Electronic conductivity of pyrrole and aniline thin films polymerized by plasma

In this article, we present a study of the influence of temperature and humidity on the electric conductivity of polyaniline and polypyrrole thin films doped with iodine and synthesized by plasma (PAn/I and PPy/I, respectively). The polymers presented the characteristic ohmic conduction mechanism via electrons; however, the conductivity was much lower than that presented by the polymers obtained by traditional chemical oxidation. We submitted the polymers to heating–cooling cycles to study the temperature dependence of the conductivity. During the heating stage of the cycles, the electric conductivity of PPy/I showed a strong dependence on the humidity content. However, during the cooling step, the plots of conductivity, as a function of the inverse temperature of PPy/I and PAn/I, showed typical Arrhenius behavior. The activation energy of PPy/I had an average value of 1.1 ± 0.1 eV and was independent of the reaction time, whereas PAn/I presented a more complex behavior with activation energies that depended on the reaction time and the regional crystallinity induced in the heating step of the cycles. All the activation energies were below 2 eV, which places them in the semiconductor regime. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 3247–3255, 2000     

Reusable thin film photocatalyst of Fe‐doped TiO2 deposited by ECR plasma

The paper presents an improved method of depositing nanocrystalline thin films of Fe‐doped TiO₂ to be used as a reusable cyclic photocatalyst for degrading the organic pollutants. The technique of electron cyclotron resonance plasma‐enhanced chemical vapor deposition was employed with titanium tetra‐isopropoxide (C₁₂H₂₈O₄Ti) and ferrocene (C₁₀H₁₀Fe) as precursors of Ti and Fe, respectively. Optical emission spectroscopy was used to identify the reactive species, to determine the electron temperature and the ion density during deposition. The films were characterized using optical absorption and photoluminescence spectra, whereas the morphological analysis was carried out with scanning electron microscopy. Strong adhesion of the deposited films with the substrate ruled out any possibility of TiO₂ particles being leached out. It was confirmed by observing the degradation rate of the same film repeatedly. Cyclic use of the film for the catalytic reactions thus makes the process much user friendly for the water treatment. Copyright © 2014 John Wiley & Sons, Ltd.     

Plasma-polymerized polyaniline films: Synthesis and characterization

The radio-frequency plasma polymerization technique was used to polymerize aniline onto polymer substrates including perfluorinated ethylene propylene copolymer. The plasma-polyaniline films were characterized by ultraviolet/visible absorption spectroscopy, Fourier transform infrared spectroscopy, electron spin resonance, X-ray photoelectron spectroscopy, scanning electron microscopy, and contact angle measurements. Preliminary conductivity measurements were also carried out. It was demonstrated that the chemical and physical characteristics of the plasma-polymerized poly-aniline films changed significantly with discharge conditions, indicating the possibility for tailoring the structure and properties of the polyaniline films by optimizing the discharge conditions. In particular, the contents of quinoid sequences and aliphatic crosslinking moieties were found to increase with increasing power input and/or discharge duration. By contrast, the number of free radicals trapped in the polyaniline films and their mobility were shown to increase with decreasing the power input and/or discharge duration within the plasma conditions covered in this study. Furthermore, a correlation was found between surface hydrophilicity of the resultant plasma-polyaniline films and the atomic ratio of C to N. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 633–643, 1998     

Characterization of plasma polymerized hydrocarbons using CP–MAS 13C-NMR

Plasma polymerized hydrocarbons made from ethane and methane were produced under different reactor conditions and probed by solid-state carbon-13 nuclear magnetic resonance (¹³C-NMR) with cross-polarization and magic-angle sample spinning. NMR experiments provided structural information about the plasma polymers. The conditions of low power, high hydrocarbon gas flow rate, and no added hydrogen gas appeared to give the highest amount of nonprotonated sp³ hybridized carbons in the films for the reactor design used. The use of methane or ethane as reactor gas did not affect plasma polymer structure significantly.     

Plasma deposition of thin films from a fluorine-containing cyclosiloxane

Thin films have been deposited from radio-frequency glow discharges fed with vapors of a silicon- and fluorine-containing organic compound, namely 2,4,6-tris[(3,3,3-trifluoropropyl) (methyl)] cyclotrisiloxane, in mixture with argon. 2,4,6-tris[(3,3,3-trifluoropropyl)(methyl)]cyclotrisiloxane A triode reactor has been utilized to deposit films by independently changing substrate temperature and bias-induced ion-bombardment. Laser interferometry, electron spectroscopy for chemical analysis and Fourier-transform infrared spectroscopy have been used to monitor film growth rate and composition. Results unambiguously show an activating effect of the ion-bombardment, which confirm the validity of the ion-assisted deposition model utilized for the plasma deposition of both teflon- and silicone-like films. In our experiments, low substrate temperature and bias conditions results in films with a “monomer-like” stoichiometry, while drastic conditions give origin to materials with a completely different composition and a markedly increased hardness. © 1994 John Wiley & Sons, Inc.     

Electrical,optical, and structural characterization of p‐type N‐doped SnO thin films prepared by thermal oxidation of sputtered SnNx thin films

We present a study of electrical and optical properties of nitrogen‐doped tin oxide thin films deposited on glass by the DC Magnetron Sputtering method. The deposition conditions to obtain p‐type thin films were a relative partial pressure between 7% and 11% (N₂ and/or O₂), a total working pressure of 1.8 mTorr and a plasma power of 30 W. The deposited thin films were oxidized after annealing at 250°C for 30 minutes. X‐ray diffraction results showed that the as‐deposited thin films exhibit a Sn tetragonal structure, and after annealing, they showed SnO tetragonal structure. X‐ray photoelectron spectroscopy results showed the presence of nitrogen in the samples before and after annealing. The measured physical parameters of the thin films were optical band gap between 1.92 and 2.68 eV, resistivity between 0.52 and 5.46 Ωcm, a concentration of p‐type carriers between 10¹⁸ and 10¹⁹ cm^?3, and a Hall mobility between 0.1 and 1.94 cm²V^?1s^?1. These thin films were used to fabricate p‐type thin film transistors.     

Synthesis and characterization of aluminum–polyaniline thin films and membranes

Polyaniline (PAni) films of different intrinsic oxidation states, including emeraldine salt, emeraldine base and leucoemeraldine base, were synthesized. Free‐standing membranes and thin film bilayers of aluminum–polyaniline were fabricated by magnetron sputter deposition of aluminum onto polyaniline films. Aluminum–polyaniline samples were analyzed by transmission electron microscopy (TEM) to investigate the microstructures of specimens, including cross‐sectional TEM micrographs of the metal‐polyaniline interfacial structure not previously reported in the literature. Auger electron spectroscopy (AES) and X‐ray photoelectron spectroscopy (XPS) were employed to study the chemical bonding and interaction between deposited aluminum and polyaniline at the interface. Results indicated that the intrinsic oxidation state of the polyaniline influenced the chemistry of the aluminum–polyaniline interface. Distinct interaction between aluminum and polyaniline in the emeraldine salt‐form was observed. However, there was no evidence of direct interactions of the aluminum with emeraldine base and leucoemeraldine base polyaniline. Copyright © 2005 John Wiley & Sons, Ltd.     

On the influence of electron energy on iodine‐doped polyaniline formation by plasma polymerization

The influences that both electron energy and density of a plasma bear on thin film formation are examined in the case of iodine‐doped polyaniline polymerization. The plasma was produced by means of 13.5‐MHz radiofrequency–generated glow discharges in low‐pressure (ca. 10⁻² mbar) air between electrodes. Four representative inner regions of the reactor were selected according to the electron incidence. Given the uneven energy distribution found on the inside of this kind of reactors, variations in the polymer structure formed in the presence of iodine were found and studied by elemental analysis, thermogravimetry, infrared spectroscopy, and X‐ray diffraction. The results indicate that the electric conductivity of polyaniline by plasma is a function of the iodine content and that such content is a function of the combined conditions of both reactor and plasma. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 175–183, 2001     

Synthesis and characterization of PAni–SiO2 and PTh–SiO2 nanocomposites' thin films by plasma polymerization

In the present work, we explore the possibility to deposit polyaniline–silicon dioxide (PAni–SiO₂) and polythiophene–silicon dioxide (PTh–SiO₂) nanocomposites through a plasma polymerization route. The films were generated by spraying of mixtures of nano-sized silica particles dispersed in the liquid monomer into a plasma stream of the DC-plasma discharge reactor. The silica in the resulted polymer matrix changes the conduction mechanisms varying from ohmic to ballistic and traps inducing the space charged limited currents (SCLC). The silica modifies the morphology and composition of the deposited films.     

Studies of Cu‐doped ZnS thin films prepared by sputtering technique

Radio frequency magnetron sputtering technique has been used to deposit Cu‐doped ZnS thin films on glass and n‐type Si(100) substrates at room temperature. Crystalline structure, surface morphology, and elemental oxidation states have been studied by X‐ray diffraction, field emission scanning electron microscopy, atomic force microscopy, and X‐ray photoelectron spectroscopy. Ultraviolet–visible spectroscopy has been employed to measure the transmittance, reflectance, and absorbance properties of coated films. The deposited thin films crystallize in zinc blende or sphalerite phases as proved by X‐ray diffraction analysis. The intensity of diffraction peaks decreases with increasing the dopant concentrations. The predominant diffraction peak related to (111) plane of ZnS is observed at 28.52° along with other peaks. The peak positions are shifted to higher angles with an increase of Cu concentrations. X‐ray photoelectron spectroscopy studies show that Cu is present in +1 oxidation state. Transmittance, reflectance, and absorbance properties of the deposited films have a slight variation with dopant concentrations. Copyright © 2016 John Wiley & Sons, Ltd.     

Single‐phase TiO2 formation by plasma oxidation of titanium thin films

Synthesis of titanium oxide film by plasma oxidization of the metallic films is investigated. Argon/oxygen gas mixture in the pressure range 30 × 10^?2 mbar is used for plasma processing at a frequency of 250 kHz. The plasma‐oxidized films are annealed in a tube furnace in argon atmosphere to establish crystalline‐phase formation. X‐ray diffraction and Raman spectroscopic results manifest peaks corresponding to rutile TiO₂. Ultraviolet‐Visible (UV‐Vis) spectroscopic analysis confirms the bandgap of rutile TiO₂, and photoluminescence spectra exhibit peaks due to oxygen defects. Homogeneity across the film's thickness and the nature of the film substrate interface is studied by depth profiling acquired using secondary ion mass spectrometry. Copyright © 2015 John Wiley & Sons, Ltd.     

Nanofibrous polyaniline thin film prepared by plasma‐induced polymerization technique for detection of NO2 gas

A nanofibrous polyaniline (PANI) thin film was fabricated using plasma‐induced polymerization method and explored its application in the fabrication of NO₂ gas sensor. The effects of substrate position, pressure, and the number of plasma pulses on the PANI film growth rate were monitored and an optimum condition for the PANI thin film preparation was established. The resulting PANI film was characterized with UV–visible spectrophotometer, FTIR, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The PANI thin film possessed nanofibers with a diameter ranging from 15 to 20 nm. The NO₂ gas sensing behavior was studied by measuring the change in electrical conductivity of PANI film with respect to NO₂ gas concentration and exposure time. The optimized sensor exhibited a sensitivity factor of 206 with a response time of 23 sec. The NO₂ gas sensor using nanofibrous PANI thin film as sensing probe showed a linear current response to the NO₂ gas concentration in the range of 10–100 ppm. Copyright © 2009 John Wiley & Sons, Ltd.     

Preparation of films from aluminum acetylacetonate by plasma sputtering

Aluminum acetylacetonate has been reported as a precursor for the deposition of alumina films using different approaches. In this work, alumina‐containing films were prepared by plasma sputtering this compound, spread directly on the powered lowermost electrode of a reactor, while grounding the substrates mounted on the topmost electrode. Radiofrequency power (13.56 MHz) was used to excite the plasma from argon atmosphere at a working pressure of 11 Pa. The effect of the plasma excitation power on the properties of the resulting films was studied. Film thickness and hardness were measured by profilometry and nanoindentation, respectively. The molecular structure and chemical composition of the layers were analyzed by Fourier transform infrared spectroscopy and energy dispersive spectroscopy. Surface micrographs, obtained by scanning electron microscopy, allowed the determination of the sample morphology. Grazing incidence X‐ray diffraction was employed to determine the structure of the films. Amorphous organic layers were deposited with thicknesses of up to 7 µm and hardness of around 1.0 GPa. The films were composed by aluminum, carbon, oxygen and hydrogen, their proportions being strongly dependent on the power used to excite the plasma. A uniform surface was obtained for low‐power depositions, but particulates and cracks appeared in the high‐power prepared materials. The presence of different proportions of aluminum oxide in the coatings is ascribed to the different activations promoted in the metalorganic molecule once in the plasma phase. Copyright © 2013 John Wiley & Sons, Ltd.     

Characterization of thin polymer‐like films formed by plasma polymerization of methylmethacrylate: A neutron reflectivity study

The microstructure of the plasma‐polymerized methylmethacrylate (ppMMA) films is characterized using neutron reflectivity (NR) as a function of the plasma reaction time or film thickness. Variation in the crosslink density normal to the substrate surface is examined by swelling the film with a solvent, d‐nitrobenzene (dNB). In the presence of dNB, uniform swelling is observed throughout the bulk as well as at the air surface, and silicon oxide interfaces. The results indicate that the MMA film prepared by plasma polymerization (ppMMA) has a uniform crosslink density from air surface to substrate surface. Additionally, the scattering length density of the plasma‐polymerized MMA film (SLD ≈ 0.750 × 10⁻⁶ Å⁻²) is much lower than that of a conventional PMMA film (SLD = 1.177 × 10⁻⁶ Å⁻²). The increase in film thickness following dNB sorption is 7.5% and at least 36% for the ppMMA and PMMA films, respectively. This suggests that the films formed by plasma polymerization are different from conventional polymers in chemical structure. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2522–2530, 2004     

Perfluoro(methylcyclohexane) plasma polymer thin film: Growth,surface morphology,and properties investigated by scanning thermal microscopy

Scanning thermal microscopy (SThM) has been used for the visualization and characterization of an ultrathin plasma polymer film of perfluoro(methylcyclohexane) at a submicrometer level. The morphology, molecular dynamics, and lateral homogeneity of the ultrathin film have all been examined precisely with SThM. The growth of the plasma polymer film on a silicon wafer (Si‐wafer) has also been precisely determined using a new burning‐hole technique. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1392–1400, 2005     

Thickness dependence of free‐standing thin films

Below a critical thickness, of about 60 nm, the glass transition temperature of polystyrene (PS) films decreases with film thickness, as demonstrated using free‐standing films. A geometrical model is developed here describing this phenomenon in the case of ideal (Gaussian) chains. This model, which can be considered as an application of the free volume model, assumes that the decrease of the glass transition temperature from thick to ultrathin films is due to the modification of the interpenetration between neighboring chains. The theoretical curve deduced from the model is in excellent agreement with the PS experimental results, without using any adjustable parameters. From these results, it can be concluded that new chain motions, usually buried in bulk samples, are expressed by the presence of the surface. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 10–17, 2007     

透光导电金属及氧化铂半导体薄膜的制备与表征

通过PPh~3对“非保护型”铂金属纳米簇进行表面修饰,并将其萃取至甲苯中,制备的PPh~3修饰的Pt金属钠米簇于空气中可自发地在玻璃表面生长出均匀透光的金属钠米簇薄膜。该金属钠米簇薄膜经空气中加热处理后可转化为透光导电的氧化铂半导体薄膜。考察了金属钠米簇薄膜生长过程中UV-vis吸收光谱的变化。采用SEM和TEM等方法,表征了纳米簇的粒径及膜的多孔结构,由此解释了其透光原因。研究了薄膜的导电性与处理条件的关系,并采用XPS表征了处理过程中的物质变化。初步探索了PPh~3-Pt纳米簇自发成膜过程的机理,确定了氧气在此过程中的重要作用。     

Conducting graft copolymers of poly(3‐methylthienyl methacrylate) with pyrrole and thiophene

A thiophene‐functionalized methacrylate monomer (3‐methylthienyl methacrylate) was synthesized via the esterification of 3‐thiophene methanol with methacryloyl chloride. The methacrylate monomer was polymerized by free‐radical polymerization in the presence of azobisisobutyronitrile as the initiator. Graft copolymers of poly(3‐methylthienyl methacrylate) (PMTM2) and polypyrrole and of PMTM2 and polythiophene were synthesized by constant‐potential electrolyses. p‐Toluene sulfonic acid, sodium dodecyl sulfate, and tetrabutylammonium tetrafluoroborate were used as the supporting electrolytes. PMTM2‐coated platinum electrodes were used as anodes in the polymerization of pyrrole and thiophene. Moreover, the oxidative polymerization of poly(3‐methylthienyl methacrylate) (PMTM1) was studied with FeCl₃ as the oxidant. The self‐polymerization of PMTM1 was also investigated by galvanostatic electrolysis both in dichloromethane and in propylene carbonate. The structures of PMTM1 and PMTM2 were investigated by several spectroscopic and thermal methods. The grafting process was elucidated with conductivity measurements, Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, and scanning electron microscopy studies. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4131–4140, 2002     

CdS和CdSe薄膜的制备及其光电化学性质

本文采用简易的化学水浴沉积法和自牺牲模板法制备CdS、CdSe薄膜,对两种薄膜进行了XRD表征,比较了两种薄膜的紫外吸收光谱并研究了CdS、CdSe薄膜作为太阳能电池中的光阳极时所产生的光电流和光电压,对两种薄膜的电化学性能进行了比较.     

Synthesis and characterization of polyaniline doped with organic acids

Spectroscopic [UV–visible and Fourier transform IR (FTIR)] and thermal properties of chemically synthesized polyanilines are found to be affected by varying the protonation media (acetic, citric, oxalic, and tartaric acid). The optical spectra show the presence of a greater fraction of fully oxidized insulating pernigraniline phase in polyaniline doped with acetic acid. In contrast, the selectivity in the formation of the conducting phase is higher in oxalic acid as a protonic acid media. The FTIR spectra of these polymers reveal a higher ratio of the relative intensities of the quinoid to benzenoid ring modes in acetic acid doped polyaniline. Scanning electron micrographs revealed a sponge‐like structure derived from the aggregation of the small granules in acetic acid and oxalic acid doped polyaniline. A three‐step decomposition pattern is observed in all the polymers, regardless of the protonic acid used for the doping. The second step loss related to the loss of dopant is found to be higher in the oxalic acid doped polymer. In accordance with these results the conductivity is also found to be higher in oxalic acid doped material. The temperature dependent conductivity measurements show the thermal activated behavior in all the polymers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2043–2049, 2004