Percolation approach to film formation from surfactant-free polystyrene particles

In this study, a film formation process from surfactant-free polystyrene (PS) latex particles is reported. Steady state fluorescence (SSF) and photon transmission (UVV) techniques were used to study the evolution of film formation. The latex films were prepared from pyrene (P)-labeled PS particles at room temperature and annealed at time intervals of 2.5?min above the glass transition temperature (T _g) of PS. During the annealing processes, the transparency of the film changed considerably. Fluorescence intensity (I _0P) from P was measured after each annealing step to monitor the stages of film formation. Evolution of transparency of latex films were monitored by using photon transmission intensity, I _tr. A drastic increase in I _tr and I _0P above the critical annealing times, t _r and t _c were attributed, respectively to percolation behavior of PS material from one side to the other side of the latex film. Critical exponents, β of percolation clusters were measured and found to be around 0.35 and 0.25 for I _tr and I _0P measurements, respectively.     

Molecular weight effect on void closure and packing at different annealing temperatures during film formation from hard latex particles

Latex particles with high and low molecular weight (HM and LM) poly(methyl methacrylate) (PMMA) were used to prepare two sets of films with various latex contents separately. These films were annealed above the glass transition temperature. A UV-Visible (UVV) technique was used to measure the transmitted photon intensity, I _tr during film formation from latex particles. Transmitted photon intensity from HM and LM films increased as the annealing temperature increased. A void closure equation was derived for I _tr by using the Vogel-Fulcher viscosity equation. It is observed that as the latex film thickness, d, increased void closure constant, B, and viscosity increased in both HM and LM films. For a given thickness, d, the lower viscosity of particles in HM films results in better packing than in LM films.     

Film formation from PS latex doped PNIPAM hydrogels at various heating and cooling rates

Film formation from polystrene (PS) latex doped poly(N-isopropylacrylamide) (PNIPAM) hydrogels was studied by using photon transmission technique. The transmitted light intensity, I _tr was monitored during film formation process. Films were prepared by annealing, 10 wt% PS doped PNIPAM particles at five different heating and cooling rates at temperatures ranging from 10 to 100°C. I _tr presented a hysteresis loops during heating–cooling cycles, which were explained by void closure and void reconstruction processes. The corresponding activation energies were measured during reversible film formation process. Void closure and void reconstruction models were introduced to produce the activation energies.     

Film formation from TiO2-polystyrene latex composite: a fluorescence study

This work reports the use of the steady state fluorescence (SSF) technique for studying film formation from TiO₂ covered polystyrene (PS) latex particles. The composite films were prepared from pyrene (P)-labeled PS particles by covering them with TiO₂ at room temperature and then annealed at elevated temperatures in 10 min time interval above glass transition (T _g) temperature of polystyrene. Five different composite films were studied in various TiO₂ layer contents. Fluorescence intensities I _P from P were measured after each annealing step to monitor the stages of film formation. Films showed considerable increase in I _P above the certain onset temperature called minimum film forming temperature, T ₀. Void closure and interdiffusion stages were modeled and related activation energies were determined and found to be 23.12 and 92.80 kJ mol^?1, respectively.     

Superconductivity and normal electrical conductivity of amorphous lead films nucleated with molybdenum

Lead films vapor quenched onto nucleating monolayers of Mo or W exhibit strong lattice disorder and can be considered to be amorphous. The amorphous-to-crystalline transformation temperatureT _tr is indicated by a sharp drop of the electrical resistivity in the course of annealing.T _tr is found to be proportional tod ^–2 for Pb thicknessd smaller than 30 nm. The superconducting transition temperatureT _c is by 0.6 to 1 K smaller in the amorphous state than after crystallization. In both states,T _c is proportional tod ^–1. Prenucleation with about half a monolayer of Mo leads to quite the sameT _c depression as observed earlier by Strongin et al. on Pb films vapor quenched onto predeposited films of SiO, Ge or Al₂O₃. For comparison, experiments have been carried out with 2.5 nm Ge predeposits. As with Mo prenucleation, a well defined transformation temperatureT _tr of about the same value has been observed.T _c of bulk amorphous Pb can be extrapolated to be about 6.6 K.     

Dissolution of Al2O3-polystyrene latex composites: a fluorescence study

This work reports the use of the steady state fluorescence (SSF) technique to study dissolution of a composite film formed from a mixture of Al₂O₃ and polystyrene (PS) latex particles. The composite films were cast from dispersion of pyrene (P)-labeled PS particles in Al₂O₃ solution at room temperature and annealed at 280°C temperature for 10 min. Eight different composite films were studied in various latex contents. Toluene was used as dissolution agent. Fluorescence intensities I _P from P were monitored during dissolution. Fickian diffusion was employed to model the dissolution processes. Dissolution coefficients, D _d, were measured and found to be increased at high PS content in the composite films.     

Electrical,optical and fluorescence percolations in P(VAc-co-BuA)/MWCNT composite films

Effects of multiwall carbon nanotube (MWCNT) addition on the electrical conductivities, optical transparencies and fluorescence emissions of poly(vinyl acetate-co-butyl acrylate) (P(VAc-co-BuA))/MWCNT composite films were studied. Optical transmission, fluorescence emission and two point probe resistivity techniques were used to determine the variations of the optical, fluorescence and electrical properties of the composites, respectively. Transmitted photon intensity (I _tr), fluorescence emission intensity (I _fl) and surface resistivity (ρ _s) of the composite films were monitored as a function of MWCNT mass fraction (M) at room temperature. All these measured quantities of the composites were decreased by increasing the content of MWCNT in the composite. The conductivity and the optical results were attributed to the classical and site percolation theories, respectively. The fluorescence results, however, possessed both the site and classical percolation theories at low and high MWCNT content regions, respectively.     

Organic dopant added polyvinylidene fluoride based solid polymer electrolytes for dye-sensitized solar cells

The effect of phenothiazine (PTZ) as dopant on PVDF/KI/I₂ electrolyte was studied for the fabrication of efficient dye-sensitized solar cell (DSSC). The different weight percentage (wt%) ratios (0, 20, 30, 40 and 50%) of PTZ doped PVDF/KI/I₂ electrolyte films were prepared by solution casting method using DMF as a solvent. The following techniques such as Fourier transform infrared (FT-IR), differential scanning calorimetry (DSC), X-ray diffractometer (XRD) and AC-impedance analysis have been employed to characterize the prepared polymer electrolyte films. The FT-IR studies revealed the complex formation between PVDF/KI/I₂ and PTZ. The crystalline and amorphous nature of polymer electrolytes were confirmed by DSC and XRD analysis respectively. The ionic conductivities of polymer electrolyte films were calculated from the AC-impedance analysis. The undoped PVDF/KI/I₂ electrolyte exhibited the ionic conductivity of 4.68×10⁻⁶ S cm⁻¹ and this value was increased to 7.43×10⁻⁵ S cm⁻¹ when PTZ was added to PVDF/KI/I₂ electrolyte. On comparison with different wt% ratios, the maximum ionic conductivity was observed for 20% PTZ-PVDF/KI/I₂ electrolyte. A DSSC assembled with the optimized wt % of PTZ doped PVDF/KI/I₂ electrolyte exhibited a power conversion efficiency of 2.92%, than the undoped PVDF/KI/I₂ electrolyte (1.41%) at similar conditions. Hence, the 20% PTZ-PVDF/KI/I₂ electrolyte was found to be optimal for DSSC applications.     

Structure and hardness of a-C:H films prepared by middle frequency plasma chemical vapor deposition

a-C:H films were prepared by middle frequency plasma chemical vapor deposition (MF-PCVD) on silicon substrates from two hydrocarbon source gases, CH₄ and a mixture of C₂H₂ + H₂, at varying bias voltage amplitudes. Raman spectroscopy shows that the structure of the a-C:H films deposited from these two precursors is different. For the films deposited from CH₄, the G peak position around 1520 cm⁻¹ and the small intensity ratio of D peak to G peak (I(D)/I(G)) indicate that the C-C sp³ fraction in this film is about 20 at.%. These films are diamond-like a-C:H films. For the films deposited from C₂H₂ + H₂, the Raman results indicate that their structure is close to graphite-like amorphous carbon. The hardness and elastic modulus of the films deposited from CH₄ increase with increasing bias voltage, while a decrease of hardness and elastic modulus of the films deposited from a mixture of C₂H₂ + H₂ with increasing bias voltage is observed.     

Photovoltaic activity in a ZnSe/PEO–chitosan blend electrolyte junction

Thin films of ZnSe and PEO–chitosan blend polymer doped with NH₄I and iodine crystals were prepared to form the two sides of a semiconductor electrolyte junction. ZnSe was electrodeposited on indium tin oxide (ITO) conducting glass. The polymer is a blend of 50 wt% chitosan and 50 wt% polyethylene oxide. The polymer blend was complexed with ammonium iodide (NH₄I), and some iodine crystals were added to the polymer–NH₄I solution to provide the I⁻/I³⁻redox couple. The room temperature ionic conductivity of the polymer electrolyte is 4.32 × 10⁻⁶ S/cm. The polymer film was sandwiched between the ZnSe semiconductor and an ITO glass to form a ZnSe/polymer electrolyte/ITO photovoltaic cell. The open circuit voltage (V _oc) of the fabricated cells ranges between 200 to 400 mV and the short circuit current between 7 to 10 μA.     

Nanoparticles for dewetting suppression of thin polymer films used in chemical sensors

Addition of fullerenes (C₆₀ or buckyballs) to a linear polymer has been found to eliminate dewetting when a thin (∼50 nm) film is exposed to solvent vapor. Based on neutron reflectivity measurements, it is found that the fullerenes form a coherent layer approximately 2 nm thick at the substrate – polymer film interface during the spin-coating process. The thickness and relative fullerene concentration (∼29 vol%) is not altered during solvent vapor annealing and it is thought this layer forms a solid-like buffer shielding the adverse van der Waals forces promoted by the underlying substrate. Several polymer films produced by spin- or spray-coating were tested on both silicon wafers and live surface acoustic wave sensors demonstrating fullerenes stabilize many different polymer types, prepared by different procedures and on various surfaces. Further, the fullerenes drastically improve sensor performance since dewetted films produce a sensor that is effectively inoperable.     

Combinatorial study of a gold nanoparticle infusion process in a polymer film

A novel two-step process is described for infusion of gold nanoparticles (5–20 nm typical diameter) into a polymer film. The technique is demonstrated for the first time in a thermoplastic polyurethane elastomer (TPU). An amine-functional monomer, 2-(diethylamino)ethyl methacrylate, and a free-radical photoinitiator are infused into the surface of the TPU, followed by photopolymerization. An amine-functional semi-interpenetrating network (SIPN) is created within a shallow (~100 μm) surface layer. In the second step, a gold salt, HAuCl₄·3H₂O, is infused into the SIPN from a ternary solvent mixture, and redox reaction with the immobilized amine functional groups produces Au⁰ nanoparticles. Combinatorial processing is conducted to visualize the interdependent effects of two variables, monomer soak time (t ₁) and gold salt solution soak time (t ₂). Combinatorial infusion is accomplished by creating orthogonal gradients in t ₁ and t ₂ in a square TPU plate, allowing examination of sample color, particle size, and polydispersity over a wide range of parameter space. Small angle X-ray scattering (SAXS) is employed as non-invasive means to characterize the Au⁰ particles at three locations in the plate. SAXS measurements are validated by TEM analysis of Au⁰ particle size in a reference sample. A rationale is developed for changing particle size and polydispersity through variation of simple process parameters.     

Crystallization Kinetics of Lamellar Crystals Confined in Polymer Thin Films

We used dynamic Monte Carlo simulations to investigate the crystallization kinetics of flat-on lamellar polymer crystals in variable thickness films. We found that the growth rates linearly reduced with decreasing film thickness for the films thinner than a transition thickness d_t , while they were constant for the films thicker than d_t . Moreover, the mean stem lengths (crystal thickness) we calculated decreased with film thickness in a similar way to the growth rates, and the intramolecular crystallinities we calculated confirmed the film thickness dependence of the crytsal thickness. Besides, the crystal melting rates in thin films were calculated and increased with decreasing film thickness. We proposed a new interpretation on the film thickness dependence of the crystal growth rate in thin films, suggesting that it is dominated by the crystal thickness in terms of the driving force term (l–l _min) expressed by Sadler, rather than the chain mobility based on experiments. The crystal thickness can determine whether a crystal grows or melts in a thin film at a fixed temperature, indicating the reversibility between the crystal growth and melting.     

Photoconductivity of poly-<Emphasis Type="Italic">p</Emphasis>-xylylene + CdS nanocomposite films over a wide temperature range

For poly-p-xylylene + CdS (PPX + CdS) nanocomposite films, the dependences of the photo-conductivity σ _ph (T) on the concentration C of CdS nanoparticles, intensity and wavelength of exciting light, and temperature T within 15–300 K are examined. An appreciable photocurrent appears at C ≥ 10 vol %, when a large percolation cluster of CdS nanoparticles is formed. The photocurrent spectrum is compared to the absorption spectrum of the film. The photocurrent I _ph (P) increases with the intensity of light flux P in a wavelength range near 435 nm according to the I _ph (P) ∼ P ⁿ power law, where n < 1. At 15 K, the photoconductivity of films with C ≈ 11.5 and 13.5 vol % is higher than that of a pure CdS film (C = 100 vol %) by factors of ≈100 and ≈30, respectively. For films with C > 11.5 vol %, the σ _ph (T) dependence at low T exhibits a metal-like character (σ _ph (T) decreases with increasing temperature). Atomic force microscopy is used to examine the surface topography of PPX + CdS films, which is found to be strongly dependent on the concentration of nanoparticles. The dark conductivity and photoconductivity of nanocomposite films arise due to the thermo- and photoexcitation transfer of electrons from the CdS nanoparticles to the PPX matrix with the formation of an electronic double layer at the PPX matrix-large percolation CdS cluster interface, a process that populates the phenyl rings of the adjacent PPX layer with excess electrons. As a result, various mechanisms of electron transfer in the polymer matrix can be realized: Mott’s hopping conduction mechanism with variable-range hopping in the matrix between CdS clusters and the metal-like behavior of the conductivity in the polymer shell of the large cluster at low temperatures. The polymer shell contains excess electrons on the phenyl rings -C₆H₄- in the composition of anion-resonances -C₆H₄⁻-.     

Solvent-related effects in MAPLE mechanism

To study the role of the solvent and of the laser fluence in the matrix-assisted pulsed laser evaporation (MAPLE) process, we used a soft polymer (polydimethylsiloxane—PDMS) as “sensing surface” and toluene as solvent. Thin films of the PDMS polymer were placed in the position of the growing film, while a frozen toluene target was irradiated with an ArF laser at the conventional fluences used in MAPLE depositions (60–250 mJ/cm²). Apart the absence of solute, the MAPLE typical experimental conditions for the deposition of thin organic layers were tested. The effects on the PDMS films of the toluene target ablation, at different fluences, were studied using atomic force microscopy and contact angles measurements. The results were compared with the effects produced on similar PDMS films by four different treatments (exposure to a drop of the solvent, to saturated toluene vapors and to plasma sources of two different powers). From this comparative study, it appears that depending on the MAPLE experimental conditions: (1) the MAPLE process may be “semidry” rather than purely dry (namely the solvent is likely to be present in the deposition environment near the growing film), (2) the solvent, if sufficiently volatile, is in form of vapor molecules (neutral, ionized and probably dissociated) rather than in liquid phase near the substrate and (3) at relatively high laser fluences (>150 mJ/cm²), the formation of an intense plasma plume results which can damage/affect a soft substrate as well as a growing polymer film.     

ESR study on radiation chemical processes in polyvinyl alcohol films at 77°k

Abstract

Trapped electrons (e_t ^?) were detected in irradiated PVA films at 77°K. Yield of e_t ^? was decreased as evaporating water from the films, indicating that water molecules contribute to construct pre-existing traps in the polymer. The radical produced at 77°K was identified as a precursor of the radical produced at room temperature.     

On the dynamics and disentanglement in thin and two-dimensional polymer films

We present results from molecular dynamics simulations of strictly two-dimensional (2D) polymer melts and thin polymer films in a slit geometry of thickness of the order of the radius of gyration. We find that the dynamics of the 2D melt is qualitatively different from that of the films. The 2D monomer mean-square displacement shows a t^8/15 power law at intermediate times instead of the t^1/2 law expected from Rouse theory for nonentangled chains. In films of finite thickness, chain entanglements may occur. The impact of confinement on the entanglement length N_e has been analyzed by a primitive path analysis. The analysis reveals that N_e increases strongly with decreasing film thickness.     

Study of ion transport and materials properties of K+-ion conducting solid polymer electrolyte (SPE): [(1-x) PEO: xCH3COOK]

Study of ion transport behavior in K⁺-ion conducting solid polymer electrolyte (SPE) films: [(1-x) PEO: xCH₃COOK] has been reported. Poly (ethylene oxide) PEO has been used as polymeric host and potassium acetate: CH₃COOK as complexing salt. SPE films in varying salt concentrations have been prepared by hot-press cast method. SPE film: [95PEO: 5CH₃COOK] has been identified as Optimum Conducting Composition (OCC) with room temperature conductivity (σ _rt) ~ 2.74 × 10⁻⁷ S/cm. As a consequence of salt complexation in polymeric host, σ _rt-enhancement of approximately two orders of magnitude was achieved in SPE OCC film. Ion transport property has been characterized in terms of ionic conductivity (σ), total ionic (t _ion)/cation (t ₊) transference numbers using different ac/dc techniques. Temperature-dependent conductivity measurement was done to explain mechanism of ion transport and to evaluate activation energy (E _a). XRD, FTIR, and DSC techniques were used to study materials property in SPE OCC film which also confirmed the complexation of salt in the polymeric host as well as increase in degree of amorphousity.

     

O2掺杂对SiCOH低k薄膜结构与电学性能的影响

以十甲基环五硅氧烷(D5)和氧气(O₂)作为反应气体，采用电子回旋共振等离子体化学气相沉积(ECR-CVD)方法制备了k＝2.62的SiCOH薄膜.研究了O₂掺杂对薄膜结构与电学性能的影响.结果表明，采用O₂掺杂可以在保持较低介电常数的前提下极大地降低薄膜的漏电流，提高薄膜的绝缘性能，这与薄膜中Si-O立体鼠笼、Si-OH结构含量的提高有关. 关键词： SiCOH薄膜 2掺杂')" href="#">O₂掺杂 介电性能 键结构     

Synthesis of nanostructured SiC films during pulsed photon treatment of Si in a carbon-containing atmosphere

The phase composition, orientation, substructure, and morphology of the films formed during pulsed photon treatment of a single-crystal Si surface by xenon lamp irradiation (λ = 0.2–1.2 μm) and polycrystalline Si films on SiO₂-Si in a gaseous atmosphere (C₃H₈)_0.2(C₄H₁₀)_0.8 are investigated using the methods of transmission electron microscopy, high-energy electron diffraction, atomic force microscopy, and IR-spectroscopy. The irradiation time (the duration of the pulse packet) varied from 1.5 to 2.0 s, which corresponded to variations in the incident’s irradiation energy (E _p ) from 215 to 285 J · cm⁻². The threshold value of E _p was determined. The films of SiC and Si are characterized by a nanocrystalline substructure and biaxial texture, corresponding to different deviations of grains from parallel epitaxial orientation. The portion of epitaxially oriented grains rising to the film surface is increasing with an increase in E _p and the film thickness. Under the conditions necessary for the formation of a eutectic melt in the near-surface zone, the crystallization yielding the formation of a uniaxial texture takes place. During the synthesis on doped poly-Si films the forming SiC film inherits the texture of the layered substructure of the initial Si’s film blocks.