Atomic force microscopy enabled roughness analysis of nanostructured poly (diaminonaphthalene) doped poly (vinyl alcohol) conducting polymer thin films

The Atomic Force Microscopy (AFM) helps in evaluating parameters like amplitude or height parameters, functional or statistical parameters and spatial parameters which describe the surface topography or the roughness. In this paper, we have evaluated the roughness parameters for the native poly (vinyl alcohol) (PVA), monomer diaminonaphthalene (DAN) doped PVA, and poly (diaminonaphthalene) (PDAN) doped PVA films prepared in different solvents. In addition, distribution of heights, skewness and Kurtosis moments which describe surface asymmetry and flatness properties of a film were also determined. At the same time line profiles, 3D and 2D images of the surface structures at different scanning areas i.e. 5 × 5 μm² and 10 × 10 μm² were also investigated. From the roughness analysis and the surface skewness and coefficient of Kurtosis parameters, it was concluded that for PVA film the surface contains more peaks than valleys and the PDAN doped PVA film has more valleys than peaks. It was also found that the PDAN doped PVA film with acetonitrile solvent was used for substrate in electronics applications because the film gives less fractal morphology. Thus, the AFM analysis with different parameters suggested that the PDAN doped PVA films are smooth at the sub-nanometer scale.     

High ionic conductive behavior of cyanoethylated polyvinylalcohol- and polyacrylonitrile-based electrolytes

New type polymer electrolyte films based on poly(acrylonitrile), (PAN), and cyanoethylated poly(vinyl alcohol), (CN-PVA), were prepared and their conducting behaviors were investigated. CN-PVA was prepared from poly(vinyl alcohol), (PVA) and acrylonitrile in the presence of sodium hydroxide and quaternary ammonium halide as a phase transfer catalyst. Free standing PAN- and CN-PVA-based electrolyte films were prepared by casting the propylene carbonate (PC) solution containing PAN, CN-PVA and LiClO₄ and removing some amount of PC. Ionic conductivity of the electrolyte film, (PAN)10(CN-PVA) 10(LiClO₄)8(PC)4 composite film was 14.6 mS cm^− 1 at 30 °C and 22.4 mS cm^− 1 at 60 °C. FTIR results for the electrolyte films suggest that the nitrile groups in the CN-PVA matrix mainly interact with the lithium ions in the films and enhance dissolution of the lithium salt in the electrolyte films.     

Effect of solvent on the characteristics of nanostructured composites of poly (1-naphthylamine) with poly (vinyl alcohol)

Efficient utilization of inherently conducting polymers in nano technological applications faces the challenge to assemble them into highly ordered structures which may yield novel properties. The present study reports for the first time the synthesis and characterization of nanostructured poly (1-naphthylamine) (PNA) dispersed polyvinyl alcohol (PVA) composites. The composites were prepared by loading PNA from 2 wt% to 10 wt% in PVA in aqueous as well as nonaqueous media. The composites were characterized by UV–visible spectroscopy, TEM, stress–strain studies, electrical conductivity measurements and moisture absorption studies under controlled humidity. A discrete but uniform distribution of nanoparticles was obtained in PNA/PVA composites synthesized in water having particle size between 5 and 30 nm. A self assembled network of nanostructured PNA particles was obtained in case of PNA/PVA composites synthesized in N-methylpyrolidone (NMP) with particle sizes between 10 and 65 nm. The variation in the nanostructured morphology of PNA particles in PVA matrix in the two cases resulted from the pronounced interaction of PVA with NMP through hydrogen bonding. This leads to the formation of a homogeneous matrix that facilitates the formation of a self assembled network of PNA nano particles. In case of PNA/PVA composites synthesized in water, lower affinity of PVA towards water was responsible for a discrete, agglomerate free distribution of PNA particles. We have found that the PNA/PVA nano composite synthesized in water exhibited good mechanical properties and electrical conductivity (8.1 × 10⁻¹ S/cm) as well as lowest moisture absorption (4 wt%) which holds potential for use in semiconductor and biomedical devices.     

PPV/PVA/ZnO nanocomposite prepared by complex precursor method and its photovoltaic application

In this article, we describe a new method to prepare a ZnO and conjugated polymer nanocomposite and its application in bulk-heterojunction solar cells. The composite was composed of zinc oxide (ZnO) and poly(phenylene vinylene)/poly(vinyl alcohol) (PPV/PVA). For the preparation, the composite was prepared first through the complex reaction between Zn²⁺ ion and –OH of the PVA–PPV precursor by simply mixing zinc salts and a PVA–PPV precursor aqueous solution at 70 °C. By addition of a concentrated aqueous ammonia into the system, highly regular Zn(OH)₂ nanodots were formed and dispersed in the PVA/PPV precusor mixed solution. The PVA/PPV precursor can well bind Zn²⁺ ion through complex interaction, so act as a template to direct the distribution of ZnO in the process. The nanocomposite films were finally obtained by solution casting and subsequently treated by heating samples at 160 °C for 6 h. TEM observations showed that ZnO nanodots uniformly dispersed in PVA–PPV mixtures. The resulting nanocomposite films possess a large interfacial area between the electron donor and acceptor of the bulk-heterojunction. Improved charge seperation and collection are evidenced by the large photoluminescence intensity difference between pure PPV and composites films, which result in the increase in both open circuit voltage and short circuit current of the hybrid solar cells.     

Excellent UV absorption in spin-coated thin films of oleic acid modified zinc oxide nanorods embedded in Polyvinyl alcohol

The aim of the study is to investigate the optical properties of spin-coated, highly transparent nanocomposite films of oleic acid modified ZnO (Zinc oxide) nanorods embedded in Polyvinyl alcohol (PVA) matrix. Pristine and oleic acid (OA) modified ZnO nanorods have been prepared by wet chemical synthesis and are characterized by X-ray diffraction, FESEM, TEM and FT–IR spectroscopy techniques. The optical properties of ZnO/PVA films are studied using UV–visible absorption and Photoluminescence (PL) spectroscopy. The results show that the optical absorption of the films in the UV region is quite high and more than 95% absorption is observed in films prepared from OA modified ZnO nanorods. The excellent UV absorption at around 300 nm offers prospects of applications of these films as efficient UV filters in this wavelength region. The PL spectrum of pristine ZnO nanorods shows almost white light emission whereas OA modified ZnO nanorods have a more intense peak centered in the blue region. The PL emission of OA modified ZnO/PVA film shows appreciable increase in intensity compared to the film obtained with pristine ZnO. The surface modification of ZnO by the polymer matrix removes defect states within ZnO and facilitates sharp near band edge PL emission at 364 nm.     

Investigation of reduced graphene oxide effects on ultra-violet detection of ZnO thin film

The reduced graphene oxide (rGO) incorporated ZnO thin films were fabricated by dip-coating method. The Raman and FT-IR spectra of 0.075 wt% incorporated composite film showed reduction of GO in composite film. The transmittanceProd. Type: FTP spectra have shown that rGO incorporation increase the visible light absorption of ZnO thin film while the calculated band gaps of samples were decreased from 3.28 to 3.25 eV by increasing the rGO content. The linear trend of I–V curve suggests an ohmic contact between ZnO and rGO. Besides, it was found that by increasing the rGO content, the electrical resistivity was decreased from 4.32×10² Ω cm for pure ZnO film to 2.4×10¹ Ω cm for 0.225 wt% rGO incorporated composite film. The composite photodetectors not only possessed a desirable UV photosensitivity, but also the response time of optimum sample containing 0.075 wt% rGO was reduced to about one-half of pure ZnO thin film. Also, the calculated signal to noise (SNR) showed that highly conductive rGO in composite thin films facilitate the carrier transportation by removing the trapping centers. The mechanism of photoresponsivity improvement of composite thin films was proposed by carrier transportation process.     

Nanocomposite materials based on poly(vinyl chloride) and bovine serum albumin modified ZnO through ultrasonic irradiation as a green technique: Optical,thermal, mechanical and morphological properties

In this project, physicochemical properties of poly(vinyl chloride) (PVC) reinforced by ZnO nanoparticles (NPs) were studied. Firstly, ZnO NPs were modified with bovine serum albumin (BSA) as an organo-modifier and biocompatible substance through ultrasound irradiation as environmental friendly, low cost and rapid means. Nanocomposite (NC) films were prepared by loadings of various ratios of ZnO/BSA NPs (3, 6 and 9 wt%) inside the PVC. Structural morphology and physical properties of the ZnO-BSA NPs and NC films were investigated via Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis (TGA), transmission electron microscopy and field emission scanning electron microscopy. According to the obtained information from the TGA, an increase in the thermal stability can be clearly observed. Also the results of contact angle analysis indicated with increasing percent of ZnO/BSA NPs into PVC the hydrophilic behaviors of NCs were increased.     

Carbon nanotube–ZnO nanocomposite electrodes for supercapacitors

Carbon nanotube (CNT)–zinc oxide (ZnO) nanocomposite and gel poly(vinyl alcohol)–phosphomolybdic acid were employed as the electrode and electrolyte of the experimental supercapacitor cell, respectively. The ZnO nanodots were deposited onto CNT films by ultrasonic spray pyrolysis in different times. The results of electrochemical measurements showed that the electrode with ZnO deposited in 5 min had the optimal capacitive properties among the experimental series, with a lowest interfacial electron transfer resistance, a very high capacitance of 323.9 F/g and good reversibility in the repetitive charge/discharge cycling test.     

Epitaxial ZnO thin films grown by pulsed electron beam deposition

In this work, the pulsed electron beam deposition method (PED) is evaluated by studying the properties of ZnO thin films grown on c-cut sapphire substrates. The film composition, structure and surface morphology were investigated by means of Rutherford backscattering spectrometry, X-ray diffraction and atomic force microscopy. Optical absorption, resistivity and Hall effect measurements were performed in order to obtain the optical and electronic properties of the ZnO films. By a fine tuning of the deposition conditions, smooth, dense, stoichiometric and textured hexagonal ZnO films were epitaxially grown on (0001) sapphire at 700 °C with a 30° rotation of the ZnO basal plane with respect to the sapphire substrate. The average transmittance of the films reaches 90% in the visible range with an optical band gap of 3.28 eV. Electrical characterization reveals a high density of charge carrier of 3.4 × 10¹⁹ cm^?3 along with a mobility of 11.53 cm²/Vs. The electrical and optical properties are discussed and compared to ZnO thin films prepared by the similar and most well-known pulsed laser deposition method.     

Characteristics of ZnO MSM UV photodetector with Ni contact electrodes on poly propylene carbonate (PPC) plastic substrate

In this study, we report the fabrication of ZnO metal-semiconductor-metal UV photodetector (MSM UV PD) by deposition ZnO thin film on poly propylene carbonate (PPC) plastic substrate using direct current (DC) sputtering technique, and Nickel (Ni) contact as electrodes. The structural, optical and electrical properties of the ZnO thin film were investigated by using atomic force microscopy (AFM), X-Ray diffraction (XRD) measurement, and photoluminescence (PL). The electrical characteristics of the detector were investigated using the current–voltage (I–V) measurements, the dark- and photo-currents were found to be 1.04 and 93.80 μA, respectively. Using forward dark conditions at 5 volt; the barrier height Φ_B was calculated to be 0.675 eV. Under incident wavelength of 385 nm, it was found that the maximum responsivity (R) of the Ni/ZnO/Ni MSM PD was found to be 1.59 A/W.     

Comparative study on structural and optical properties of ZnO thin films prepared by PLD using ZnO powder target and ceramic target

Zinc oxide thin films have been obtained in O₂ ambient at a pressure of 1.3 Pa by pulsed laser deposition (PLD) using ZnO powder target and ceramic target. The effect of temperature on structural and optical properties of ZnO thin films was investigated systematically by XRD, SEM, FTIR and PL spectra. The results show that the best structural and optical properties can be achieved for ZnO thin film fabricated at 700 °C using powder target and at 400 °C using ceramic target, respectively. The PL spectrum reveals that the efficiency of UV emission of ZnO thin film fabricated by using powder target is low, and the defect emission of ZnO thin film derived from Zn_i and O_i is high.     

Ac and Dc conductivities of polyaniline/poly vinyl formal blend films

The synthesis and characterization of polyaniline (PANI)/poly vinyl formal (PVF) blend films were carried out in this work. Polyaniline base was doped using dodecylbenzene sulfonic acid (DBSA). These blend films were characterized by UV–Visible, FTIR spectra and scanning electron microscopy (SEM) to investigate their optical, structural and morphological properties. It was found that the percolation threshold of these blends is 4.4 wt% of PANI. The dc and ac conductivities of these blend films have been measured at a temperature range from 300 to 100 K in the frequency range of 10 kHz to 1 MHz. The electrical conductivity of the blend films enhanced with the increase of polyaniline amount up to a value of 2.5 × 10⁻⁴ S cm⁻¹ at 65 wt% of polyaniline. The dc conductivity of the PANI/PVF blend films follows the three-dimension variable range hopping. Temperature variation of frequency exponents in this blend suggests that ac conduction is attributed to be correlated barrier hopping.     

Influence of CdO-doping on the photoluminescence properties of ZnO nanofibers: Effective visible light photocatalyst for waste water treatment

Among the various nanostructural morphologies, nanofibers have a distinct interest due to the long axial ratio which strongly modifies the photocatalytic activity. In this work, study of the effect of CdO-doping on the photoluminescence properties of ZnO nanofibers was carried out. Nanofibers composed of the two oxides (ZnO and CdO) were prepared using facile, effective, simple and high yield technique; electrospinning. Typically, a sol–gel consisting of poly(vinyl alcohol), cadmium acetate and zinc acetate was electrospun. Calcination of the produced nanofibers in air did not affect the nanofibrous morphology and led to produce ZnO/CdO alloy nanofibers. Interestingly, variation of Zn to Cd ratio in the original electrospun solution did not influence the morphology, so nanofibers having CdO of 39.4, 56.5 and 72.2 wt% could be prepared. Optical properties study indicated that addition of CdO to ZnO decreases the band gap and consequently the introduced nanofibers can be utilized as photocatalyst under a visible light radiation. Moreover, the results indicated that increasing the CdO content causes to increase the solid solubility. Accordingly, the low content CdO nanofibers (39.4 wt%) reveal two band gaps in the PL spectra. Consequently, these nanofibers have the best photocatalytic activity among the prepared samples; the methylene blue dye was completely eliminated within 4.5 h. However, full dye degradation was obtained at relatively longer times when the other formulations were utilized. Beside the simplicity and low cost aspects in the proposed preparation strategy, utilizing the solar radiation as activation energy to initiate the photoreactions might recommend the introduced nanofibers to be exploited as photocatalyts in the field of waste water treatment.     

Synthesis of oligomeric poly[(1, 2-propanediamine)-alt-(oxalic acid)] and anomalous proton conductivities of the thin films

New proton-conductive polyamide oligomers, oligomeric poly[(1, 2-propanediamine)-alt-(oxalic acid)], were synthesized to investigate the proton transport properties of bulk and thin films. The obtained oligomers were characterized by the X-ray diffraction, FT-IR spectra, ¹H NMR, Matrix Assisted Laser Desorption/Ionization Time of Flight (MALDI-TOF) mass spectrum, and electrical conductivity measurements. The bulk proton conductivity is 3.0 × 10^? 4 S cm^? 1 at the relative humidity (RH) of 80%. The proton conductivity of thin film is relatively higher than that of bulk sample. Thickness dependence of the proton conductivity was observed in these thin films. The maximum proton conductivity of the thin film is 4.0 × 10^? 3 S cm^? 1 at the relative humidity (RH) of 80%, which is higher one order magnitude than that of the bulk sample. The activation energies of bulk and 200 nm thick film are 1.0 and 0.69 eV at the RH of 60%, respectively.     

ZnO nanoparticles dispersed PVA–PVP blend matrix based high performance flexible nanodielectrics for multifunctional microelectronic devices

Polymer nanocomposite (PNC) films based on the blend matrix of poly(vinyl alcohol) (PVA) and poly(vinyl pyrrolidone) (PVP) (50/50 wt%) incorporated with zinc oxide (ZnO) nanoparticles (i.e., (PVA–PVP)–x wt% ZnO; x = 0, 1, 3 and 5) were prepared by solution-cast method. The behaviour of polymer-polymer and polymer-nanoparticle interactions in the PNC films was ascertained by employing X-ray diffraction, energy dispersive X-ray, and Fourier transform infra-red spectroscopies. Scanning electron microscopy and atomic force microscopy were performed for the morphological characterization, whereas the thermal and optical properties of the PNC films were investigated by using differential scanning calorimetry and ultraviolet–visible spectroscopy, respectively. The dielectric and electrical behaviour of these PNC materials were determined by employing the dielectric relaxation spectroscopy over the frequency range from 20 Hz to 1 MHz. The influence of ZnO concentration on the degree of PVA crystalline phase and the crystallite size, surface morphology and roughness of the films, the glass phase transition and melting phase transition temperatures, direct and indirect optical energy band gap, refractive index, complex permittivity, electrical conductivity, activation energy and the structural dynamics of these PNC materials were explored. The investigated properties of the PNC films were credited to an innovation and engineering of novel high performance flexible nanodielectrics in the area of advanced functional materials for their promising applications especially in the next generation optoelectronic, gas sensor and microelectronic devices.     

Investigations on electrical properties of (PVA:NaF) polymer electrolytes for electrochemical cell applications

Solid polymer electrolytes based on poly (vinyl alcohol) (PVA) complexed with sodium fluoride (NaF) at different weight percent ratios were prepared using solution cast technique. The structural properties of these electrolyte films were examined by XRD studies. The XRD data revealed that the amorphous domains of PVA polymer matrix increased with increase of NaF salt concentration. The complexation of the salt with the polymer was confirmed by FT-IR studies. Electrical conductivity was measured in the temperature range of 303–373 K and the conductivity was found to increase with the increase of dopant concentration as well as temperature. The dielectric constant (ε′) increased with the increase in temperature and decreased with the increase in frequency. A loss peak was identified at 365 K in the dielectric loss spectra and is attributed to the orientation of polar groups. Measurement of transference number was carried out to investigate the nature of charge transport in these polymer electrolyte films using Wagner’s polarization technique and Watanabe technique. Transport number data showed that the charge transport in these polymer electrolyte systems was predominantly due to ions and in particular due to anions. Using these polymer electrolytes, solid state electrochemical cells were fabricated. Various cell parameters like open circuit voltage (OCV), short circuit current (SCC), power density and energy density were determined.     

Thermal,dielectric and conductivity studies on PVA/Ionic liquid [EMIM][EtSO4] based polymer electrolytes

Polymer electrolyte films of (PVA+15 wt% LiClO₄)+x wt% Ionic liquid (IL) 1-ethyl-3-methylimidazolium ethylsulfate [EMIM][EtSO₄] (x=0, 5, 10, 15) were prepared by solution cast technique. These films were characterized using TGA, DSC, XRD and ac impedance spectroscopic techniques. XRD result shows that amorphosity increases as the amount of the IL in PVA+salt (LiClO₄) is increased. DSC results confirm the same (except (PVA+15 wt% LiClO₄)+10 wt% IL). The dielectric and conductivity measurements were carried out on these films as a function of frequency and temperature. The addition of IL significantly improved the ionic conductivity of polymer electrolytes. Relaxation frequency vs. temperature plot for (PVA+15 wt% LiClO₄)+x wt% IL were found to follow an Arrhenius nature. The dielectric behavior was analyzed using real and imaginary parts of dielectric constant, dielectric loss tangent (tan δ) and electric modulus (M′ and M″).     

Photoluminescence of chemical solution-derived amorphous ZnO layers prepared by low-temperature process

Growth characteristic and optical properties of the amorphous ZnO thin films prepared on soda-lime–silica glass substrates by chemical solution process at 100 and 200 °C were investigated by using X-ray diffraction analysis, scanning probe microscope, ultraviolet spectrophotometer, and photoluminescence. The films exhibited an amorphous pattern even when finally heat treated at 100–200 °C for 60 min. The photoluminescence spectrum of amorphous ZnO films shows a strong near-band-edge emission, while the visible emission is nearly quenched.     

Structural and optical properties of Mn-doped ZnO nanocrystalline thin films with the different dopant concentrations

The transparent nanocrystalline thin films of undoped zinc oxide and Mn-doped (Zn_1−xMn_xO) have been deposited on glass substrates via the sol–gel technique using zinc acetate dehydrate and manganese chloride as precursor. The as-deposited films with the different manganese compositions in the range of 2.5–20 at% were pre-heated at 100 °C for 1 h and 200 °C for 2 h, respectively, and then crystallized in air at 560 °C for 2 h. The structural properties and morphologies of the undoped and doped ZnO thin films have been investigated. X-ray diffraction (XRD) spectra, scanning electron microscopy (SEM), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS) were used to examine the morphology and microstructure of the thin films. Optical properties of the thin films were determined by photoluminescence (PL) and UV/Vis spectroscopy. The analyzed results indicates that the obtained films are of good crystal quality and have smooth surfaces, which have a pure hexagonal wurtzite ZnO structure without any Mn related phases. Room temperature photoluminescence is observed for the ZnO and Mn-doped ZnO thin films.     

Ultrasound-assisted synthesis of poly(MMA–co–BA)/ZnO nanocomposites with enhanced physical properties

The present study reports synthesis and characterization of poly(MMA–co–BA)/ZnO nanocomposites using ultrasound-assisted in-situ emulsion polymerization. Methyl methacrylate (MMA) was copolymerized with butyl acrylate (BA), for enhanced ductility of copolymer matrix, in presence of nanoscale ZnO particles. Ultrasound generated strong micro-turbulence in reaction mixture, which resulted in higher encapsulation and uniform dispersion of ZnO (in native form – without surface modification) in polymer matrix, as compared to mechanical stirring. The nanocomposites were characterized for physical properties and structural morphology using standard techniques such as XRD, FTIR, particle size analysis, UV–Visible spectroscopy, electrical conductivity, TGA, DSC, FE-SEM and TEM. Copolymerization of MMA and BA (in presence of ZnO) followed second order kinetics. Thermal stability (T_10% = 324.9 °C) and glass transition temperature (T_g = 67.8 °C) of poly(MMA-co-BA)/ZnO nanocomposites showed significant enhancement (35.1 °C for 1 wt% ZnO and 15.7 °C for 4 wt% ZnO, respectively), as compared to pristine poly(MMA–co–BA). poly(MMA–co–BA)/ZnO (5 wt%) nanocomposites possessed the highest electrical conductivity of 0.192 μS/cm and peak UV absorptivity of 0.55 at 372 nm. Solution rheological study of nanocomposites revealed enhancement in viscosity with increasing ZnO loading. Maximum viscosity of 0.01 Pa-s was obtained for 5 wt% ZnO loading.