Electrochemiluminescence sensor using tris(2,2 '-bipyridyl)ruthenium(II) immobilized in Eastman-AQ55D-silica composite thin-films

An electrochemiluminescence (ECL) sensor with good long-term stability and fast response time has been developed. The sensor was based on the immobilization of tris(2,2'-bipyridyl)ruthenium(II) (Ru(bpy)(3)(2+)) into the Eastman-AQ55D-silica composite thin films on a glassy carbon electrode. The ECL and electrochemistry of Ru(bpy)(3)(2+) immobilized in the composite thin films have been investigated, and the modified electrode was used for the ECL detection of oxalate, tripropylamine (TPA) and chlorpromazine (CPZ) in a flow injection analysis system and showed high sensitivity. Because of the strong electrostatic interaction and low hydrophobicity of Eastman-AQ55D, the sensor showed no loss of response over 2 months of dry storage. In use, the electrode showed only a 5% decrease in response over 100 potential cycles. The detection limit was 1 mumol l(-1) for oxalate and 0.1 mumol l(-1) for both TPA and CPZ (S/N = 3), respectively. The linear range extended from 50 mumol l(-1) to 5 mmol l(-1) for oxalate, from 20 mumol l(-1) to 1 mmol l(-1) for TPA, and from 1 mumol l(-1) to 200 mumol l(-1) for CPZ.

Electrochemiluminescence of tris(2,2 '-bipyridyl)ruthenium (II) ion-exchanged in polyelectrolyte-silica composite thin-films

The organic-inorganic hybrid, PSS-silica composite material was developed for the immobilization of tris(2,2'-bipyridyl)ruthenium(II) (Ru(bpy)(3)(2+)) on glassy carbon electrode via ion-exchange (PSS stands for poly(sodium 4-styrene-sulfonate)). The electrochemiluminescence (ECL) and electrochemistry of Ru(bpy)(3)(2-) immobilized in the composite thin films have been investigated with tripropylamine (TPA) as the coreactant. The immobilized Ru(bpy)(3)(2-) underwent a surface process. The modified electrode was used for the ECL detection of TPA and showed high sensitivity. Detection limit was 0,1 mumol L-1 for TPA (S/N = 3) with a linear range from 0.5 mumol L-1 to 5 mmol L-1 (R = 0.998), Moreover, the resulting modified electrode was stable over six months and the good stability may be due to the strong interaction between Ru(bpy)(3)(2-) and the high ion-exchange able PSS-silica composite films on GCE. Compared with other materials. the PSS-silica composite films containing incorporated Ru(bpy)(3)(2-) showed improved sensitivity and long-term stability, Thus, such composite thin film can be a promising material for the construction of ECL sensor.

Electrochemiluminescence of tris(2,2 '-bipyridine)ruthenium(II) immobilized in poly(p-styrenesulfonate)-silica-Triton X-100 composite thin-films

The electrochemiluminescence (ECL) of tris(2,2'-bipyridine)ruthenium(ii) [Ru(bpy)(3)(2+)] immobilized in poly(p-styrenesulfonate) (PSS)-silica-Triton X-100 composite films was investigated. The cooperative action of PSS, sol-gel and Triton X-100 attached Ru(bpy)(3)(2+) to the electrode strongly, and the presence of Triton X-100 prevented drying fractures of the sol-gel films during gelation and even on repeated wet-dry cycles. The modified electrode was used for the ECL detection of oxalate, tripropylamine (TPA) and NADH in a flow injection analysis (FIA) system with a newly designed flow cell. The detection scheme exhibited good stability, short response time and high sensitivity. Detection limits were 0.1, 0.1 and 0.5 mu mol L-1 for oxalate, TPA and NADH, respectively, and the linear concentration range extended from 0.001 to 1 mmol L-1 for the three analytes. Applications of the flow cell in ECL and electrochemical detection, as well as the immobilization of reagents based on the cooperative action, are suggested.

Investigation of the Mechanical Properties of Thin Films by Nanoindentation, Considering the Effects of Thickness and Different Coating-Substrate Combinations

In order to further investigate nanoindentation data of film-substrate systems and to learn more about the mechanical properties of nanometer film-substrate systems, two kinds of films on different substrate systems have been tested with a systematic variation in film thickness and substrate characteristics. The two kinds of films are aluminum and tungsten, which have been sputtered on to glass and silicon substrates, respectively. Indentation experiments were performed with a Nano Indent XP II with indenter displacements typically about two times the nominal film thicknesses. The resulting data are analyzed in terms of load-displacement curves and various comparative parameters, such as hardness, Young's modulus, unloading stiffness and elastic recovery. Hardness and Young's modulus are investigated when the substrate effects are considered. The results show how the composite hardness and Young's modulus are different for different substrates, different films and different film thicknesses. An assumption of constant Young's modulus is used for the film-substrate system, in which the film and substrate have similar Young's moduli. Composite hardness obtained by the Joslin and Oliver method is compared with the directly measured hardness obtained by the Oliver and Pharr method.

Fracture Properties of LPCVD Silicon Nitride and Thermally Grown Silicon Oxide Thin Films From the Load-Deflection of Long Si3N4 and SiO2/Si3N4 Diaphragms

The bulge test is successfully extended to the determination of the fracture properties of silicon nitride and oxide thin films. This is achieved by using long diaphragms made of silicon nitride single layers and oxide/nitride bilayers, and applying comprehensive mechanical model that describes the mechanical response of the diaphragms under uniform differential pressure. The model is valid for thin films with arbitrary z-dependent plane-strain modulus and prestress, where z denotes the coordinate perpendicular to the diaphragm. It takes into account the bending rigidity and stretching stiffness of the layered materials and the compliance of the supporting edges. This enables the accurate computation of the load-deflection response and stress distribution throughout the composite diaphragm as a function of the load, in particular at the critical pressure leading to the fracture of the diaphragms. The method is applied to diaphragms made of single layers of 300-nm-thick silicon nitride deposited by low-pressure chemical vapor deposition and composite diaphragms of silicon nitride grown on top of thermal silicon oxide films produced by wet thermal oxidation at 950 degrees C and 1050 degrees C with target thicknesses of 500, 750, and 1000 mn. All films characterized have an amorphous structure. Plane-strain moduli E-ps and prestress levels sigma(0) of 304.8 +/- 12.2 GPa and 1132.3 +/- 34.4 MPa, respectively, are extracted for Si3N4, whereas E-ps = 49.1 +/- 7.4 GPa and sigma(0) = -258.6 +/- 23.1 MPa are obtained for SiO2 films. The fracture data are analyzed using the standardized form of the Weibull distribution. The Si3N4 films present relatively high values of maximum stress at fracture and Weibull moduli, i.e., sigma(max) = 7.89 +/- 0.23 GPa and m = 50.0 +/- 3.6, respectively, when compared to the thermal oxides (sigma(max) = 0.89 +/- 0.07 GPa and m = 12.1 +/- 0.5 for 507-nm-thick 950 degrees C layers). A marginal decrease of sigma(max) with thickness is observed for SiO2, with no significant differences between the films grown at 950 degrees C and 1050 degrees C. Weibull moduli of oxide thin films are found to lie between 4.5 +/- 1.2 and 19.8 +/- 4.2, depending on the oxidation temperature and film thickness.

Characterization of stress induced in SOS and Si/gamma-Al2O3/Si heteroepitaxial thin films by Raman spectroscopy

Raman spectroscopy technique has been performed to investigate the stress induced in as-grown silicon-on-sapphire (SOS), solid-phase-epitaxy (SPE) re-grown SOS, and Si/gamma-Al2O3/Si double-heteroepitaxial thin films. It was demonstrated that the residual stress in SOS film, arising from mismatch and difference of thermal expansion coefficient between silicon and sapphire, was reduced efficiently by SPE process, and that the stress in Si/gamma-Al2O3/Si thin film is much smaller than that of as-grown SOS and SPE upgraded SOS films. The stress decrease for double heteroepitaxial film Si/gamma-Al2O3/Si mainly arises from the smaller lattice mismatching of 2.4% between silicon top layer and the gamma-Al2O3/Si epitaxiial composite substrate, comparing with the large lattice mismatch of 13% for SOS films. It indicated that gamma-Al2O3/Si as a silicon-based epitaxial substrate benefits for reducing the residual stress for further growth of silicon layer, compared with on bulk sapphire substrate. (c) 2005 Elsevier B.V. All rights reserved.

Effects of polymerization conditions on hydrophilic groups in aromatic polyamide thin films

For polyamide used in reverse osmosis (RO) membranes, the content of pendant acid groups is critical to its performance. In this work, FTIR was used to analyze the acid contents in the polyamide films prepared via interfacial polymerization of trimesic acid trichloride (TMC) in hexane and 1,3-phenylenediamine (MPDA) in water, and the effects of reaction conditions, including monomer concentrations, time, and temperature, were studied. It was found that more pendant acid groups are present in the polyramide film at higher TMC concentrations or lower MPDA concentrations, and longer reaction times and lower temperatures also favor the formation of the free acids. These results can be explained by the monomer diffusion in the interfacial polymerization process. This work may help the design and fabrication of RO membranes with different hydrophilicity and target performance.

Surface plasmon resonance and electrochemistry characterization of layer-by-layer self-assembled DNA and Zr4+ thin films, and their interaction with cytochrome c

Through electrostatic layer-by-layer (LbL) assembly, negatively charged calf thymus double stranded DNA (CTds-DNA), and positively charged Zr4+ ions were alternately deposited on gold substrate modified with chemisorbed cysteamine. Thus-prepared three-dimensional DNA networks were characterized by surface plasmon resonance (SPR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and infrared reflection-absorption spectroscopy (IR-RAS). SPR spectroscopy indicates that the effective thickness of DNA monolayer in the (DNA/Zr4+), bilayer was 1.5 +/- 0.1 nm, which corresponds to the surface coverage of 79% of its full packed monolayer. At the same time, a linear increase of film thickness with increasing number of layers was also confirmed by SPR characterizations. The data of XPS and IR-RAS show that Zr4+ ions interact with both the phosphate groups and nitrogenous bases of DNA and load into the framework of DNA. Furthermore, the interactions between this composite film and heme protein cytochrome c (Cyt c) were investigated by SPR spectroscopy and electrochemistry.

Surface plasmon resonance and electrochemistry characterization of layer-by-layer self-assembled DNA and Zr4+ thin films, and their interaction with cytochrome c

Through electrostatic layer-by-layer (LbL) assembly, negatively charged calf thymus double stranded DNA (CTds-DNA), and positively charged Zr4+ ions were alternately deposited on gold substrate modified with chemisorbed cysteamine. Thus-prepared three-dimensional DNA networks were characterized by surface plasmon resonance (SPR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and infrared reflection-absorption spectroscopy (IR-RAS). SPR spectroscopy indicates that the effective thickness of DNA monolayer in the (DNA/Zr4+), bilayer was 1.5 +/- 0.1 nm, which corresponds to the surface coverage of 79% of its full packed monolayer. At the same time, a linear increase of film thickness with increasing number of layers was also confirmed by SPR characterizations. The data of XPS and IR-RAS show that Zr4+ ions interact with both the phosphate groups and nitrogenous bases of DNA and load into the framework of DNA. Furthermore, the interactions between this composite film and heme protein cytochrome c (Cyt c) were investigated by SPR spectroscopy and electrochemistry. Compared with the adsorption of Cyt c on DNA monolayer, this composite multilayer film can obviously enhance the amount of immobilized Cyt c confirmed by SPR reflectivity-incident angle (R-theta) curves.

Polyhedral oligomeric silsesquioxane nanocomposite thin films via layer-by-layer electrostatic self-assembly

Fabrication of ultrathin polymer composite films with low dielectric constants has been demonstrated. Octa( aminophenyl) silsesquioxane (OAPS) was synthesized and assembled with poly( acrylic acid) (PAA) and poly( styrene sulfonate) (PSS) via a layer-by-layer electrostatic self-assembly technique to yield nanoporous ultrathin films. The OAPS was soluble in water at pH 3 or lower, and suitable pH conditions for the OAPS/PAA and OAPS/PSS assemblies were determined. The multilayer formation process was studied by contact angle analysis, X-ray photoelectron spectroscopy, atomic force microscopy, quartz crystal microgravimetry, UV-vis spectroscopy, and ellipsometry. The multilayer growth was found to be steady and uniform, and the analysis of the film surface revealed a rough topography due to OAPS aggregates. The incorporation of porous OAPS molecules into the thin films significantly lowered their dielectric constants. The OAPS/PAA multilayer thin film thus prepared exhibited a dielectric constant of 2.06 compared to 2.58 for pure PAA film. The OAPS/PAA multilayer film was heated to effect cross-linking between the OAPS and the PAA layers, and the transformation was verified by reflection-absorption Fourier transform infrared spectroscopy.

Study on the self-packing of SnO2 nanoparticles at the air-hydrosol interface and its composite LB films with arachidic acid

SnO2 nanoparticles were found to self-pack at the air-hydrosol interface and form a nanoparticulate film. The self-packed films were observed under a Brewster angle microscope, and investigated by recording the time evolution of surface pressure and pi-A isotherms. The results show that SnO2 nanoparticles take 3 h to form a complete film at the air-hydrosol interface. Composite monolayers of SnO2 and arachidic acid were obtained by spreading arachidic acid onto a fresh hydrosol surface. Composite Y-type LB films were transferred from the air-hydrosol interface onto substrates, and characterized by FTIR, UV-vis, X-ray diffraction spectroscopy and TEM techniques. The results show that the composite films have good structure, with SnO2 nanoparticles uniformly and compactly distributed in the arachidate matrix. (C) 1998 Elsevier Science S.A. All rights reserved.

Essential and Non-Essential Work of Fracture of PI/SiO2 Hybrid Thin Films

Essential work of fracture (EWF) analysis is used to study the effect of the silica doping level on fracture toughness of polyimide/silica (PI/SiO2) hybrid films. By using double-edge-notched-tension (DENT) specimens with different ligament lengths, it seems that the introduction of silica additive can improve the specific essential work of fracture (w (e) ) of PI thin films, but the specific non-essential work of fracture (beta w (p) ) will decease significantly as the silica doping level increasing from 1 to 5 wt.%, and even lower than that of neat PI. The failure process of the fracture is investigated with online scanning electron microscope (SEM) observation and the parameters of non-essential work of fracture, beta and w (p) , are calculated based on finite element (FE) method.

Modeling Nonlinear Peeling of Ductile Thin Films-Critical Assessment of Analytical Bending Models Using FE Simulations

Three analytical double-parameter criteria based on a bending model and a two-dimensional finite element analysis model are presented for the modeling of ductile thin film undergoing a nonlinear peeling process. The bending model is based on different governing parameters: (1) the interfacial fracture toughness and the separation strength, (2) the interfacial fracture toughness and the crack tip slope angle, and (3) the interfacial fracture toughness and the critical Mises effective strain of the delaminated thin film at the crack tip. Thin film nonlinear peeling under steady-state condition is solved with the different governing parameters. In addition, the peeling test problem is simulated by using the elastic-plastic finite element analysis model. A critical assessment of the three analytical bending models is made by comparison of the bending model solutions with the finite element analysis model solutions. Furthermore, through analyses and comparisons for solutions based on both the bending model and the finite element analysis model, some connections between the bending model and the finite element analysis model are developed. Moreover, in the present research, the effect of different selections for cohesive zone shape on the ductile film peeling solutions is discussed.

Peeling Experiments Of Ductile Thin Films Along Ceramic Substrates - Critical Assessment Of Analytical Models

Two types of peeling experiments are performed in the present research. One is for the Al film/Al2O3 substrate system with an adhesive layer between the film and the substrate. The other one is for the Cu film/Al2O3 substrate system without adhesive layer between the film and the substrate, and the Cu films are electroplated onto the Al2O3 substrates. For the case with adhesive layer, two kinds of adhesives are selected, which are all the mixtures of epoxy and polyimide with mass ratios 1:1.5 and 1:1, respectively. The relationships between energy release rate, the film thickness and the adhesive layer thickness are measured during the steady-state peeling process. The effects of the adhesive layer on the energy release rate are analyzed. Using the experimental results, several analytical criteria for the steady-state peeling based on the bending model and on the two-dimensional finite element analysis model are critically assessed. Through assessment of analytical models, we find that the cohesive zone criterion based on the beam bend model is suitable for a weak interface strength case and it describes a macroscale fracture process zone case, while the two-dimensional finite element model is effective to both the strong interface and weak interface, and it describes a small-scale fracture process zone case. (C) 2007 Elsevier Ltd. All rights reserved.

Structural and magnetic properties of insulating Zn1-xCoxO thin films

Cobalt-doped ZnO (Zn1-xCoxO) thin films were fabricated by reactive magnetron cosputtering. The processing conditions were carefully designed to avoid the occurrence of Co precipitations. The films are c-axis oriented, and the solubility limit of Co in ZnO is less than 17%, determined by x-ray diffraction. X-ray photoemission spectroscopy measurements show Co ions have a chemical valance of 2+. In this paper, hysteresis loops were clearly observed for Zn1-xCoxO films at room temperature. The coercive field, as well as saturation magnetization per Co atom, decreases with increasing Co content, within the range of 0.07