Structural properties of silver particulate films deposited on softened polymer blends of polystyrene/poly (2-vinyl pyridine)

Results of the structural studies of silver particulate films deposited at a rate of 0.4 nm/s on polymeric blends of polystyrene/poly (2-vinyl pyridine), PS/P2VP held at a temperature 457 K by evaporation in a vacuum of 8 × 10⁻⁶ Torr are reported here. The morphology of silver particulate films, characterized by their size, size distribution, shape and inter-particle separation, was observed to modify due to blending of PS with P2VP and amount of silver deposited. The red shift in the plasmon resonance indicates the effect of blending P2VP with PS. Scanning electron microscopy was used to study the change in morphology of the silver nanoparticles in correlation with the optical properties of silver particulate films on PS/P2VP blends. The silver nanoparticles on the thin layers of polymer blends exhibited much smaller, narrower dispersion and wide size distribution due to blending of PS with P2VP.     

Fabrication of poly(FOMA-b-EO)/silver nanocomposite hybrid films

A facile synthesis of silver nanoparticles (with a diameter of 5 nm)/polymer hybrid films was studied through auto-reduction of silver nitrate (AgNO3) in poly(1H,1H-dihydroperfluorooctyl methacrylate-b-ethylene oxide) (poly(FOMA(10k)-b-EO(10k micellar thin films at ambient temperature. Silver nanoparticles well dispersed in the block copolymeric micellar films were prepared by rendering the silver precursor AgNO3 to interact favorably with PEO blocks. With annealing of the micellar film containing AgNO3 in supercritical CO2, the domains and continuous phase of the micellar film morphology were inverted and silver nanoparticles with a diameter of 10 nm were produced in PEO domains. The synthesis of silver nanoparticles in the copolymeric films was confirmed by transmission electron microscope and UV-visible spectrophotometric analysis.     

Micropatterning of polymer-embedded metal nanoparticles by an ion beam contact lithography

A convenient and effective method to pattern polymer-embedded metal nanoparticles by ion irradiation has been developed. The thin Pluronic films containing silver nitrate as a precursor of silver nanoparticles were irradiated through a pattern mask with accelerated proton (H+) ions. It was found from the UV-Vis measurement that the formation of silver nanoparticles in the Pluronic matrix was dependant on the amount of silver nitrate. The 50 microm line (pitch 150 microm) patterns of the Pluronic containing silver nanoparticles were obtained with the thin film irradiated to 1 x 10(16) ions/cm2. The heat treatment effect on the morphology of the patterns was investigated by using a scanning electron microscope with an energy dispersive X-ray spectrometer. The results confirmed that the silver nanoparticles were successfully embedded in the Pluronic patterns and the patterns were changed into large silver particles by a heat treatment above 350 degrees C.     

自组装功能膜诱导合成铁酸铋薄膜的研究

采用分子自组装技术在玻璃基片表面制备了十八烷基三氯硅烷自组装单层膜(OTS-SAMs),并在功能化的基板表面诱导生成铁酸铋(BiFeO3)薄膜,采用接触角测试仪、X射线衍射(XRD)、扫描电镜(SEM)和能谱分析(EDS)测试手段对OTS膜和BiFeO3薄膜进行了表征.实验结果表明,在SAMs功能化的玻璃基底上所制备的铁酸铋薄膜结晶良好,薄膜表面平整光滑,结构致密均一,而且形成BiFeO3多晶聚集体,多晶聚集体的大小在2μm左右.     

Multilayer self-assembly of TiO₂ nanoparticles and polyaniline-grafted-chitosan copolymer (CPANI) for photocatalysis

A photocatalytic thin film of TiO? nanoparticles and polyaniline-grafted-chitosan (CPANI) was fabricated by layer-by-layer (LbL) approach. The growth of the self-assembly of polymer nanocomposite was monitored by UV-vis spectroscopy and the thin film morphology was analyzed from scanning electron microscopy (SEM). Poly(styrene sulfonate) (PSS) was used as a bridging layer between TiO? nanoparticles and CPANI. Incorporation of CPANI within the LbL self-assembly of polymer nanocomposites enhanced the dye degradation ability of the thin film. These results indicate that the presence of CPANI improves the adsorption of dye in the self-assembly. The effect of surface area and the amount of catalyst was also examined. The reusability of the thin films for dye degradation study ensures the stability of the self-assembly.     

A note on the use of ellipsometry for studying the kinetics of formation of self-assembled monolayers

Ellipsometry is currently one of the most important techniques for characterization of the deposition and growth mode of ultra thin organic films. However, it is well known that for thicknesses normally encountered in organic monolayer films, as would occur for example in self-assembled monolayers, ellipsometry cannot be used to simultaneously determine the thickness and refractive index of the monolayer film. Current practice is to assume a reasonable value for the film refractive index and calculate an effective ‘ellipsometric thickness’. This communication seeks to show that the alternative approach of assuming a thickness for the monolayer (determined by the length of the molecule) and calculating the effective film refractive index lends itself to easier and more meaningful physical interpretation. The Lorentz-Lorenz formula is then used to transform the effective refractive index into a surface coverage and hence to an effective mass coverage. The methodology advanced is applied to the kinetics of formation of a self-assembled monolayer of a well-studied molecule, octadecanethiol on Au.     

纳米银-聚合物薄膜的制备及力电性能测试

聚合物基底上纳米银颗粒薄膜的制备工艺相对简单,成本较低,且该薄膜具有成为高敏感性压阻应力/应变传感材料的潜力。本文采用银镜制备法在聚酰亚胺(PI)和聚乙烯(PE)上合成了纳米银颗粒薄膜,系统研究了该薄膜制备工艺、结构特性、材料性能之间的关系。实验考察了材料“浸泡”时间及聚合物材料前处理等因素对材料表面吸附纳米颗粒含量的影响,研究了 “浸泡”时间对纳米银颗粒粒径大小、颗粒含量及分布的影响,并探讨了不同聚合物基体的颗粒特性对薄膜二维导电渗滤,压阻特性及拉伸性能的影响。研究表明,增加“浸泡”时间能够增加纳米银颗粒粒径大小,提高银颗粒的含量及分布均匀性；在相同的制备条件下,PI基底较PE基底对纳米银颗粒具有更加优异的吸附效果；在PI 和PE基底上的纳米银颗粒薄膜均表现出显著的压阻性能,且电阻对应变的敏感性随应变的增大及银颗粒含量的减少而显著提高。     

Long-term aging of Ag/a-C:H:O nanocomposite coatings in air and in aqueous environment

Nanocomposite coatings of silver particles embedded in a plasma polymer matrix possess interesting properties depending on their microstructure. The film microstructure is affected among others also by the RF power supplied during the deposition, as shown by transmission electron microscopy. The optical properties are characterized by UV–vis–NIR spectroscopy. An anomalous optical absorption peak from the Ag nanoparticles is observed and related to the microstructure of the nanocomposite films. Furthermore, a long-term aging of the coatings is studied in-depth in ambient air and in aqueous environments. It is shown that the studied films are not entirely stable. The deposition conditions and the microstructure of the films affect the processes taking place during their aging in both environments.     

In situ synthesis of metal nanoparticles in polymer matrix and their optical limiting applications

We present an overview of the simple and environmentally benign protocol we have developed recently, for the in situ generation of metal nanoparticles inside polymer films by mild thermal annealing, leading to free-standing as well as supported thin films of nanoparticle-embedded polymer. The fabrication chemistry is discussed and spectroscopic/microscopic characterizations of silver and gold nanoparticles in poly(vinyl alcohol) film are presented. Optical limiting characteristics of the silver-polymer system are investigated in detail and preliminary results for the gold-polymer system are reported.     

Long-term aging of Ag/a-C:H:O nanocomposite coatings in air and in aqueous environment

Abstract

Nanocomposite coatings of silver particles embedded in a plasma polymer matrix possess interesting properties depending on their microstructure. The film microstructure is affected among others also by the RF power supplied during the deposition, as shown by transmission electron microscopy. The optical properties are characterized by UV–vis–NIR spectroscopy. An anomalous optical absorption peak from the Ag nanoparticles is observed and related to the microstructure of the nanocomposite films. Furthermore, a long-term aging of the coatings is studied in-depth in ambient air and in aqueous environments. It is shown that the studied films are not entirely stable. The deposition conditions and the microstructure of the films affect the processes taking place during their aging in both environments.     

Microstructure and optical properties of plasmapolymer thin films with embedded silver nanoparticles

Plasmapolymer thin films with embedded silver nanoparticles were deposited by simultaneous plasma polymerization and metal evaporation. The particle size and shape were determined by transmission electron microscopy (TEM) and analysed by optical image processing. The optical properties in the UV/ VIS/NIR spectral region were determined by the plasma resonance absorption of the silver particles. Transmittance spectra were calculated with the Bergman effective medium theory and compared with experimental spectra.     

Electron microscopy reveals structure and morphology of one molecule thin organic films

Transmission electron microscopy was used to determine the structure of molecular films of self-assembled monolayers of pentathiophene derivatives supported on various electron transparent substrates. Despite the extreme beam sensitivity of the monolayers, structural crystallographic maps were obtained that revealed the nanoscale structure of the film. The image resolution is determined by the minimum beam diameter that the radiation hardness of the monolayer can support, which in our case is about 90 nm for a beam current of 5 × 10(6) e(-)/s. Electron diffraction patterns were collected while scanning a parallel electron beam over the film. These maps contain uncompromised information of the size, symmetry and orientation of the unit cell, orientation and structure of the domains, degree of crystallinity, and their variation on the micrometer scale, which are crucial to understand the electrical transport properties of the organic films. This information allowed us to track small changes in the unit cell size driven by the chemical modification of the support film.     

Oxygen plasma etching of silver-incorporated diamond-like carbon films

Diamond-like carbon (DLC) film as a solid lubricant coating represents an important area of investigation related to space devices. The environment for such devices involves high vacuum and high concentration of atomic oxygen. The purpose of this paper is to study the behavior of silver-incorporated DLC thin films against oxygen plasma etching. Silver nanoparticles were produced through an electrochemical process and incorporated into DLC bulk during the deposition process using plasma enhanced chemical vapor deposition technique. The presence of silver does not affect significantly DLC quality and reduces by more than 50% the oxygen plasma etching. Our results demonstrated that silver nanoparticles protect DLC films against etching process, which may increase their lifetime in low earth orbit environment.     

Phase separation and surface morphology of spin-coated films of polyetherimide/polycaprolactone immiscible polymer blends

The surface morphology in thin films of immiscible polyetherimide and polycaprolactone blends was studied using scanning electron and atomic force microscopy. The thin films were obtained by spin-coating from dichloromethane solution. A self-assembled periodic pattern of phase separated domains was observed, which was induced by capillary effects along with the solution radial flow and the unsteady air flow field above the film during the initial stages of spin-coating. A secondary phase separation was observed during the solvent evaporation stage of spin-coating. The differences in surface topographies of the two distinct phases are attributed to different solvent evaporation rates within each phase. In addition, a great variety of domain structures and surface morphologies were observed as a function of polymer blend composition.     

钛酸锶薄膜的液相自组装制备与表征

采用自组装单层膜技术在玻璃基板上成功制备了钛酸锶薄膜,利用接触角仪对前期处理后的基片润湿角进行表征,利用X射线衍射(XRD),扫描电镜(SEM)等手段表征了薄膜的物相和微观结构。实验结果表明:采用自组装单层膜技术制备的钛酸锶薄膜结晶良好,样品表面均匀,颗粒尺寸大约在300nm～500nm之间。     

非织造基磁控溅射纳米银薄膜导电性能的研究

在室温条件下采用射频磁控溅射在丙纶(PP)、聚乳酸(PLA)熔喷非织造布表面生长纳米银(Ag)薄膜,并且用等离子体预处理样品进行对比。采用扫描电子显微镜(SEM)对其形貌进行表征,采用四探针测试仪对所制备的纳米薄膜的导电性能进行表征。研究溅射时间、孔隙率及孔径分布和等离子处理对非织造基纳米银薄膜的导电性能的影响。实验表明:随着反应溅射时间的增加,薄膜的方块电阻值下降,导电性能增加;孔径大小也影响薄膜的导电性能,随着孔径的增大,薄膜的导电性能降低;等离子体处理对织物表面进行刻蚀,增加了纤维的比表面积,提高了纤维的润湿性能,改善了织物的导电性能。     

Electrodeposition of polypyrrole-heparin and polypyrrole-hydroxyapatite films

Composite films containing heparin and hydroxyapatite in a polypyrrole (PPY) matrix were electrochemically deposited as monolayers or bi-layers on conductive substrates. The deposition on stainless steel substrates was achieved using a thin prime layer of PPY deposited by anodic electropolymerization in the presence of salicylate anions, which passivated the substrate surface. The deposition mechanism, film composition and morphology were investigated. The films containing heparin may have improved anticoagulant activity as suggested by their ability to bind antithrombin from plasma.     

SiO2-Ag纳米复合颗粒自组装的制备与表征

利用自组装法在空气-水界面制备了SiO2薄膜粒子,将所制薄膜粒子先后用AgNO3溶液与Na2S2O3溶液浸泡,并充分曝光,形成了一种形状如"西瓜"的SiO2-Ag纳米复合颗粒.采用X射线衍射(XRD)、透射电子显微镜(TEM)、紫外可见吸收光谱(UV-Vis)对其结构进行了表征和分析,并初步探讨了其结构的形成机理.结果表明,纳米Ag"瓜子"均匀地分散于SiO2"瓜瓤"颗粒中,形成的复合颗粒呈球形,粒径均匀.     

Kinetically driven self assembly of highly ordered nanoparticle monolayers

When a drop of a colloidal solution of nanoparticles dries on a surface, it leaves behind coffee-stain-like rings of material with lace-like patterns or clumps of particles in the interior. These non-uniform mass distributions are manifestations of far-from-equilibrium effects, such as fluid flows and solvent fluctuations during late-stage drying. However, recently a strikingly different drying regime promising highly uniform, long-range-ordered nanocrystal monolayers has been found. Here we make direct, real-time and real-space observations of nanocrystal self-assembly to reveal the mechanism. We show how the morphology of drop-deposited nanoparticle films is controlled by evaporation kinetics and particle interactions with the liquid-air interface. In the presence of an attractive particle-interface interaction, rapid early-stage evaporation dynamically produces a two-dimensional solution of nanoparticles at the liquid-air interface, from which nanoparticle islands nucleate and grow. This self-assembly mechanism produces monolayers with exceptional long-range ordering that are compact over macroscopic areas, despite the far-from-equilibrium evaporation process. This new drop-drying regime is simple, robust and scalable, is insensitive to the substrate material and topography, and has a strong preference for forming monolayer films. As such, it stands out as an excellent candidate for the fabrication of technologically important ultra thin film materials for sensors, optical devices and magnetic storage media.     

Nanocrystalline TiO2 thin films for NH3 monitoring: microstructural and physical characterization

Nanocrystalline titanium oxide thin films have been deposited by spin coating technique and then have been analyzed to test their application in NH₃ gas-sensing technology. In particular, spectrophotometric and conductivity measurements have been performed in order to determine the optical and electrical properties of titanium oxide thin films. The structure and the morphology of such material have been investigated by X ray diffraction, Scanning microscopy, high resolution electron microscopy and selected area electron diffraction. The X-ray diffraction measurements confirmed that the films grown by this technique have good crystalline tetragonal mixed anatase and rutile phase structure. The HRTEM image of TiO₂ thin film showed grains of about 50–60 nm in size with aggregation of 10–15 nm crystallites. Selected area electron diffraction pattern shows that the TiO₂ films exhibited tetragonal structure. The surface morphology (SEM) of the TiO₂ film showed that the nanoparticles are fine with an average grain size of about 50–60 nm. The optical band gap of TiO₂ film is 3.26 eV. Gas sensing properties showed that TiO₂ films were sensitive as well as fast in responding to NH₃. A high sensitivity for ammonia indicates that the TiO₂ films are selective for this gas.