the low-energy and high-energy regions due to rearrangement of the molecules in the LB films and the migration of the AA molecules towards the air.     

Monolayer Packing of Submicrometer Ceramic Spheres by Employing a Langmuir–Blodgett Film of Dicarboxylic Acid

A closely packed monolayer of spherical SiO₂ or SiO₂–TiO₂ particles of submicrometer size has been fabricated on a silicon or glass substrate by employing a Langmuir–Blodgett (LB) film of 1,12-dodecanedicarboxylic acid, followed by dehydration–condensation reaction between carboxyl groups of the dicarboxylic acid and surface hydroxyl groups of both the substrate and the ceramic spheres. Deposition of the LB film on the substrate was essential for immobilization of ceramic spheres. The flexibility of an alkyl chain in the dicarboxylic acid may have resulted in better capturing of ceramic spheres compared with surface hydroxyl groups on the substrate. Two-dimensional packing of the ceramic spheres immobilized became dense with decreasing molecular area of the dicarboxylic acid in the LB film and the temperature of the LB medium (water), although partial three-dimensional attachment of ceramic spheres was observed, especially when an LB film of quite small molecular area was used. In addition, the amount of surface hydroxyl groups on the substrate was found to significantly affect the microstructure of the two-dimensionally packed ceramic spheres. The closest two-dimensional packing was observed on a glass substrate by employing an LB film with a molecular area of 0.03 nm²·molecule⁻¹ at 20°C.     

新型两亲性酞菁锌LB膜的研究

本文合成了一种新型的两亲性酞菁分子，研究了它在不同溶剂中的聚集行为，考察了酞菁及酞菁与正十六烷混俣的成膜性能，制备了混合的多层ＬＢ膜，并利用紫外光谱研究ＬＢ膜内的分子聚集状况，用分子激子理论对实验结果和以分析，还应用偏振紫外的方法对ＬＢ膜内酞菁分子大环的取向进行了研究。     

Photo-reversible Reaction in Polymer Langmuir-Blodgett Films

Preparation of photoreactive Langmuir-Blodgett (LB) films was carried out using polymers/oligomers prepared from long-chain dialkyl esters of di-and tetra-olefins and having cyclobutane rings in the main chain. These polymers/oligomers formed stable monolayers on a water surface when mixed with arachidic acid. These monolayers could be deposited onto a substrate successfully forming Y-type films. The oligomer LB films were polymerized on irradiation. The polymer LB films showed a photo-reversible process between polymers and oligomers, depending on wavelength of the irradiating light. On the basis of spectral data and molecular weight change, this behaviour was found to be caused by cleavage and formation of cyclobutane rings.     

Langmuir and Langmuir–Blodgett films of low‐bandgap polymers

Low‐bandgap conjugated polymers have provided a considerable increase in organic photovoltaic efficiencies, however, an understanding of class‐specific nanostructures, necessary to further improve device qualities, remains scarce. Their self‐assembly and associated electronic behaviors in Langmuir?Blodgett (LB) films are used here to provide relationships specific to each polymer, clarifying their structure?property characteristics. The behavior of two low‐bandgap polymers based on cyclopentadithiophene (PCPDTBT) and dithienosilole (Si‐PCPDTBT) units in the Langmuir trough were investigated and it is shown that it is possible to fabricate nanostructured films of low‐bandgap polymers on solid substrates with the LB deposition technique. The polymers were mixed with amphiphilic molecules at well‐defined concentrations to improve the formation of the LB films. The polymers were also deposited by drop‐casting and LB techniques onto interdigitated electrodes to evaluate their electrical properties, and the LB films were characterized for their optical and morphological properties. It was found that both LB and drop‐cast films of PCPDTBT showed higher electrical conductivities than those of Si‐PCPDTBT. Importantly, LB films resulted in higher electrical conductivities – by an order of magnitude ? compared to their equivalent mixtures with stearic acid in drop‐cast films, although drop‐cast films without stearic acid gave higher conductivities. This fine‐tuning of the molecular architectures of the films is thus demonstrated to directly affect the physical properties and may lead to an improvement in device efficiencies in future applications. © 2018 Society of Chemical Industry     

Langmuir and Langmuir-Blodgett Films of Polyfluorenes and Their Use in Polymer Light-Emitting Diodes

The Langmuir and Langmuir-Blodgett (LB) film properties of two polyfluorene derivatives, namely poly(2,7-9,9′-dihexylfluorene-dyil) (PDHF) and poly(9,9 dihexylfluorene-dyil-vynilene-alt-1,4-phenylene-vyninele) (PDHF-PV), are reported. Surface pressure (П-A) and surface potential (ΔV-A) isotherms indicated that PDHF-PV forms true monolayers at the air/water interface, but PDHF does not. LB films could be transferred onto various types of substrate for both PDHF and PDHF-PV. Only the LB films from PDHF-PV could withstand deposition of a layer of evaporated metal to form a light-emitting diode (PLED), which had typical rectifying characteristics and emitted blue light. It is inferred that the ability of the polymer to form true monomolecular layers at the air/water interface seems to be associated with the viability of the LB films in PLEDs.     

Ultra Thin Organic and Polymer Films

Abstract

Preparation of ultra thin organic and polymer films could be divided into two methods. One is the wet process such as Langmuir-Blodgett (LB), spreading, dipping and casting methods. The other is dry processing, such as vapor deposition, sputtering, chemical vapor deposition, plasma polymerization and vapor deposition polymerization methods. Of these methods, the LB method has been attractive for the last decade to prepare a monolayer film, however, the vapor deposition method has also attracted attention for the preparation of well organized ultra thin films. It is important to investigate a molecular assembly in terms of the extent of aggregation, the crystalline regularity and their orientation in the thin film, since they are closely related to the physical, electrical and functional properties. This review focuses on an evaluation of the structure, molecular assembly and orientation in the thin films prepared by the LB and vapor deposition methods.     

Studies on the release of polymeric Langmuir-Blodgett multilayers from the solid supports on which they were prepared

It has been shown that polymeric Langmuir-Blodgett (LB) multilayers may be released from the supports on which they were prepared by first thermally evaporating thin films of stearic acid onto the support. The acid can subsequently be washed away, so undercutting the film and releasing it to float to the water surface. The films were redeposited onto fresh silicon wafers or onto glass microscope slides. Under the optical microscope, the films on the glass microscope slides were clear and featureless. By XRD the transferred films had the same or fewer orders of Bragg peaks and the corresponding bilayer spacings were the same or slightly larger than those of the original films. Thus, it appears that most films lose a small amount of their order in the transfer process. By second harmonic generation (SHG) the transferred alternating LB films formed from a poly(4-vinylpyridine) partially quaternised by reaction with n-docosyl bromide and from the poly(4-vinylpyridinium bromide) formed by the zwitterionic polymerisation of 4-vinylpyridine with 4(12-bromododecyloxy)-4′-trifluoromethylazobenzene displayed essentially the same SHG properties as the original films. Moreover, the SHG films could be stacked successfully to give thicker films. Several of the transferred films, but not all, contained traces of stearic acid, which appears to be present as small domains of Y-type layers. In one typical case, where the LB film consisted of 100 layers of a poly(4-vinylpyridine), it was shown that the amount of stearic acid present corresponded to an average of one monolayer.     

Langmuir and Langmuir-Blodgett (LB) films of poly[(2-methoxy,5-n-octadecyl)-p-phenylenevinylene] (OC1OC18-PPV)

A PPV derivative, poly(2-methoxy,5-(n-octadecyl)-p-phenylenevinylene) (OC₁OC₁₈-PPV), has been synthesized via the Gilch route and used to fabricate Langmuir and Langmuir-Blodgett (LB) films. True monomolecular films were formed at the air/water interface, which were successfully transferred onto different types of substrate. Using UV-visible absorption, FTIR, fluorescence and Raman scattering spectroscopies we observed that the polymer molecules were randomly distributed in the LB film, with no detectable anisotropy. This is in contrast to the anisotropic LB films of a previously reported PPV derivative, poly(2-methoxy-5-n-hexyloxy)-p-phenylenevinylene (OC₁OC₆-PPV), which is surprising because the longer chain of OC₁OC₁₈-PPV investigated here was expected to lead to more ordered films. As a consequence of the lack of order, LB films of OC₁OC₁₈-PPV exhibit lower photoconductivity and require higher operating voltage in a polymer light-emitting diode (PLED) in comparison with LB films of OC₁OC₆-PPV. This result confirms the importance of molecular organization in the LB film to obtain efficient PLEDs.     

Preparation of TiO2 thin films using octadecylamine Langmuir-Blodgett films and evaluation of their photocatalytic activity

A study was conducted to demonstrate that nanometer-thick titanium dioxide (TiO(2)) thin films could be prepared by the hydrolysis of titanium potassium oxalate using octadecylamine (ODA) Langmuir-Blodgett (LB) films as templates. The amount of TiO(2) generated in the LB film was found to be proportional to the number of deposited ODA layers, which enables precise control of the TiO(2) film thickness. After heat treatment of the LB films at 300-600°C, the photocatalytic activities of the resulting TiO(2) films were determined from the decomposition of stearic acid cast films when irradiated with UV light for different time periods. Higher photocatalytic activity was observed in TiO(2) films heat treated at lower temperatures.     

LB膜技术的应用研究进展

LB膜技术是在分子水平上制备有序分子超薄膜的先进技术。对LB膜技术的研究和应用进行了综述，介绍了目前LB技术在实现超微细粒子的二维有序组装，在光学，电化学器件和气体传感器中的应用以及通过LB膜技术组装生物仿生膜等方面的最新研究成果。     

Generation of disk-like domains with nanometer scale thickness in merocyanine dye LB film induced by hydrothermal treatment

We have characterized the binary LB films of merocyanine dye (MS) and arachidic acid (C₂₀) before and after hydrothermal treatment (HTT), which is defined as a heat treatment under relative humidity of 100%, focusing on the morphology studied by bright field (BF) microscopy and fluorescence (FL) microscopy. BF microscopy observation has revealed that the as-deposited MS-C₂₀ binary LB film is found to emit intense red fluorescence over the whole film area by 540-nm excitation. Since the surface image is almost featureless, it is considered that the crystallite sizes of J-aggregate are less than 10 μm. Interestingly, after HTT, round-shaped domains are observed in the LB systems, and the sizes are reaching 100 μm in diameter. Crystallites of J-aggregate, which are bluish in color and emit intense red fluorescence, tend to be in the round domains. We have observed two different types of domains, i.e., blue-rimmed domains and white-rimmed domains, which are postulated to be confined in the inner layers and located at the outermost layer, respectively. The thickness of the domains is equal to or less than that of the double layer of the MS-C₂₀ mixed LB film, which is ca. 5.52 nm. The molecular order of MS in the J-aggregate is improved by the HTT process leading to the significant sharpening of the band shape together with the further red shift of the band (from 590 to 594 nm up to 597 to 599 nm). The reorganized J-band is considered to be ‘apparently’ isotropic owing to the random growth of the J-aggregate in the film plane. We consider that the lubrication effect by the presence of water molecules predominates in the HTT process.