Orientation control of ferroelectric polymer molecules using contact-mode AFM

We have developed an orientation control technique for polymer molecules utilizing contact-mode atomic force microscopy (AFM). In this technique, the molecular chains were directly modified by scanning an AFM cantilever tip in contact with the film surface at the temperature just below its melting point. We call this process “modification scan”. Here, we applied this technique to poly(vinylidenefluoride-trifluoroethylene) (P(VDF-TrFE)) thin films on graphite and glass. We prepared a 75-nm thick copolymer crystalline film on graphite whose lamellar plane was perpendicular to the substrate (edge-on), and also prepared a film of the same thickness on glass whose lamellar plane was parallel to the substrate (flat-on). After applying this technique on both films, molecular chains were stretched and aligned to the modification scan direction, and new edge-on crystals were obtained, whose lamellar planes were well-aligned perpendicular to the modification scan direction.     

Model experiments for a molecular understanding of polymer crystallization

Time‐resolved real‐space observations of morphology and pattern formation resulting from crystallization of ultrathin films of low‐molecular‐weight poly(ethylene oxide) (PEO) or diblock copolymers containing PEO shed light on the mechanisms of how polymer crystals are formed. We used simple but restricted geometries like thin films of controlled thickness or confinement resulting from block copolymer mesotructures. Under such conditions, we were able to relate the observed morphology and its temporal evolution directly to molecular processes and the kinetics of crystal growth. We demonstrate that changes in the morphology with time are due to different thermal histories and are the consequence of the mestable nature of polymer crystals. Information about the nucleation process was obtained by examining crystal formation in 12‐nm small spherical cells of a block copolymer mesostructure. We discuss the advantages of thin‐film studies for a better understanding of polymer crystallization. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1869–1877, 2003     

Dewetting Behavior of Random Copolymer Films Induced by Solvent Vapor Annealing

In recent years, the dewetting behavior of block copolymer films has been studied a lot, but that of random copolymer films was rarely studied. In this study, effects of film thickness and solvent vapor annealing duration (0 s–24 h) on the dewetting behavior of the spin-coated poly(styrene-co-acrylonitrile) (SAN) random copolymer films were mainly investigated by atomic force microscopy and contact angle method for the first time. The film thicknesses of the SAN films prepared at different concentrations were characterized by X-ray reflectometry to be 6–34 nm. With the annealing of acetone vapor, the SAN films first appear holes and then rupture into droplets which fuse and break periodically. The periodic evolutions of the droplets are due to the preferred affinity of acetone molecules with the AN segments and the change of surface energy. This phenomenon is different from the single evolutions in the spin-coated polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) block copolymer films. This illustrates the interactions between AN segments and the substrate are stronger than those between PMMA segments and the substrate in the spin-coated films.     

Comparative characterisation by atomic force microscopy and ellipsometry of soft and solid thin films

Ellipsometry and atomic force microscopy (AFM) were used to study the film thickness and the surface roughness of both ‘soft’ and solid thin films. ‘Soft’ polymer thin films of polystyrene and poly(styrene–ethylene/butylene–styrene) block copolymer were prepared by spin‐coating onto planar silicon wafers. Ellipsometric parameters were fitted by the Cauchy approach using a two‐layer model with planar boundaries between the layers. The smooth surfaces of the prepared polymer films were confirmed by AFM. There is good agreement between AFM and ellipsometry in the 80–130 nm thickness range. Semiconductor surfaces (Si) obtained by anisotropic chemical etching were investigated as an example of a randomly rough surface. To define roughness parameters by ellipsometry, the top rough layers were treated as thin films according to the Bruggeman effective medium approximation (BEMA). Surface roughness values measured by AFM and ellipsometry show the same tendency of increasing roughness with increased etching time, although AFM results depend on the used window size. The combined use of both methods appears to offer the most comprehensive route to quantitative surface roughness characterisation of solid films. Copyright © 2007 John Wiley & Sons, Ltd.     

Ultrathin Films of Porous Metal–Organic Polyhedra for Gas Separation

Ultrathin films of a robust Rh^II-based porous metal–organic polyhedra (MOP) have been obtained. Homogeneous and compact monolayer films (ca. 2.5 nm thick) were first formed at the air–water interface, deposited onto different substrates and characterized using spectroscopic methods, scanning transmission electron microscopy and atomic force microscopy. As a proof of concept, the gas separation performance of MOP-supported membranes has also been evaluated. Selective MOP ultrathin films (thickness ca. 60 nm) exhibit remarkable CO₂ permeance and CO₂/N₂ selectivity, demonstrating the great combined potential of MOP and Langmuir-based techniques in separation technologies.     

聚苯乙烯/聚二甲基硅氧烷嵌段共聚物的表面形态研究

采用原子力显微镜(AFM)和透射电镜(TEM)研究了聚苯乙烯/聚二甲基硅氧烷嵌段共聚物(PS-b-PDMS)薄膜的相形态.结果表明,当采用甲苯作为溶剂,旋转涂膜的薄膜样品呈现网络状的形态分布在表面,而样品所对应的透射电镜照片中,PDMS相作为球状分布在PS的连续相中.退火温度对共聚物表面形态有一定的影响,当退火温度高于PDMS的玻璃化温度,表面中PDMS相增多.PS-b-PDMS嵌段共聚物的表面形态随着所用溶剂的变化而有所不同,当采用甲苯作为溶剂时,样品的PS相形成凹坑分布在PDMS的相区之中,而采用环己烷作为溶剂时,PS相作为突起分布在PDMS相区之中.另外,基底对共聚物薄膜表面形态的有较大的影响,当采用硅晶片作为基底时,样品中的PDMS相和PS相呈现近似平行于表面的层状结构.     

Entanglement of polymer chains in ultrathin films

This investigation aimed to clarify the issue of whether polymer chains are entangled in ultrathin films spin-coated onto substrates. This was done using a fluorescence probe method to observe the behavior of two types of poly(methyl methacrylate) (PMMA), one having a carbazolyl (Cz) moiety (PMMA-Cz) and the other having an anthryl (At) moiety (PMMA-At). In both cases, the moiety fraction was 1 unit for 400 units of polymer. We prepared ultrathin films (thickness: 4-88 nm) on quartz substrates from PMMA-Cz, PMMA-At, and a mixture of the two using a spin-coating method. When the PMMA films prepared from the mixture of the two PMMAs were excited at 292 nm, which is preferentially absorbed by Cz rather than At, the Cz fluorescence was found to be quenched dramatically while the At fluorescence increased significantly. This effect is due to the proximity of the Cz to the At, which permits the transfer of excitation energy between them. The average distance between Cz and At can be calculated using the F?rster mechanism. When the ultrathin film thickness was between 12 and 88 nm, the average distance was found to be 2 nm. This is much shorter than the radii of gyration of the polymers. From this it is clear that two polymer molecules in an ultrathin film do experience entanglement, as has been hypothesized. Thus, we conclude that the difference between certain properties of ultrathin films and the properties of the same materials in bulk are not induced by a decrease in the level of polymer chain entanglement.     

Stability and disintegration of ultrathin heptane films in water: molecular dynamics simulations

Molecular dynamics simulations of ultrathin heptane films (less than 5 nm in thickness) in water were conducted to study their stability and disintegration behavior. The density distributions of heptane and water molecules across the film were determined for different equilibrium film thicknesses ranging from 1.5 to 4 nm. The potential energy of the system was computed as a function of the heptane number fraction, and the results were employed to determine the excess energy of mixing of heptane in water. The diffusion coefficients of heptane and water obtained from the MD simulations were also compared with experimental data. A good agreement was found between the heptane self-diffusivity obtained from the MD simulations and its literature reported value. Following an analysis of the equilibrium properties of the heptane films and associated structures, we performed simulations where the shapes of the heptane films were initially perturbed. Different perturbations of these ultrathin films led to formation of various associated structures, including cylindrical rodlike heptane droplets, films with holes, and intact films. The different shapes are formed in systems with the same heptane/water composition. An analysis of this behavior is presented showing the possibility of multiple associated structures with similar total energy in these highly confined systems.     

Surface force spectroscopy of elastomeric nanoscale films

We studied nanomechanical properties for a series of ultrathin films of elastomeric materials from polyisoprene rubbers and tri‐block styrene‐butadiene‐styrene copolymer, SEBS. As we observed, the Hertzian approximation for elastic mechanical deformation of double layer films can be used for the analysis of force‐distance data at modest indentation depths and film thickness higher than 3 nm. For thinner films, the influence of solid substrate becomes very significant. On the other hand, the applicability of the Hertzian approximation is limited by the rate dependent elastomeric deformation. We demonstrated that Johnson modification of the contact mechanics model that includes a viscoelastic contribution could be utilized to obtain reasonable fitting of loading data for elastomeric materials.     

Characterization of Ultrathin Films of Cellulose Esters

The adsorption of cellulose acetate (CA), cellulose acetate propionate (CAP) and cellulose acetate butyrate (CAB) from solutions prepared in acetone onto silicon wafers led to ultrathin films, which were characterized by ellipsometry, atomic force microscopy (AFM) and contact angle measurements. The polysaccharides films were characterized in the air just after their formation and after annealing at temperatures higher than their glass transition temperature or melt temperature. The films thickness close to 2 nm and surface roughness did not vary significantly upon annealing. AFM images revealed the presence of small clumps dispersed on a homogeneous layer, which covered completely the Si wafers. Such topographic details were also observed after annealing. However, upon annealing the films surfaces changed from hydrophilic to hydrophobic, evidencing molecular re-orientation at the solid–air interface. The adhesion of bovine serum albumin (BSA) and lipase onto the cellulose esters films was quantified in order to evaluate the possibility of applying such films as selective support for biomolecules.     

Strain‐Induced Phase Morphology in Melt Drawn Ultrathin Highly Oriented Block Copolymer Films

A strain‐induced microphase morphology has been established by the melt drawing process in a high molecular weight asymmetric polystyrene‐block‐poly(vinyl‐2‐pyridine) (PS‐b‐P2VP) diblock copolymer. For the first time to the best knowledge of the authors, the melt drawing process has been applied to block copolymers to produce free‐standing, ultrathin block copolymer films with a thickness of ≈100 nm. Intriguingly, during the melt drawing of the polymer a global strain‐induced unidirectional order of the microphase separated needle‐like domains of the block copolymer was generated. This morphology consists of a PS matrix with embedded highly oriented P2VP needle‐like domains oriented parallel to the drawing direction. The needle‐like morphology is explained by a simplified extended chain model of the diblock copolymer chains. Annealing of the films leads to a transition from the strain‐induced needle‐like morphology toward the quasi‐equilibrium sphere‐like morphology.

     

Stimuli-responsive properties of N-isopropylacrylamide-based ultrathin hydrogel films prepared by photo-cross-linking

To develop stimuli-responsive ultrathin polymer films on a solid substrate, a novel photo-cross-linkable polymer with both temperature- and pH-responsive properties was prepared. The photoreactive 4-aminobenzophenone (BP) was introduced onto the side groups of poly(N-isopropylaclylamide-co-2-carboxyisopropylaclylamide) [poly(NIPAAm-co-CIPAAm)]. This copolymer was designed for highly random sequences of comonomers. After the formation of spin-coated polymer films on a solid substrate, UV-light irradiation started the cross-linking reaction. The spin-coating processes and stability of the polymer films were quantitatively monitored by a quartz crystal microbalance (QCM), and the thickness was estimated using an atomic force microscope (AFM). These measurements confirmed the formation of a very plain polymer film, and the film thickness was precisely controlled by the concentration of the polymer solution used for spin coating. Moreover, the obtained films showed a high stability due to the cross-liking reaction and UV irradiation. Cyclic voltammetry using potassium ferricyanide revealed that the ions could permeate the photo-cross-linked ultrathin polymer films. The permeability of the ultrathin hydrogel films was dramatically changed by varying the pH and temperature of the aqueous media. These observations suggest that the preparation of isopropylacrylamide-based stimuli-responsive ultrathin hydrogel films is possible.     

Facile measurement of polymer film thickness ranging from nanometer to micrometer scale using atomic force microscopy

As many properties of polymer thin films critically depend on their thickness, a convenient and cost‐effective method for precise measurement of film thickness in a wide range is highly desirable. Here, we present a method which enables polymer film thickness, ranging from nanometer to micrometer scale, to be facilely determined by measuring the height of an artificially created film step on smooth substrates with atomic force microscopy (AFM). Three polymeric films (polystyrene, poly(methyl methacrylate) and poly(styrene–ethylene/butylene–styrene) films), spin‐coated on either mica or quartz substrate with thickness ranging from 5.7 nm to 4.4 µm, were employed to demonstrate the procedure and feasibility of our method. The proposed method is particularly suitable for thicker polymer films, thus complementing the traditional AFM ‘tip‐scratch’ method which is generally limited to polymer films of no more than 100 nm thickness. Copyright © 2010 John Wiley & Sons, Ltd.     

Modification of indium-tin oxide electrodes with thiophene copolymer thin films: optimizing electron transfer to solution probe molecules

We describe the modification of indium-tin oxide (ITO) electrodes via the chemisorption and electropolymerization of 6-{2,3-dihydrothieno[3,4-b]-1.4-dioxyn-2-yl methoxy}hexanoic acid (EDOTCA) and the electrochemical co-polymerization of 3,4-ethylenedioxythiophene (EDOT) and EDOTCA to form ultrathin films that optimize electron-transfer rates to solution probe molecules. ITO electrodes were first activated using brief exposure to strong haloacids, to remove the top approximately 8 nm of the electrode surface, followed by immediate immersion into a 50:50 EDOT/EDOTCA co-monomer solution. Potential step electrodeposition for brief deposition times was used to grow copolymer films of thickness 10-100 nm. The composition of these copolymer films was characterized by solution depletion studies of the monomers and atomic force microscopy (AFM), X-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy (reflection-absorption infrared spectroscopy (RAIRS)) of the product films. The spectroscopic data suggest that the composition of the copolymer approaches 80% EDOTCA when electropolymerization occurs from concentrated (10 mM) solutions. AFM characterization shows that electrodeposited poly(EDOT)/poly(EDOTCA) (PEDOT/PEDOTCA) films are quite smooth, with texturing on the nanometer scale. RAIRS studies indicate that these films consist of a combination of EDOTCA units with noninteracting -COOH groups and adjacent hydrogen-bonded -COOH groups. The EDOTCA-containing polymer chains appear to grow as columnar clusters from specific regions, oriented nearly vertically to the substrate plane. As they grow, these columnar clusters overlap to form a nearly continuous redox active polymer film. ITO activation and formation of these copolymer films enhances the electroactive fraction of the electrode surface relative to a nonactivated, unmodified "blocked" ITO electrode. Outer-sphere solution redox probes (dimethylferrocene) give standard rate coefficients, kS > or = 0.4 cm.s-1, at 10 nm thick copolymer films of PEDOT/PEDOTCA, which is 3 orders of magnitude greater than that on the unmodified ITO surface and approaches the values for kS seen on clean gold surfaces.     

聚甲基丙烯酸甲酯/石墨薄片纳米复合及其导电性能研究

在聚合物绝缘材料基体中添加入足够数量的导电填料 ,聚合物便具有导电性或半导体性能 .石墨材料 ,由于资源丰富、价廉、性质稳定 ,被广泛用作导电聚合物复合材料的填料 .一般 ,填料含量越高 ,复合材料的导电性能越好 ,但是材料的力学性能也随之劣化 ,特别是材料脆性增加 .将石墨加工成纳米级粒子 ,再与聚合物纳米复合 ,有望用较少的石墨填充量使复合材料具有良好的电传导性能 ,从而保持材料的力学性能 .最近报道的利用膨胀石墨与聚合物实现纳米复合的研究引起了人们的兴趣 ,如所报道的尼龙 6 膨胀石墨[1] 、PS PMMA 膨胀石墨[2 ] 、PP …     

Impact of film thickness on the morphology of mesoporous carbon films using organic-organic self-assembly

Mesoporous polymer and carbon thin films are prepared by the organic-organic self-assembly of an oligomeric phenolic resin with an amphiphilic triblock copolymer template, Pluronic F127. The ratio of resin to template is selected such that a body-centered cubic (Im3m) mesostructure is formed in the bulk. However, well-ordered mesoporous films are not always obtained for thin films (<100 nm), and this behavior is found to be directly correlated with the initial phenolic resin to template ratio. Furthermore, the symmetry of ordered phases is highly dependent on the number of layers of spheres in the film: Monolayers and bilayers are characterized by hexagonal close-packed (HCP) symmetry, while films with approximately 5 layers of spheres exhibit a mixture of HCP and face-centered orthorhombic (FCO) structures. Ultrathick films having more than 30 layers of spheres are similar to the bulk body-centered cubic symmetry with a preferential orientation of the closest-packed (110) plane parallel to the substrate. Film thickness and initial composition of the carbonizable precursors in the template are critical factors in determining the morphology of mesoporous carbon films. These results provide insight into why difficulties have been reported in producing ultrathin ordered mesoporous carbon films using cooperative organic-organic self-assembly.     

Deposition of densely packed gold film on an alkane derivative monolayer modified graphite surface

The growth of thin metal films is an important step in the fabrication of electronic and magnetic devices. In this work, an atomically flat graphite surface was used as a model system to understand the details of gold film growth mechanisms and kinetics. Ordered assembling monolayers of 1‐octadecanethiol and stearic acid are used to modify the surface and uniform, densely packed ultrathin gold film with the thickness less than 5 nm are formed on these monolayer‐modified graphite surfaces in a large area. The amount of gold needed to be deposited in order to form a continuous gold film is significantly reduced as compared to that needed on a bare graphite surface. Copyright © 2006 John Wiley & Sons, Ltd.     

Fluorescent quantum yield of pyrene probe in ultrathin polymer films

The fluorescently labelled polymers including pyrene-labelled polystyrene (PyPS) and pyrene-labelled poly(methyl methacrylate) (PyPMMA) with narrow molecular weight distributions were synthesized by the atom transfer radical copolymerization (ATRCP) of styrene or methyl methacrylate with 1-pyrenemethyl methacrylate (PyMMA). The ultrathin PyPS and PyPMMA films with the thickness ranging from 30 nm to 400 nm supported on the quartz slides were prepared by spin-coating. The fluorescent quantum yield (QY) of the pyrene probe in the ultrathin polymer films was investigated by the photoluminescence spectrometer using an integrating sphere detector. The QY decreased with the reduction of film thickness in the sub-200 nm range.     

Preparation of a Large Amount of Ultrathin Graphdiyne

We report a facile strategy to prepare a large amount of ultrathin graphdiyne (GDY) with good crystallinity in the mixture of oil–water systems. By simply mixing the solution of GDY monomer in CHCl₃ and the copper acetate solution as a catalyst in water and stirring at room temperature, ultrathin GDY films with a thickness of ∼4 nm were obtained in a yield of 95 %. This work provides a feasible path for the substantial preparation of GDY films and may pave the way to the development of substantial preparation of the GDY materials.     

Optical Properties of Noble Metal Clusters in Ultrathin Solid Films

We report on the optical properties (absorption, Raman response) of thin and ultrathin phthalocyanine and amorphous silicon films with incorporated noble metal clusters. The metal clusters cause the typical absorption features originating from their surface plasmon resonance. In ultrathin films, due to the spatially close interface, the plasmon absorption may be displaced from its resonance frequency in the bulk, and its average position may be controlled by the average thickness of the ultrathin optical film. For example, we observe a shift of the plasmon resonance of silver clusters in amorphous silicon films (on fused silica) from 440 nm to 740 nm, when the silicon thickness increases from zero up to 9 nm. The deposition experiments are accompanied by investigations of the film structure, particularly in order to estimate the silver cluster diameter, which is around 3 nm or less.