Effect of surface modification on the properties of plasma-polymerized hexamethyldisiloxane thin films

Plasma-polymerized hexamethyldisiloxane (pp-HMDSO) thin films have been deposited in a radiofrequency (RF) remote plasma-enhanced chemical vapor deposition (PECVD) system, on different types of substrates: silicon wafers, glass, quartz crystals, and chemiresistor structure. The as-grown thin films have been post treated in two types of reactive plasmas produced in SF₆ and O₂ gases. The effect of this surface modification on different properties of the as-grown pp-HMDSO thin film (chemical structure, elemental composition, surface morphology, film density and thickness, optical bandgap, and electrical resistivity) has been investigated. It is found that SF₆ plasma and O₂ plasma surface modifications of the as-grown pp-HMDSO thin film induce property changes different from each other. SF₆ plasma converted the as-grown pp-HMDSO film to a more porous material and caused a narrowing of its optical band gap of about 33%, while O₂ plasma induced a lowering of film electrical resistivity of about two orders of magnitude.     

Spectroscopic study on chemical structure of plasma-polymerized hexamethyldisiloxane

A plasma-polymerized material was produced from hexamethyldisiloxane vapor by a glow discharge polymerization technique. Spectroscopic interpretation of the chemical structure of the polymerized hexamethyldisiloxane was studied by spectroscopic means such as IR, XPS, and NMR. The plasma polymer was barely soluble in the usual organic solvents, although it contained a small amount of the monomer and its oligomers. The IR spectrum indicated that the polymer consisted of Si? CH₃, Si? O, Si? CH₂, and Si? H groups. The surface of the polymer was found to retain structural units similar to the monomer from the XPS measurement. On the other hand, the ¹³C and ²⁹Si high-resolution, solid-state NMR measurements revealed that the plasma polymer was highly crosslinked with a variety of conformations and a number of O atoms surrounding a Si atom. Results from the XPS and NMR spectra suggested that the bulk of the polymer was more oxidized than the surface layer; Si atom was preferentially oxidized. A hypothetical chemical structure was proposed for the polymerized hexamethyl-disiloxane.     

Surface structure and photoluminescence properties of AZO thin films on polymer substrates

Al‐doped zinc oxide (AZO) thin films were deposited on indium tin oxide (ITO) coated polyethylene terephthalate (PET) substrates by radio frequency (RF) magnetron sputtering method at room temperature. The effects of film thickness on the surface structure and the photoluminescence properties of the films were investigated by atomic force microscopy (AFM), secondary ion mass spectroscopy (SIMS) and room temperature photoluminescence (PL). AFM analysis showed that the surface of all films was extremely flat and uniform at nanoscale. Root mean square (RMS) value of the surface roughness which scanned the surface area of 3 µm by 3 µm and grain size increased with increasing the film thickness. Thus, the surface morphology of the films became rough because of the coarse grains. The depth profile of AZO layers was analyzed by SIMS. It was found that the thickness of the AZO layer is almost same with the desired film thickness. The PL intensity of the dominant peak decreased and shifted slightly towards the shorter wavelengths with increasing the film thickness. According to the relationships between luminescence intensity and crystalline characteristics, it was observed that the intensity of the peak decreased by the increased surface area of the grains. Copyright © 2014 John Wiley & Sons, Ltd.     

Magnetic properties of lanthanum orthoferrite fine powders prepared by different chemical routes

Fine powders of lanthanum iron oxide, LaFeO₃, have been prepared by solid state reaction as well as sol-gel synthesis and nebulized spray pyrolysis. Structures, morphologies and magnetic susceptibility measurements of these powders have been examined. The powders prepared by all the three low-temperature routes contain nearly spherical particles with an average diameter of 40 nm. These samples show a lower Neel temperature than the powder prepared by solid state reaction besides showing much lower magnetic susceptibility at low temperatures. Dedicated to Professor C N R Rao on his 70th birthday     

Effects of the grain boundary on phase structure and surface morphology of TiO2 films prepared by MAO technology

Some porous titanium dioxide (TiO₂) films were prepared on flexible substrates by the method of micro‐arc oxidation (MAO) combined with magnetron sputtering (MS). The original material of MAO was Ti films prepared by MS, which was composed of columnar crystals with a diameter of less than 150 nm. The results indicated that the phase of the oxide films was mainly anatase structure, and the pore diameter of the films was about 100–300 nm. However, the phases of the oxide films prepared on Ti plates, which composed of equiaxed crystals with a diameter of 2–5 µm, were anatase and rutile structure. The pore diameter of those films was about 4–10 µm. It was suggested that the changes of the grain boundary structure of the original material could have a significant impact on the phase structure and surface morphology of the resultant TiOx films. Copyright © 2011 John Wiley & Sons, Ltd.     

Electron Spectroscopy (ESCA) on technical oxidic thin films prepared by different methods

Summary Technical oxidic thin films (SiO₂, TiO₂, Ta₂O₅ and WO₃) prepared by different deposition methods (dip coating, evaporation and ion plating) have been analysed by electron spectroscopy (ESCA). Different peak structures were obtained in the spectra depending on the deposition technique and the conditions during the coating process. The differences in the spectra due to the binding states were analysed by means of deconvolution and fitting of the spectra. The obtained results are discussed in connection with further investigations.     

Synthesis,structure and capacitive properties of cobalt hydroxide films on stainless steel substrates

Cobalt (hydro)oxide films on AISI 304 stainless steel and sintered metal fibre filter Bekipor ST 20AL3 were prepared using electrochemical deposition from neutral cobalt acetate solutions under galvanostatic conditions. Deposited films were structurally characterized using X-ray diffraction, Fourier transform infrared spectroscopy and scanning electron microscopy. All electrochemical measurements were performed in aqueous NaOH solution. Capacitive behavior of different films was evaluated using cyclic voltammetry data. The highest specific capacitance (965 F g^?1) was reached when Bekipor ST 20AL3 mesh was used as a support for electroactive substance.      

Rodlike/flexible polyimide composite films prepared from soluble poly(amic diethyl ester) precursors: Miscibility,structure, and properties

Homogeneous precursor/precursor solutions with various compositions were obtained with appreciably high solid contents in N-methyl-2-pyrrolidone from soluble poly(amic diethyl ester) precursors of rodlike poly(p-phenylene biphenyltetracarboximide) (BPDA-PDA) and flexible poly(4,4′-oxydiphenylene biphenyltetracarboximide) (BPDA-ODA), which are hydrolytically more stable as well as more soluble than the corresponding poly(amic acid)s being equilibrated with the constituent monomers. Both optical microscopic and light scattering measurements showed that the dried precursor blend films and resultant polyimide composite films were optically transparent, regardless of compositions and process conditions. The composite films showed a single T_g behavior. However, for the composite of 30 wt % BPDA-PDA dispersed in the matrix of 70 wt % BPDA-ODA, a smectic crystalline-like aggregation of the BPDA-PDA component was detected on wide-angle x-ray diffraction patterns, indicative of microscopic phase separation between the two components. This phase separation was not detected on the optical microscopy, light scattering, and dynamic mechanical thermal analysis because of their resolution limits: Optical microscopy has a resolution of submicrometers, whereas dynamic mechanical thermal analysis and light scattering have a resolution of ca. 50 Å. Therefore, it is speculated that in the composite films BPDA-PDA and BPDA-ODA polyimide molecules have demixed on the scale of a few nanometers. The mean long periodicity, which was estimated from the small-angle x-ray scattering pattern, varied from 134 to 170 Å as the content of BPDA-ODA component increased. In addition, mechanical properties of the composite films were characterized. ©1995 John Wiley & Sons, Inc.     

X-ray absorption fine structure study of amorphous metal oxide thin films prepared by photochemical metalorganic deposition

The oxidation state and local geometry of the metal centers in amorphous thin films of Fe₂O₃ (Fe³⁺ oxidation state), CoFe₂O₄ (Co²⁺/Fe³⁺ oxidation states), and Cr₂O₃ (Cr³⁺ oxidation state) are determined using K edge X-ray absorption near-edge structure (XANES) spectroscopy and extended X-ray absorption fine structure (EXAFS) spectroscopy. The metal oxide thin films were prepared by the solid-state photochemical decomposition of the relevant metal 2-ethylhexanoates, spin cast as thin films. No peaks are observed in the X-ray diffraction patterns, indicating the metal oxides are X-ray amorphous. The oxidation state of the metals is determined from the edge position of the K absorption edges, and in the case of iron-containing samples, an analysis of the pre-edge peaks. In all cases, the EXAFS analysis indicates the first coordination shell consists of oxygen atoms in an octahedral geometry, with a second shell consisting of metals. No higher shells are observed beyond 3.5 Å for all samples, indicating the metal oxides are truly amorphous, consistent with X-ray diffraction results.     

Crystal‐structure dependence of electroactive properties in differently prepared poly(vinylidene fluoride/hexafluoropropylene) copolymer films

The electroactive properties of two random copolymers of vinylidene fluoride (VDF) and hexafluoropropylene (HFP) were studied. The compositions were 95/5 and 85/15 mol % P(VDF/HFP). For each composition, three different film‐preparation methods were used—solvent casting, melt‐pressed quenched, and melt‐pressed slow‐cooled. The ferroelectric properties observed were strongly dependent on the preparation methods of the films as well as the HFP molar content of the samples. The highest remanent polarizations (P_r) obtained from electric displacement versus electric field (D‐E) hysteresis data are 80 and 50 mC/m² for the 5 and 15% HFP solvent‐cast samples, respectively. The slow‐cooled samples do not exhibit any ferroelectric behavior for either the 5 or 15% HFP copolymers. It was also observed that both the 5 and 15% HFP slow‐cooled samples have a smaller electrostrictive response relative to the other two types of samples. Wide‐angle X‐ray diffraction and DSC results suggest that the 5% HFP sample has a higher crystallinity relative to the 15% HFP sample for each preparation method. In addition, different crystal phases form in the samples resulting from the different preparation methods. Fourier transform infrared results suggest that the slow‐cooled samples are in the nonpolar α phase, whereas the quenched and solvent‐cast samples are more likely in the polar β phase. The slow‐cooled samples do not show a switching peak in their nonpolar α‐phase crystalline state. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2793–2799, 2001     

Coating and water permeation properties of SiO2 thin films prepared by the sol-gel method on nylon-6 substrates

Nylon-6 substrates were coated with SiO₂ thin films by the sol-gel method and their water permeability coefficient was evaluated. Methyltriethoxysilane (MTES) and tetraethoxysilane (TEOS) were used as starting materials. The addition of MTES to TEOS has enabled the formation of crack-free thin films on the substrates. The thin films strongly adhered to the substrates. The water permeability coefficients of nylon-6 substrates coated with these thin films decreased with the increase in the ratio of TEOS to the total alkoxides. The pretreatment of the nylon-6 substrates with -aminopropyltriethoxysilane was found to be effective to suppress the water permeability. The water permeability was suppressed by about 40% under the optimal condition.     

Effects of surface chemical composition on the early growth stages of alpha-sexithienyl films on silicon oxide substrates

In organic field effect transistors, charge transport is confined to a narrow region next to the organic/dielectric interface. It is thus extremely important to determine the morphology and the molecular arrangement of the organic films at their early growth stages. On a substrate of technological interest, such as thermally grown silicon oxide, it has been recently found that alpha-sexithienyl aggregates made of flat-lying molecules can simultaneously nucleate besides islands made of molecules standing vertical. In this paper, we investigate the effects due to variations in surface chemical composition on alpha-sexithienyl ultrathin film formation. Flat-lying molecules are no longer detected when Si-OH groups present at the surface are chemically removed but also when the Si-OH or Si-H group density is maximized. This gives evidence that variations in the surface chemical composition can largely affect the nucleation and growth processes of organic/dielectric interfaces. We hypothesize that isolated OH groups can interact with alpha-sexithienyl molecules and anchor them down flat with respect to the surface.     

Effect of bias and temperature on the bulk and surface properties of gold-containing plasma-polymerized fluorocarbons

Gold-containing plasma-polymerized fluorocarbon thin films have been deposited in an RF glow discharge fed with hexafluoroethane, while a gold target was simultaneously sputtered. Tile temperatureT _s and RF-induced biasU _s of a third electrode, used as a substrate holder, were separately varied. The influence ofT _s andU _s on the plasma and file lihn characteristics were individually studied using actinometric optical emission spectroscopy, X-ray photoelectron spectroscopy, infrared spectroscopy, and measurements of optical transmission and surface contact angles. IncreasingU _s (up to –200 V) andT _s (up to 90°C) resulted in similar effects, namely a higher degree of cross-linking, higher gold concentration, better film stability with time, and increased wettability. A key role of the energy flux of particles impinging on the growing surface has been shown to account far the experimental results.On leave from the Faculty of Mathematics and Physics, Charles University, Praha, Czechoslovakia.     

Plasma polymerization of aniline on different surface functionalized substrates

The plasma polymerization of aniline on different surface functionlized low-density polyethylene (LDPE) substrates was investigated, and the resulting polymer was characterized by X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, scanning electron microscopy, and atomic force microscopy. The results showed that the structure of plasma-polymerized polyaniline was rather different from polyaniline synthesized by conventional chemical and electrochemical methods. This difference may be due to extensive coupling reactions and cross-linking reactions during the plasma polymerization process. The use of acrylic acid graft copolymerized LDPE substrate significantly enhanced the adhesion of the polyaniline to the substrate over that observed with pristine LDPE. The plasma polymerized polyaniline can be rendered electrically conductive if the polymerization is carried out on a polystyrenesulfonic acid-coated LDPE substrate. Conductivity can also be induced by acid protonation of the polyaniline by HClO(4). The reaction of the plasma-polymerized polyaniline with viologen grafted on the substrate under UV irradiation and with AuCl(3) and Pd(NO(3))(2) in acid solutions was also investigated.     

Preparation and characterization of thin films of SiO(x) on gold substrates for surface plasmon resonance studies

We report here on the fabrication and characterization of stable thin films of amorphous silica (SiO(x)) deposited on glass slides coated with a 5 nm adhesion layer of titanium and 50 nm of gold, using the plasma-enhanced chemical vapor deposition (PECVD) technique. The resulting surfaces were characterized using atomic force microscopy (AFM), ellipsometry, contact angle measurements, and surface plasmon resonance (SPR). AFM analysis indicates that homogeneous films of silica with low roughness were formed on the gold surface. The deposited silica films showed excellent stability in different solvents and in piranha solution. There was no significant variation in the thickness or in the SPR signal after these harsh treatments. The Au/SiO(x) interfaces were investigated for their potential applications as new surface plasmon resonance sensor chips. Silica films with thicknesses up to 40 nm allowed visualization of the surface plasmon effect, while thicker films resulted in the loss of the SPR characteristics. SPR allowed further the determination of the silica thickness and was compared to ellipsometric results. Chemical treatment of the SiO(x) film with piranha solution led to the generation of silanol surface groups that have been coupled with a trichlorosilane.     

Thermoelectric properties of nanocomposite thin films prepared with poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) and graphene

Carbon nanotubes (CNTs), either single wall carbon nanotubes (SWNTs) or multiwall carbon nanotubes (MWNTs), can improve the thermoelectric properties of poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT?:?PSS), but it requires addition of 30-40 wt% CNTs. We report that the figure of merit (ZT) value of PEDOT?:?PSS thin film for thermoelectric property is increased about 10 times by incorporating 2 wt% of graphene. PEDOT?:?PSS thin films containing 1, 2, 3 wt% graphene are prepared by solution spin coating method. X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy analyses identified the strong π-π interactions which facilitated the dispersion between graphene and PEDOT?:?PSS. The uniformly distributed graphene increased the interfacial area by 2-10 times as compared with CNT based on the same weight. The power factor and ZT value of PEDOT?:?PSS thin film containing 2 wt% graphene was 11.09 μW mK(-2) and 2.1 × 10(-2), respectively. This enhancement arises from the facilitated carrier transfer between PEDOT?:?PSS and graphene as well as the high electron mobility of graphene (200,000 cm(2) V(-1) s(-1)). Furthermore the porous structure of the thin film decreases the thermal conductivity resulting in a high ZT value, which is higher by 20% than that for a PEDOT?:?PSS thin film containing 35 wt% SWNTs.     

Composition and structure of platinum-containing thin composite films prepared from silica sols

Chemical processes that can occur during aging of sols based on water–alcohol solutions of tetraethoxysilane (TEOS) and hexachloroplatinic acid and during formation of films from these sols are analyzed by the results of visible and UV spectroscopy and X-ray powder diffraction. The sizes and compositions of the platinum particles that are formed in xerogels and in thin films on the nanometer and submicron levels are estimated based on X-ray crystallography, energy dispersive spectral analysis, high-resolution scanning and transmission electron microscopy, and grazing incidence small-angle X-ray scattering studies.     

Effects of polymer concentration and coagulation temperature on the properties of regenerated cellulose films prepared from LiOH/urea solution

Aqueous 5 wt% LiOH/12 wt% urea solution pre-cooled to −12 °C has a more powerful ability to dissolve cellulose compared to that of NaOH/urea and NaOH/thiourea solution system. The influences of the cellulose concentration and coagulation temperature on the structure, pore size and mechanical properties of the cellulose films prepared from LiOH/urea system were investigated. The cellulose films exhibited good mechanical properties either at wet or dry state and their pore size and water permeability at wet state can be controlled by changing the cellulose concentration or coagulation temperature. With a decrease of the coagulation temperature, the mechanical properties and optical transmittance of the cellulose films enhanced, as a result of the formation of relative smaller pore size and denser structures. This work provided a promising way to prepare cellulose films with different pore sizes at wet state and good physical properties at dry state.