Long-Term Stability at High Temperatures for Birefringence in PAZO/PAH Layer-by-Layer Films

Optical memories with long-term stability at high temperatures have long been pursued in azopolymers with photoinduced birefringence. In this study, we show that the residual birefringence in layer-by-layer (LbL) films made with poly[1-[4-(3-carboxy-4 hydroxyphenylazo)benzene sulfonamido]-1,2-ethanediyl, sodium salt] (PAZO) alternated with poly(allylamine hydrochloride) (PAH) can be tuned by varying the extent of electrostatic interactions with film fabrication at different pHs for PAH. The dynamics of both writing and relaxation processes could be explained with a two-stage mechanism involving the orientation of the chromophores per se and the chain movement. Upon calculating the activation energies for these processes, we demonstrate semiquantitatively that reduced electrostatic interactions in films prepared at higher pH, for which PAH is less charged, are responsible for the longer stability at high temperatures. This is attributed to orientation of PAZO chromophores via cooperative aggregation, where the presence of counterions hindered relaxation.

Tailoring Molecular Architectures with Cobalt Tetrasulfonated Phthalocyanine: Immobilization in Layer-by-Layer Films and Sensing Applications

In the field of organic thin films, manipulation at the nanoscale can be obtained by immobilization of different materials on platforms designed to enhance a specific property via the layer-by-layer technique. In this paper we describe the fabrication of nanostructured films containing cobalt tetrasulfonated phthalocyanine (CoTsPc) obtained through the layer-by-layer architecture and assembled with linear poly(allylamine hydrochloride) (PAH) and poly(amidoamine) dendrimer (PAMAM) polyelectrolytes. Film growth was monitored by UV-vis spectroscopy following the Q band of CoTsPc and revealed a linear growth for both systems. Fourier transform infrared (FTIR) spectroscopy showed that the driving force keeping the structure of the films was achieved upon interactions of CoTsPc sulfonic groups with protonated amine groups present in the positive polyelectrolyte. A comprehensive SPR investigation on film growth reproduced the deposition process dynamically and provided an estimation of the thicknesses of the layers. Both FTIR and SPR techniques suggested a preferential orientation of the Pc ring parallel to the substrate. The electrical conductivity of the PAH films deposited on interdigitated electrodes was found to be very sensitive to water vapor. These results point to the development of a phthalocyanine-based humidity sensor obtained from a simple thin film deposition technique, whose ability to tailor molecular organization was crucial to achieve high sensitivity.

Determination of degree of ionization of poly(allylamine hydrochloride) (PAH) and poly[1-[4-(3-carboxy‑4 hydroxyphenylazo)benzene sulfonamido]-1,2-ethanediyl, sodium salt] (PAZO) in layer-by-layer films using vacuum photoabsorption spectroscopy

Electrostatic and hydrophobic interactions govern most of the properties of supramolecular systems, which is the reason determining the degree of ionization of macromolecules has become crucial for many applications. In this paper, we show that highresolution ultraviolet spectroscopy (VUV) can be used to determine the degree of ionization and its effect on the electronic excitation energies of layer-by-layer (LbL) films of poly(allylamine hydrochloride) (PAH) and poly[1-[4-(3-carboxy-4 hydroxyphenylazo)- benzene sulfonamido]-1,2-ethanediyl, sodium salt] (PAZO). A full assignment of the VUV peaks of these polyelectrolytes in solution and in cast or LbL films could be made, with their pH dependence allowing us to determine the p'K IND. a' using the Henderson-Hasselbach equation. The p'K IND. a' for PAZO increased from ca. 6 in solution to ca. 7.3 in LbL films owing to the charge transfer from PAH. Significantly, even using solutions at a fixed pH for PAH, the amount adsorbed on the LbL films still varied with the pH of the PAZO solutions due to these molecular-level interactions. Therefore, the procedure based on a comparison of VUV spectra from solutions and films obtained under distinct conditions is useful to determine the degree of dissociation of macromolecules, in addition to permitting interrogation of interface effects in multilayer films.

Thin functional conducting polymer films

In the present study, thin functional conducting polyaniline (PANI) films, either doped or undoped, patterned or unpatterned, were prepared by different approaches. The properties of the obtained PANI films were investigated in detail by a combination of electrochemistry with several other techniques, such as SPR, QCM, SPFS, diffraction, etc. The sensing applications (especially biosensing applications) of the prepared PANI films were explored. Firstly, the pure PANI films were prepared by the electropolymerisation method and their doping/dedoping properties in acidic conditions were investigated in detail by a combination of electrochemistry with SPR and QCM. Dielectric constants of PANI at different oxidation states were obtained quantitatively. The results obtained here laid a good foundation for the following investigations of PANI films in neutral pH conditions. Next, PANI multilayer films doped by a variety of materials were prepared by the layer-by-layer method in order to explore their biosensing applications, because of the loss of redox activity of pure PANI in neutral pH conditions. The dopants used include not only the traditionally used linear polyelectrolytes, but also, for the first tim, some other novel materials, like modified gold nanoparticles or modified carbon nanotubes. Our results showed that all the used dopants could form stable multilayer films with PANI. All the obtained PANI multilayer films showed good redox activity in a neutral pH environment, which makes them feasible for bioassays. We found that all the prepared PANI multilayer films can electrocatalyze the oxidation of NADH in neutral conditions at a low potential, although their catalytic efficiencies are different. Among them, PANI/carbon nanotube system showed the highest catalytic efficiency toward the oxidation of NADH, which makes it a good candidate as a NADH sensor. Besides, because some of the prepared PANI multilayer systems were end-terminated with –COOH groups (like PANI/Au nanoparticles system), which can be utilized to easily link biomolecules for biosensing applications. Here, we demonstrated, for the first time, to use the prepared PANI multilayer films for the DNA hybridisation detection. The detection event was monitored either by direct electrochemical method, or by enzyme-amplified electrochemical method, or by surface plasmon enhanced fluorescence spectroscopic method. All the methods can effectively differentiate non-complementary DNA from the complementary ones, even at the single-base mismatch level. It should also be noted that, our success in fabricating PANI multilayer films with modified Au nanoparticles or carbon nanotubes also offered another novel method for incorporating such novel materials into (conducting) polymers. Because of the unique electrochemical and optical properties of each component of the obtained PANI multilayer films, they should also find potential applications in many other fields such as microelectronics, or for electrochromic and photovoltaic devices. Finally, patterned PANI films were fabricated by the combination of several patterning techniques, such as the combination of electrocopolymerization with micromolding in capillaries (EP-MIMIC), the combination of microcontact printing with the layer-by-layer technique (µCP-LBL), and the polystyrene (PS) template induced electropolymerisation method. Using the obtained stripe-shaped PANI/PSS film, a redox-switchable polymer grating based on the surface-plasmon-enhanced mode was constructed and its application in the field of biosensing was explored. It was found that the diffraction efficiency (DE) of the grating was very sensitive to the applied potential (i.e. redox state of the film) as well as the pH environment of the dielectric medium. Moreover, the DE could also be effectively tuned by an electrocatalytic event, such as the electrocatalytic oxidation of NADH by the grating film. By using PS colloidal crystal assemblies as templates, well-ordered 3D interconnected macroporous PANI arrays (PANI inverse opals) were fabricated via electropolymerisation method. The quality of the obtained inverse opals was much higher than those reported by chemical synthesis method. By electrochemical method, the structures of the prepared inverse opals can be easily controlled. To explore the possible biosensing applications of PANI inverse opals, efforts were also done toward the fabrication of PANI composite inverse opals. By selecting proper dopants, high quality inverse opals of PANI composites were fabricated for the first time. And the obtained opaline films remained redox-active in neutral pH conditions, pointing to their possible applications for electrobioassays.

The structure of ultrathin Langmuir-Blodgett films of cadmium behenate

Grazing incidence x-ray-diffraction investigations of the structures of Langmuir-Blodgett films of cadmium behenate with 1, 2, 3, 5, and 21 monolayers are reported. The single monolayer film, deposited on a hydrophilic substrate, showed a hexagonal structure, whereas the bilayer film, deposited on a hydrophobic substrate, had a rectangular structure with herringbone orientation of the acyl chains. With multilayer films formed on a hydrophilic substrate, it was possible to detect that the hexagonal structure of the first layer was retained when additional layers were deposited and that the additional layers had the same rectangular structure as the bilayer. (c) 2005 American Institute of Physics.

Size-dependent radiation tolerance in ion irradiated TiN/AlN nanolayer films

Interface effects on ion-irradiation tolerance properties are investigated in nanolayered TiN/AlN films with individual layer thickness varied from 5 nm to 50 nm, prepared by pulsed laser deposition. Evolution of the microstructure and hardness of the multilayer films are examined on the specimens before and after He ion-implantation to a fluence of 4 × 10 m at 50 keV. The suppression of amorphization in AlN layers and the reduction of radiation-induced softening are observed in all nanolayer films. A clear size-dependent radiation tolerance characteristic is observed in the nanolayer films, i.e., the samples with the optimum layer thickness from 10 nm to 20 nm show the best ion irradiation tolerance properties, and a critical layer thickness of more than 5 nm is necessary to prevent severe intermixing. This study suggests that both the interface characteristics and the critical length scale (layer thickness) contribute to the reduction of the radiation-induced damages in nitride-based ceramic materials. © 2013 Elsevier B.V. All rights reserved.

A comparative study of the interaction of nickel clusters with buckminsterfullerene, C60, and graphite

Interaction of nickel deposited on multilayer films of C60 has been investigated in comparison with that on amorphized graphite by employing photoemission spectroscopy. It is shown that unlike with graphite, Ni interacts strongly with C60 causing large changes in C(1s) and C(2p) binding energies. The increase in the Ni(2p) binding energy at small Ni coverages is also far greater on c60 than on graphite.

Layer-by-Layer Assembly of Nafion on Surlyn with Ultrahigh Water Vapor Barrier

A layer-by-layer approach was used for the fabrication of multilayer films for ultra high gas barrier applications. The ultra high gas barrier material was designed by incorporating Nafion layer in between bilayers of poly(ethylene imine) and poly(acrylic acid) on a Surlyn substrate. When the barrier film with self-assembled Nafion is exposed to the moist environment, Nafion absorbs and desorbs water molecules simultaneously, thereby reducing the ingress of moisture in to the film. In order to study the effect of Nafion, the fabricated barrier materials with and without the presence of Nafion were tested for water vapor barrier properties. The barrier films were further used for encapsulating organic photovoltaic devices and were evaluated for their potential use in barrier applications. The devices encapsulated with the films containing Nafion exhibited better performance when subjected to accelerated aging conditions. Therefore, this study demonstrates the effectiveness of self-assembled Nafion in reducing the water vapor permeability by nearly five orders of magnitude and in increasing the lifetimes of organic devices by similar to 22 times under accelerated weathering conditions.

退火对HfO2/SiO2多层膜残余应力的影响

用电子束蒸发方法在BK7基底上沉积了HfO2/SiO2多层膜。研究了200℃到400℃的退火对残余应力的影响。结果表明退火前的薄膜残余应力为压应力，在200℃退火后发展为张应力，然后张应力值随着退火温度的升高而增大。在400℃退火后，由于张应力太大，薄膜表面出现了裂纹。同时，随着退火温度的升高，晶粒尺寸长大，晶面间距降低。残余应力的变化与结构的演变相对应。

Altering the ordering and disordering of a triangular nanographene at room temperature.

Molecular self-organization has the potential to serve as an efficient and versatile tool for the spontaneous creation of low-dimensional nanostructures on surfaces. We demonstrate how the subtle balance between intermolecular interactions and molecule-surface interactions can be altered by modifying the environment or through manipulation by means of the tip in a scanning tunnelling microscope (STM) at room temperature. We show how this leads to the distinctive ordering and disordering of a triangular nanographene molecule, the trizigzag-hexa-peri-hexabenzocoronenes-phenyl-6 (trizigzagHBC-Ph6), on two different surfaces: graphite and Au(111). The assembly of submonolayer films on graphite reveals a sixfold packing symmetry under UHV conditions, whereas at the graphite-phenyloctane interface, they reorganize into a fourfold packing symmetry, mediated by the solvent molecules. On Au(111) under UHV conditions in the multilayer films we investigated, although disorder prevails with the molecules being randomly distributed, their packing behaviour can be altered by the scanning motion of the tip. The asymmetric diode-like current-voltage characteristics of the molecules are retained when deposited on both substrates. This paper highlights the importance of the surrounding medium and any external stimulus in influencing the molecular organization process, and offers a unique approach for controlling the assembly of molecules at a desired location on a substrate.

Growth of thicker zinc-blende CrSb layers by using (In,Ga)As buffer layers

Zinc-blende CrSb (zb-CrSb) layers with room-temperature ferromagnetism have been grown on (In,Ga)As buffer layers epitaxially prepared on (001) GaAs substrates by molecular-beam epitaxy. Compared with the typical thickness [2-3 ML (ML denotes monolayers)] of zb-CrSb grown directly on GaAs, the thickness of zb-CrSb grown on (In,Ga)As has been increased largely; the maximum can be up to similar to 9 ML. High-resolution cross sectional transmission electron microscopy images show that the zb-CrSb layer is combined with (In,Ga)As buffer layer without any dislocations at the interface. (C) 2006 American Institute of Physics.

多层膜组装及其电催化研究

本论文主要是利用在化学修饰电极基础上建立起来的有序分子自组装膜技术，来制备能高效催化氧还原的有机一无机复合膜以及贵金属纳米粒子膜，以达到对氧的四电子还原。具体工作为：1．金属叶琳如钻叶琳单独修饰在电极表面通常只能通过两电子还原氧生成过氧化氢。而杂多酸是一种很好的电子媒介体，对很多小分子比如过氧化氢等都有很好的催化作用。我们用杂多阴离子作为对离子制备了含金属叶琳的复合膜，由于这两种物质的协同催化作用，所制备有机一无机复合膜表现了很高的催化活性，几乎达到了氧的四电子还原。2．很早人们就发现杂多酸电聚合在电极表面在酸性介质中可以催化析氢。我们通过层层组装的方法在功能化玻碳电极表面制备SiW_(12)／CoTMPyP多层复合膜，该复合膜可以高效催化析氢，同时该多层膜又能两电子催化氧还原。3．通过在一定电位下直接还原在CoTMPyP夹层间的氯铂酸根离子，在电极表面合成了三维铂纳米粒子膜。该纳米粒子膜对氧有很高的催化作用，旋转圆盘电极实验和旋转环盘电极实验证明该铂纳米粒子膜在0.5 MH_2SO_4溶液中可以实现对氧的四电子还原。4．在裸的金电极表面成功地欠电位沉积了把纳米粒子单层膜，该纳米粒子单层膜对氧还原有很好的催化作用。在这一工作基础上，研制了DO在线监侧仪。5．通过层层组装的方法，金溶胶纳米粒子与CoTMPyP的复合膜成功地组装在各种基底上。被聚丙烯酸稳定的金纳米粒子很容易吸附在CoTMPyP上，形成非常紧密分布的纳米粒子膜。6．在多壁碳纳米管表面吸附MP-11，实现了MP-11的直接电化学，同时研究了其对氧和过氧化氢的催化作用。

Photo- and Thermo-Chromic Study of the Ethylenediamine Trimolybdate

The ethylenediamine trimolybdate (ENTMo) can show unusually photochromic and thermochromic properties and there exists in the difference of chromic mechanisms, which has been proved in our previous work [I]. In this paper, X-ray powder diffraction (XRD), Fourier transform infrared (FTIR) and laser Raman spectroscopy (LRS) of the colored samples are characterized and analyzed in detail. The crystal structure, the inorganic skeleton and the microenvironment of center ions of the colored samples do not substantively change except distortion. The color difference of the photochromic and the thermochromic samples is discussed and that the difference of reduction sites result in their different chromic mechanisms is suggested.

Layer-by-layer assembly of carbon nanotubes and Prussian blue nanoparticles: A potential tool for biosensing devices

A promising method for assembling carbon nanotubes (CNTs) and poly(diallyldimethylammonium chloride) protected Prussian blue nanoparticles (P-PB) to form three-dimensional (3D) nanostructured films is proposed. The electrostatic interaction, combined with layer-by-layer self-assembly (LBL), between negatively charged CNTs and positively charged P-PB is strong enough to drive the formation of the 3D nanostructured films. Thus, prepared multilayer films were characterized by ultraviolet-visible-near-infrared spectroscopy (UV-vis-NIR), scanning electron microscopy (SEM) and cyclic voltammetry (CV).

Solid-state electrochemiluminescence of tris(2,2 '-bipyridyl) ruthenium

Electrochemiluminescence (ECL) of tris(2,2'-bipyridyl) ruthenium [Ru(bpy)(3)(2+)] has received considerable attention. By immobilizing Ru(bpy)(3)(2+) on an e electrode surface, solid-state ECL provides several advantages over solution-phase ECL, such as reducing consumption of expensive reagent, simplifying experimental design and enhancing the ECL signal.This review presents the state of the art in solid-state ECL of Ru(bpy)(3)(2+).