Effects of confinement on static and dynamical properties of water

Molecular-dynamics results on water confined in a silica pore are reviewed and discussed in connection with experiments performed on water in Vycor and with studies of water in contact with proteins. The properties of confined water are studied as a function of both temperature and hydration level. The interaction of water in the film close to the substrate with the silica atoms induces a strong distortion of the hydrogen bond network. At high hydration levels a double dynamical regime is observed. At low hydration an anomalous diffusion is found upon supercooling with a transition from a Brownian to a non-Brownian regime on approaching the substrate in agreement with results found in studies of water in contact with globular proteins.Received: 1 January 2003, Published online: 14 October 2003PACS: 61.20.-p Structure of liquids - 61.20.Ja Computer simulation of liquid structure     

The kinetics of homogeneous nucleation of silver nanoparticles stabilized by polymers

The formation of Ag nanoparticles synthesized by homogeneous nucleation, stabilized by polymers (PVA and PVP) was monitored by UV–Vis spectrophotometry and transmission electron microscopy. Our aim was to differentiate between the two main phases of particle formation, i.e. nucleation and growth and to characterize their rates with the help of appropriate kinetic equations. Time resolved spectrophotometric measurements revealed that particle formation is an autocatalytic process: a slow, continuous nucleation phase (3–5 min) is followed by a rapid, autocatalytic growth phase where the maximal particle size is 5–7 nm. By freezing the reaction mixture, the process of particle growth can be followed from 5 to 40 min on TEM pictures. The first order rate constants were calculated and they are strongly depend on the polymer concentration. If the growing particles are attached by PEI to the surface of a solid support, the formation of silver nanoparticles can also be followed by atomic force microscopy (AFM) and we can control the particle growth on mica surface. The cross section analysis of the pictures show, that the particle growing process can be also monitored at solid–liquid interface.     

AFM study of BSA adlayers on Au stripes

Thin narrow Au stripes suitable for propagating long-range surface plasmon-polaritons were deposited by evaporation and lift-off on a thermal oxide layer on a silicon substrate, and modified by direct adsorption of bovine serum albumin (BSA). Atomic force microscopy (AFM) measurements reveal that BSA adsorbs onto the Au stripes from phosphate buffer solutions forming an adlayer having an average thickness of about 2 nm (surface mass density of about 2 ng/mm²). Comparisons with a simple adsorption model suggest the side-on adsorption of a single monolayer of BSA followed by denaturation and flattening. The BSA-coated stripes have an increased surface roughness compared to a virgin stripe.     

Improved surface morphology of flow-modulated MOVPE grown AIN on sapphire using thin medium-temperature AIN buffer layer

High-temperature (HT) AIN films were grown on (0 0 0 1) sapphire by low-pressure flow-modulated (FM) metal organic vapor phase epitaxy (MOVPE) with and without inserting a thin medium-temperature (MT) AIN layer. To suppress parasitic reactions between the sources of trimethylaluminum (TMA) and ammonia (NH₃), TMA and NH₃ was introduced to the reactor of MOVPE by alternating supply way. Surface morphology and crystalline quality were characterized by a scanning electronic microscopy (SEM), atomic force microscopy (AFM) and X-ray rocking curve (XRC) measurements of (0 0 0 2) and (10-12) diffractions. The AFM and SEM measurements indicated that the thin MT-AIN layer had a strong influence on the surface morphology of the HT-AIN films. The surface morphology became quite smooth by inserting the thin MT-AIN layer and surface RMS roughness values were 0.84 nm and 13.4 nm for the HT-AIN films with and without inserting the thin MT-AIN buffer layer, respectively. By etching the samples in aqueous KOH solution, it was found that the polarity of AIN films was different, the HT-AIN film with the thin MT-AIN layer could not be etched, indicating that the film had an Al-polar surface; however, the film without the MT-AIN layer was etched, which was explained that that film had a N- or mixed-polar surface. The mechanism for the origin of the different polarity of HT-AIN with and without the thin MT-AIN layer was proposed and discussed in detail.     

Electrochemically deposited photoactive CdIn2Se4 thin films: Structural and optical studies

Electrochemical synthesis of photoactive cadmium-indium-selenide (CdIn₂Se₄) thin films at ambient temperature was reported. The nanocrystalline nature and 1:2:4 elemental chemical stoichiometric ratio for Cd, In and Se were obtained from the X-ray diffraction and energy dispersive X-ray analysis, respectively. Irregular shaped islands of about 400-500 nm in sizes composed of large number of small (∼30-40 nm) spherical grains were confirmed from the atomic force microscopy and the scanning electron microscopy images. The photoelectrochemical measurement of CdIn₂Se₄ film electrode in presence of 1 M polysulphide electrolyte revealed 0.42% photoelectrochemical device conversion efficiency, under the light illumination intensity of 80 mW/cm².     

Thiolated poly(ε-caprolactone) macroligand with vacant coordination sites on gold substrate: Synthesis and surface characterization

Surface-confined telechelic poly(ε-caprolactone) macroligand with two distinct functional groups per polymeric chain has been synthesized and characterized. The molecular microstructure of the macroligand with regard to the properties of the end-capped functionalities and with those on surface substrate has been studied by solution and surface analytical methods (i.e., X-ray photoelectron spectroscopy (XPS), grazing angle reflectance-Fourier transform IR spectroscopy (GA-FTIR), water contact angle measurements, and atomic force microscopy (AFM)) to elucidate the structure and properties of such multifunctional polymer on gold (1 1 1) substrate.     

Polycrystalline silicon films prepared by metal-induced crystallisation using pre- and post-deposited aluminium on amorphous silicon

We report on the successful fabrication of polycrystalline silicon films by aluminium-induced crystallisation (AIC) of Radio frequency (rf) plasma-enhanced chemical vapour deposited (PECVD) a-Si films. The effects of annealing at different temperatures (300 and 400°C), below the eutectic temperature of the Si–Al binary system, on the crystallisation process have been studied. This work emphasises the important role of the position of the Al layer with respect to the Si layer on the crystallisation process. The properties of the crystallised films were characterised using X-ray diffraction, Raman spectroscopy, ellipsometry, field-emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM). With an increase in the annealing temperature, it was found that the degree of crystallisation of annealed a-Si/Al and Al/a-Si films increased. The results showed that the arrangement where the Al was on top of the a-Si had a more prominent effect on crystallisation enhancement than when Al was below the a-Si. The interfacial layer between the Al and a-Si film is crucial because it influences the layer-exchange process during annealing. The oxide layer formed between the Al and the a-Si layers greatly retards the crystallisation process in the case of the Al/Si arrangement. Our investigations suggest that polycrystalline Si films formed by AIC can be used as a seed layer in solar cell fabrication.     

Block copolymer containing poly(3‐hexylthiophene) and poly(4‐vinylpyridine): Synthesis and its interaction with CdSe quantum dots for hybrid organic applications

Poly(3‐hexylthiophene)‐b‐poly(4‐vinylpyridine) diblock copolymer was synthesized by RAFT polymerization of 4‐vinyl pyridine using a trithiocarbonate‐terminated poly(3‐hexylthiophene) macro‐RAFT agent. The optoelectronic properties and the morphology of the block copolymer blends with CdSe quantum dots were investigated. UV‐vis and fluorescence experiments were performed to prove the charge transfer between CdSe and poly(3‐hexylthiophene)‐b‐poly(4‐vinylpyridine) diblock copolymer. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Enhancement of OFET performance of semiconducting polymers containing benzodithiophene upon surface treatment with organic silanes

Poly{4,8‐bis(4‐decylphenylethynyl)benzo[1,2‐b:4,5‐b′]dithiophene} ( P1 ) homopolymer and poly{4,8‐bis(4‐decylphenylethynyl)benzo[1,2‐b:4,5‐b′]dithiophene ‐alt‐thiophene} ( P2 ) alternating copolymer have been synthesized by Stille coupling polymerization. The field‐effect mobilities of both polymers were measured on both untreated and silane‐treated OFET devices. Various silanes were selected to allow an incremental increase in the hydrophobicity of the silicon dioxide dielectric. A direct correlation was observed between the hydrophobicity of the silicon dioxide dielectric surface and the enhancement of the field‐effect mobilities. The highest mobilities for both polymers were measured on the OFET devices treated with heptadecafluoro‐1,1,2,2‐tetrahydro‐decyl‐1‐trimethoxysilane (FS) which generated the most hydrophobic surface. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011