Optical characterization of plasma‐polymerized pyrrole‐N,N,3,5‐tetramethylaniline bilayer thin films

A capacitively coupled parallel‐plate reactor has been used to deposit plasma‐polymerized pyrrole (PPPy), plasma‐polymerized N,N,3,5‐tetramethylaniline (PPTMA), and plasma‐polymerized pyrrole‐N,N,3,5‐tetramethylaniline (PPPy‐PPTMA) bilayer thin films on to glass substrates at room temperature. To deposit the bilayer films, pyrrole monomer has been used as the mother material and N,N,3,5‐tetramethylaniline monomer has been deposited in different deposition time ratios after the pyrrole films were formed. Fourier transform infrared (FTIR) and ultraviolet–visible (UV–vis) spectroscopy techniques have been used to characterize the as‐grown thin films of about 500‐nm thick. The structural analyses by FTIR spectroscopy have indicated that the monomer has undergone the reorganization and the ring structure is retained during the plasma polymerization. From the UV–vis absorption spectra, allowed direct transition (E_qd) and allowed indirect transition (E_qi) energy gaps were determined. The E_qd for PPPy, PPTMA, and PPPy‐PPTMA bilayer films are found to be 3.30, 2.85, and 3.65 eV respectively. On the other hand, the E_qi for the same series are 2.25, 1.80, and 2.35 eV, respectively. From these results, it is seen that the energy gaps of the PPPy‐PPTMA bilayer films have been increased compared with the PPPy and PPTMA films. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Plasma‐polymerized hexamethyldisiloxane films characterized by variable‐energy positron lifetime spectroscopy

Nanometer‐size holes in plasma‐polymerized thin films were characterized by variable‐energy positron lifetime spectroscopy for the first time. Hexamethyldisiloxane (HMDSiO) was plasma‐polymerized at different discharge powers (30–105 W) and monomer pressures (1.0–4.9 Pa). The positron lifetime spectra of deposited films were collected at positron energies of 1 and 5 keV. All films showed a well‐defined long‐lived component due to pick‐off annihilation of ortho‐positronium (o‐Ps). The o‐Ps lifetime τ₃, reflecting the average size of free‐volume holes in the film, increased with an increasing ratio of plasma discharge power, W, and monomer flow rate, F. Based on the empirical relationship between the o‐Ps lifetime and the cavity radius, hole volumes were estimated to be 0.19–0.36 nm³. We also found that the o‐Ps intensity, I₃, depends strongly on the same parameter, W/F. Comparison with infrared (IR) absorption spectroscopy data showed that Ps formation is suppressed in films with fewer organic bonds and higher disorder, i.e., those increasingly inorganic in nature. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2522–2528, 1999     

A study on the characteristics of plasma polymer thin film with controlled nitrogen flow rate

Nitrogen-doped thiophene plasma polymer [N-ThioPP] thin films were deposited by radio frequency (13.56 MHz) plasma-enhanced chemical vapor deposition method. Thiophene was used as organic precursor (carbon source) with hydrogen gas as the precursor bubbler gas. Additionally, nitrogen gas [N₂] was used as nitrogen dopant. Furthermore, additional argon was used as a carrier gas. The as-grown polymerized thin films were analyzed using ellipsometry, Fourier-transform infrared [FT-IR] spectroscopy, Raman spectroscopy, and water contact angle measurement. The ellipsometry results showed the refractive index change of the N-ThioPP film. The FT-IR spectra showed that the N-ThioPP films were completely fragmented and polymerized from thiophene.     

Novel redox‐active polycarbazole‐functionalized polycatechol network films produced by controlled electropolymerization

A novel precursor, 1,2‐bis[6‐(9H‐carbazol‐9‐yl)hexyloxy] benzene (BCHB), was successfully synthesized. Its polycarbazole‐functionalized polycatechol network films, poly{1,2‐bis[6‐(9H‐carbazol‐9‐yl)hexyloxy] benzene} (PBCHB), with good redox activity were formed by the direct anodic oxidation of BCHB in CH₂Cl₂ and boron trifluoride diethyl etherate binary solvent solution. Ultraviolet–visible spectroscopy, Fourier transform infrared spectroscopy, ¹H‐NMR, and matrix‐assisted laser desorption ionization–time of flight mass spectrometry were used to characterize the polymers. The results indicate that the network polymers could be synthesized electrochemically with different polymerized units by controlled electropolymerization. The PBCHB films prepared at low potential were oligomers with short conjugation lengths and were soluble in common organic solvents, whereas the polymers with long conjugation lengths and hyperbranched network structures obtained at high potential were insoluble. The electrosynthesized polymers exhibited blue emission maxima around 450 nm and were much more redshifted than their monomer. The emissions were also brighter; this indicated the polymers are potential good blue‐light emitters. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Conjugated polythiophene/Ni doped ZnO hetero bilayer nanocomposite thin films: Its structural,optical and photoluminescence properties

In this study, synthesis and characterization of plasma polymerized Thiophene/ Nickel doped Zinc Oxide (PTNZO) bilayer nanocomposite films were carried out. Nickel doped zinc oxide (NZO) thin films were obtained by magnetron sputtering technique on glass substrates at 40 W Radio Frequency (RF) power. Plasma polymerized Thiophene (PT) thin films were deposited on the NZO thin films obtained on the glass substrate by Radio Frequency (RF) plasma polymerisation technique. X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM), FTIR and Photoluminescence (PL) analyzes were performed for the characterization of PTNZO hetero bilayer nanocomposite films. In the XRD spectra of PTNZO bilayer nanocomposite thin films, (002) planes were determined as the most basic peak, and it was determined that the intensity of this peak, changed depending on the RF power of polymer thin films. Optical properties of nanocomposite thin films such as transmittance, absorbance and optical band gap were determined by UV–Vis spectroscopy. Optical band gap for PTNZO nanocomposites were 2.72?eV, 2.34?eV, and 2.45?eV, respectively, with increasing RF power. For NZO thin films, this value is 3.12?eV. The optical band gaps calculated from the absorption and transmittance spectra obtained using UV–visible spectroscopy had a good compatibility with those of the optical band spectra calculated from the PL spectra. The tetragonal wurtzite structure of the NZO thin films was examined by SEM analysis. The grain size of NZO nanostructure was found to be approximately 59?nm.     

Synthesis of poly(N‐isopropylacrylamide) under atmospheric pressure plasma conditions

This work is focused on obtaining and characterizing thin films of a certain thermosensitive polymer, i.e., poly(N‐isopropylacrylamide). To obtain such polymers dielectric barrier discharge plasma working at atmospheric pressure in plan–plan geometry was used. The plasma parameters were monitored during polymerization reaction by its electrical and optical signals. The obtained films were analyzed by different techniques such as X‐photoelectron spectroscopy, Fourier transform infrared spectroscopy, atomic force microscopy, contact angle, impedance spectroscopy measurements, and light interferometry for thickness measurements. Chemical analyses of obtained films showed that they sort well with the polymers obtained by other methods in literature. It has been proved that plasma polymerized films have a superhydrophilic character at room temperature, the measured contact angle being around 13°, the lower critical solution temperature was also identified at about 30–31°C. The films' thickness for a 10‐min duration deposition was 400 nm. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Structural, chemical and electrochemical characterization of poly(3,4-ethylenedioxythiophene) (PEDOT) prepared with various counter-ions and heat treatments

Electrochemical deposition of the conjugated polymer poly(3,4-ethylenedioxythiophene) (PEDOT) forms thin, conductive films that are especially suitable for charge transfer at the tissue-electrode interface of neural implants. For this study, the effects of counter-ion choice and annealing parameters on the electrical and structural properties of PEDOT were investigated. Films were polymerized with various organic and inorganic counter-ions. Studies of crystalline order were conducted via X-ray diffraction (XRD). Electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) were used to investigate the electrical properties of these films. X-ray photoelectron spectroscopy (XPS) was used to investigate surface chemistry of PEDOT films. The results of XRD experiments showed that films polymerized with certain small counter-ions have a regular structure with strong (100) edge-to-edge correlations of PEDOT chains at ∼1.3 nm. After annealing at 170 °C for 1 h, the XRD peaks attributed to PEDOT disappeared. PEDOT polymerized with LiClO₄ as a counter-ion showed improved impedance and charge storage capacity after annealing at 160 °C.     

Characterization on polymerized thin films for low-k insulator using PECVD

Plasma polymerized cyclohexane and TEOS hybrid thin films have been deposited on silicon substrates at room temperature with varying RF power by plasma-enhanced chemical vapor deposition (PECVD) method. As-grown thin films were annealed in vacuum. Cyclohexane monomer was utilized as organic precursor and TEOS monomer as inorganic precursor. Hydrogen and argon were used as bubbler and carrier gases, respectively. The as-grown plasma polymerized hybrid thin films were analyzed by FT-IR spectroscopy, hardness and modulus measurements, and electrical properties. Annealed hybrid thin films were also analyzed. The dielectric constant of thin films increases with increasing plasma power.     

Synthesis and characterizations of magnetite nanocomposite films for radiation shielding

Polyvinyl alcohol (PVA) films containing magnetite Fe₃O₄ nanoparticles have been prepared by co‐precipitation method for use in gamma ray shielding and protection. Characterizations of the magnetite/PVA nanocomposite films were investigated by X‐ray diffraction (XRD), transmission electron microscopy (TEM), UV–vis spectroscopy, and magnetization measurements. TEM images showed that the synthesized magnetite particles had about 6–11 nm dimensions. Optical study's results revealed that the optical energy band gaps of thin films range between 1.82 and 2.81 eV at room temperature using UV–visible absorption spectroscopy. The saturation magnetization (MS) value measured by vibrating sample magnetometer VSM was found to be 8.1 emu/g with superparamagnetic nature. The radiation shielding properties such as linear attenuation coefficients (μ ) and half‐value thickness (HVT) for the magnetite nanocomposite films have been obtained experimentally for different photon energies. The results imply that these nanocomposites films are promising radiation shielding materials. POLYM. COMPOS., 38:974–980, 2017. © 2015 Society of Plastics Engineers     

Experimental investigations of semi-crystalline plasma polymerized polypyrrole for surface coating

Plasma polymerized thin film of conducting polypyrrole were deposited at room temperature by plasma enhanced chemical vapor deposition method using pyrrole monomer as precursor. The radio frequency (RF: 13.56 MHz, power supply: 30 W) was applied at constant argon gas pressure for the formation of plasma. The as grown thin films of polypyrrole have been characterized by ellipsometry, Fourier transform infrared spectroscopy (FTIR), UV–vis spectroscopy, atomic force microscopy (AFM), X-ray diffractometry (XRD) and high-resolution transmission electron microscopy (HRTEM). UV–vis spectra showed the optical energy band gap of 2.3 eV. XRD pattern of plasma polymerized polypyrrole has revealed a clear peak at inter-planer separation of 0.687 nm. It was also noticed by HRTEM analysis that the distinguished reflection at d =  0.687 nm has a broadening effect that may be correlated with the crystallinity of the material.     

Exceptionally good,transparent and flexible FeS2/poly(vinyl pyrrolidone) and FeS2/poly(vinyl alcohol) nanocomposite thin films with excellent UV‐shielding properties

Composites of nanocrystalline iron disulfide (FeS₂) coated with poly(vinyl pyrrolidone) (PVP) or poly(vinyl alcohol) (PVA) have been successfully synthesized using a solvothermal process, in which PVP and PVA serve as soft templates. Transparent, flexible thin films of these nanocomposites were prepared from homogeneous solution using a solution‐casting approach. X‐ray diffraction and thermogravimetric analysis and energy‐dispersive X‐ray, Fourier transform infrared and UV‐visible absorption spectroscopic techniques were employed to study the structural and optical properties of these nanocomposite films. UV‐visible spectra in transmission mode reveal the UV‐shielding efficiency of these nanocomposite films and the films are found to be exceptionally good for UV‐shielding applications in the wavelength range 200 to 400 nm. The present work aims at developing transparent and flexible UV‐shielding materials and colour filters using cost‐effective and non‐toxic inorganic–polymer nanocomposites. © 2012 Society of Chemical Industry     

Synthesis and characterization of conducting homopolymers and copolymers of o‐anisidine and o‐toluidine in inorganic and organic supporting electrolytes

The influence of inorganic and organic supporting electrolytes on the electrochemical, optical, and conducting properties of poly(o‐anisidine), poly(o‐toluidine), and poly(o‐anisidine‐co‐o‐toluidine) thin films was investigated. Homopolymer and copolymer thin films were synthesized electrochemically, under cyclic voltammetry conditions, in aqueous solutions of inorganic acids (H₂SO₄, HCl, HNO₃, H₃PO₄, and HClO₄) and organic acids (benzoic acid, cinnamic acid, oxalic acid, malonic acid, succinic acid, and adipic acid) at room temperature. The films were characterized by cyclic voltammetry, ultraviolet–visible spectroscopy, and conductivity measurements with a four‐probe technique. The ultraviolet–visible spectra were obtained ex situ in dimethyl sulfoxide. The optical absorption spectra indicated that the formation of the conducting emeraldine salt (ES) phase took place in all the inorganic electrolytes used, whereas in organic acid supporting electrolytes, ES formed only with oxalic acid. Moreover, the current density and conductivity of the thin films was greatly affected by the nature and size of the anion present in the electrolyte. For the copolymer, the conductivity lay between the conductivity of the homopolymers, regardless of the supporting electrolyte used. The formation of the copolymer was also confirmed with differential scanning colorimetry. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2634–2642, 2003     

Plasma polymerized ferrocene films

This communication describes the formation of high index of refraction polymer thin films using a novel plasma polymerization deposition process. A flowing afterglow plasma reactor was modified to enable sublimation of solid samples into the gas phase for subsequent plasma polymerization. Thin films of plasma polymerized ferrocene were deposited on substrates and subsequently characterized. The refractive index as a function of processing conditions was obtained. Relatively high values of n (∼1.73 at 589 nm) were obtained. The chemical nature of the polymer thin films was characterized using FTIR and XPS spectroscopy. This work demonstrates that plasma polymerization is an enabling technology for the fabrication of photonic thin films that utilize solid state precursors.     

Influence of water addition on the structure of plasma-deposited allyl alcohol polymer films

One hundred and fifty nanometre thick polymer films made of allyl alcohol and H₂O addition were deposited onto aluminium substrates using the radio-frequency (rf) pulsed plasma mode. The structure–property relationships of polymer films were studied in dependence on the precursor ratio allyl alcohol-water. Both the regularity of structure and composition of such thin films in comparison to chemically polymerized allyl alcohol were investigated using by bulk-sensitive Fourier transform infrared spectroscopy (FTIR) in the spectral range of 4000–500 cm^?1 as well as surface-sensitive X-ray photoelectron spectroscopy (XPS). The intention of this work was to increase the yield in OH groups by addition of water to the allyl alcohol precursor. For an unambiguous identification of the functionality of the deposited films, the OH groups were labelled with trifluoroacetic anhydride and subsequently measured by XPS as well as quantitatively by FTIR. As expected, the O/C ratio grew with increasing water admixture by oxidation of both the plasma polymerized allyl alcohol layer to preferably aldehyde and/or carboxylic acid groups. In contrary, the concentration of OH groups in the deposited polymer film decreases dramatically with increasing admixture of water to the allyl alcohol plasma. It has been shown that the additional water has produced preferably higher oxidized C-O_x species with two or three C–O bonds. This fits also very well with the observation that almost no deuterium is introduced into the surface of plasma polymer if D₂O was added instead of H₂O.     

Formation of nanocrystalline and amorphous carbon by high fluence swift heavy ion irradiation of a plasma polymerized polyterpenol thin film precursor

This study aimed to produce graphitic‐polymer nanocomposite thin films via the swift heavy ion irradiation of polyterpenol thin films synthesized from an environmentally sustainable precursor by radio‐frequency plasma enhanced chemical vapor deposition. Atomic force microscopy and scanning electron microscopy revealed fluence‐dependent surface restructuring of the thin films leading to the formation of interconnected island structures, with no discernible delamination from the underlying aluminum substrate. Raman spectroscopy confirmed the development of D and G peaks associated with graphitic materials, whilst Fourier transform infrared spectroscopy indicated retention of the plasma polymer's chemical functionalities (including hydroxyl groups) within the material after irradiation. Graphitic‐polymer nanocomposite films prepared by this dry and solvent‐free process have numerous potential applications in biological assay, organic electronics, and membrane technology. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46498.     

Hybrid polyaniline–TiO2 nanocomposite Langmuir–Blodgett thin films: Self‐assembly and their characterization

Polyaniline (PANi)–titanium dioxide (TiO₂) nanocomposite materials were prepared by chemical polymerization of aniline doped with TiO₂ nanoparticles. Surface pressure–area (π‐A) isotherms of these nanocomposites show phase transformations in the monolayer during compression process. Multiple isotherms indicate that the monolayer of the nanocomposite material can retain its configuration during compression‐expansion cycles. Langmuir–Blodgett thin films of PANi–TiO₂ nanocomposite were deposited on the quartz and indium tin oxide coated conducting glass substrates. Fourier transfer infrared spectroscopy and UV–visible spectroscopy study indicates the presence of TiO₂ in PANi, whereas X‐ray Diffraction study confirmed the anatase phase of TiO₂ and particle size (～nm) of PANi–TiO₂. The morphology of Langmuir–Blodgett films of these nanocomposites was also characterized by atomic force microscopy. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41386.     

Low‐Temperature Deposition of Hexagonal Boron Nitride via Sequential Injection of Triethylboron and N2/H2 Plasma

Hexagonal boron nitride (hBN) thin films were deposited on silicon and quartz substrates using sequential exposures of triethylboron and N₂/H₂ plasma in a hollow‐cathode plasma‐assisted atomic layer deposition reactor at low temperatures (≤450°C). A non‐saturating film deposition rate was observed for substrate temperatures above 250°C. BN films were characterized for their chemical composition, crystallinity, surface morphology, and optical properties. X‐ray photoelectron spectroscopy (XPS) depicted the peaks of boron, nitrogen, carbon, and oxygen at the film surface. B 1s and N 1s high‐resolution XPS spectra confirmed the presence of BN with peaks located at 190.8 and 398.3 eV, respectively. As deposited films were polycrystalline, single‐phase hBN irrespective of the deposition temperature. Absorption spectra exhibited an optical band edge at ~5.25 eV and an optical transmittance greater than 90% in the visible region of the spectrum. Refractive index of the hBN film deposited at 450°C was 1.60 at 550 nm, which increased to 1.64 after postdeposition annealing at 800°C for 30 min. These results represent the first demonstration of hBN deposition using low‐temperature hollow‐cathode plasma‐assisted sequential deposition technique.     

Optoelectronic properties of In-doped SnS thin films

Nanostructured un- and In-doped SnS thin films were deposited on fluorine-doped tin oxide (FTO) substrates via an electrochemical deposition technique. The deposited thin films were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), energy dispersive spectroscopy (EDS), atomic force microscopy (AFM), electrochemical impedance spectroscopy (EIS), photoluminescence (PL) spectroscopy and UV–visible spectroscopy. The XRD patterns demonstrated that all deposited thin films are made of polycrystalline SnS particles. The AFM images illustrated a distinct change in the surface topography of the SnS thin films due to In-doping. The PL spectra showed two blue emission peaks and a green emission peak for all samples. Also, they highlighted a PL peak for the In-doped thin films. The incorporation of In-dopant leads to enhance in the optical absorption of SnS lattice. The optical energy band gap (E_g) of the deposited thin films was estimated using UV–vis spectroscopy, which indicated that In-doping decreases the E_g value of SnS thin films by creating defect levels. The photocurrent results demonstrated a higher photocurrent response and photocurrent amplitude for the In-doped SnS samples relative to the un-doped SnS thin film. The Mott–Schottky analysis revealed p-type conductivity for all samples. In addition, the carrier concentration of SnS was increased after In doping. The EIS spectra declared that In-doping improves the rate of charge transfer for SnS thin films. The charge transfer resistance of In-doped SnS decreased compared to the undoped SnS thin film. Finally, according to the J-V characteristics, the conversion efficiency of the In-doped SnS thin films was higher than that of the un-doped SnS sample. Therefore, the optical and electrical performance of SnS thin films were improved due to In-doping.     

Synthesis and properties of PMMA‐ZrO2 organic–inorganic hybrid films

In this work we report the synthesis process and properties of PMMA‐ZrO₂ organic–inorganic hybrid films. The hybrid films were deposited by a modified sol‐gel process using zirconium propoxide (ZP) as the inorganic (zirconia) source, methyl methacrylate (MMA) as the organic source, and 3‐trimetoxy‐silyl‐propyl‐methacrylate (TMSPM) as the coupling agent between organic and inorganic phases. The films were deposited by dip coating on glass slide substrates from a hybrid precursor solution containing the three precursors with molar ratio 1 : 0.25 : 0.25 for ZP, TMSPM, and MMA, respectively. After deposition, the hybrid thin films were heat‐treated at 100°C for 24 h. The macroscopic characteristics of the hybrid films such as high homogeneity and high optical transparence evidenced the formation of a cross‐linked, interpenetrated organic–inorganic network. The deposited PMMA‐ZrO₂ hybrid films were homogeneous, highly transparent and very well adhered to substrates. Fourier Transform Infra‐Red measurements of the hybrid films display absorption bands of chemical groups associated with both PMMA and ZrO₂ phases. The amounts of organic and inorganic phases in the hybrid films were determined from thermogravimetric measurements. The surface morphology and homogeneity of the hybrid films at microscopic level were analyzed by scanning electron microscopy and atomic force microscopy images. From the analysis of optical transmission and reflection spectra, the optical constants (refraction index and extinction coefficient) of the hybrid films were determined, employing a physical model to simulate the hybrid optical layers. The refraction index of the hybrid films at 532 nm was 1.56. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42738.     

Comparative study of photoelectric properties of regiosymmetrical poly(3,4-dialkoxythiophene)s

A series of regiosymmetrical poly(3,4-dialkoxythiophene)s: poly(3,4-diamyloxythiophene), poly(3,4-dioctyloxythiophene), poly(3,4-di(2-ethyl-1-hexyloxy)thiophene), and poly(3,4-didodecyloxythiophene) were synthesized by the FeCl₃-oxidative approach. All these polymers were evaluated with NMR, FT-IR, gel permeation chromatography (GPC), thermo-gravimetric analysis (TGA), UV–Vis spectroscopy, and photoluminescence (PL). The polymers have excellent solubility in common organic solvents, and TGA studies show that the polymers lost 5% of their weights on heating to 250 °C above. Investigations of the UV–Vis spectroscopy show that the absorption maxima of the polymer thin films are similar to those in solutions, and the optical band gaps of the polymer thin films are ranging from 2.27 to 2.69 eV. In PL spectra, maxima emission peaks of the polymer thin films lie at 527 to 589 nm, embodying colors from green to yellow, and the quantum yields of the polymers are in the range of 22–28%. All the data indicate that the polymers have good solubility, outstanding thermal stabilities, low band gaps, and high PL quantum yields, and they might be excellent polymeric materials for applications in organic light-emitting diodes (OLEDs), light-emitting electrochemical cells, polymer solar cells, and so on.