Morphological and physicochemical properties of spin-coated poly(3-octylthiophene)/polystyrene composite thin films

Poly(3-octylthiophene) (P3OT) was synthesized by direct oxidation of 3-octylthiophene with FeCl₃ as oxidant. Molecular weight of P3OT polymer was measured by size exclusion chromatography. Homogeneous poly(3-octylthiophene) (P3OT) and polystyrene (PS) composite films have been synthesized by spin-coating technique from toluene with different polymer concentrations. The doped films were obtained by immersion for 30 s in a 0.3 M ferric chloride (FeCl₃) solution in nitromethane. A classical percolation phenomenon was observed in the electrical properties of these blends, it was smaller than 5% of P3OT in the blend. Surface topographical changes were studied by atomic force microscopy (AFM). AFM images of the composite films revealed surface morphology variation as a function of different P3OT concentration in PS, phase segregation was observed, and PS is shown to segregate to the surface of the films. The higher PS solubility, in comparison with the P3OT solubility, in toluene resulted in PS/P3OT bilayers. The films exhibited pit and island like topography, the pit size changed with the polymer concentration. Optical absorption properties of the polymeric films were analyzed in pristine and doped state. In doped state, the bipolaronic bands at 0.5 and 1.6 eV are shown in a 4% conductive polymer in the PS/P3OT film. Finally thermogravimetric analysis was also made on the simple and composite polymers.     

Structural and optical properties of both pure poly(3-octylthiophene) (P3OT) and P3OT/fullerene films

We have investigated the structural and optical properties of P3OT and P3OT/fullerene thin films in view of their application as active layer in plastic solar cells. Films of these materials were prepared by spin coating from toluene solutions onto silicon substrates. Their optical properties were studied by spectroscopic ellipsometry, which provides the anisotropic dielectric function of the films. Moreover, structural properties were studied using X-ray diffraction. A close correlation between the results obtained by both methods could be found. Especially, the strong optical anisotropy of the films can be explained in terms of a preferable orientation of the polymer chains parallel to the substrate. The effect of the optical anisotropy on the performance of optoelectronic devices is discussed.     

Influence of P3HT concentration on morphological, optical and electrical properties of P3HT/PS and P3HT/PMMA binary blends

Poly(3-hexylthiophene) (P3HT) has interesting optoelectronic properties and a wide variety of applications such as solar cells and O-FET devices. It is a soluble conductive polymer but their mechanical properties are poor and its conductivity is unstable in environmental condition. With the finality of overcome these disadvantages, P3HT binary blends with two insulating polymers, polystyrene (PS) and polymethylmetacrilate (PMMA), have been synthesized by direct oxidation of 3-hexylthiophene with FeCl₃ as oxidant inside the insulator polymers. Molecular weight and polydispersity of P3HT polymer were measured by size exclusion chromatography and the degree of regioregularity by ¹H RMN. P3HT/PS and P3HT/PMMA thin films were prepared by spin-coating technique from toluene solution at different P3HT concentrations. The doped films were obtained by immersion during 30 s in a 0.3 M ferric chloride (FeCl₃) solution in nitromethane. A classical percolation phenomenon was observed in the electrical properties of the binary blends, it was smaller than 4 wt.% of P3HT in the blend. Atomic force microscopy and confocal microscopy showed a phase-separated morphology. Variation in the surface morphology of the blends was observed, which was a function of the polymer concentration and the type of insulator polymer used in the blends. The insulator polymer was segregated on the surface of the films and showed pit and island-like topography. The pit and island size changed as a function of the polymer concentration. Optical absorption properties as a function of the P3HT concentration in the undoped and doped state were analyzed. In doped state, the bipolaron bands in the PS/P3HT and PMMA/P3HT blends were observed from a P3HT concentration of 1 wt.% and 3 wt.%, respectively. Finally, the polymers were analyzed by thermogravimetric analysis and infrared spectroscopy.     

Schottky and heterojunction diodes based on poly(3-octylthiophene) and poly(3-methylthiophene) films of high tensile strength

Schottky and heterojunction diodes were fabricated using high tensile strength polymers. The heterojunction diode was fabricated by sequential electrochemical polymerisation of 3-methyl thiophene and 3-octyl thiophene on an indium-tin oxide (ITO) coated glass substrate. The high tensile strength enabled the bilayer (used in heterojunction diodes) or the poly 3-octyl thiophene films (used in the Schottky diodes) to be peeled of from the substrate and sandwich it between any two desired metals. It was found that the Schottky diodes of ITO (or Si)/POT/Al (or Zn) exhibit moderate rectifying behaviour and ITO (or Si)/POT/Cu devices exhibit ohmic contact. The POT/PMT heterojunction diode showed excellent rectification effect when sandwiched between any two metals irrespective of their work function. This shows that the results observed were solely due to the polymer/polymer interface. The Cu/POT/PMT/Cu heterojunction system was used in this study. The carrier-flow of the two semiconductors in the Cu/POT/PMT/Cu heterojunction diode was discussed in details. The rectification ratio, the barrier height, and the ideality factor for the heterojunction diode were found to be 64 (±1.2 V), 0.81 eV, and 5.7 under ambient conditions, respectively. Some of the important energy band parameters were also determined.     

Optical properties of Cd1−xZnxS thin films for CuInGaSe2 solar cell application

The photovoltaic Cd_1−xZn_xS thin films, fabricated by chemical bath deposition, were successfully used as n-type buffer layer in CuInGaSe₂ (CIGS) solar cells. Comprehensive optical properties of the Cd_1−xZn_xS thin films were measured and modeled by spectroscopic ellipsometry (SE), which is proven to be an excellent and non-destructive technique to determine optical properties of thin films. The optical band gap of Cd_1−xZn_xS thin films can be tuned from 2.43 eV to 3.25 eV by controlling the Zn content (x) and deposition conditions. The wider-band-gap Cd_1−xZn_xS film was found to be favorable to improve the quantum efficiency in the wavelength range of 450-550 nm, resulting in an increase of short-circuits current for solar cells. From the characterization of quantum efficiency (QE) and current-voltage curve (J-V) of CIGS cells, the Cd_1−xZn_xS films (x = 0.32, 0.45) were demonstrated to significantly enhance the photovoltaic performance of CIGS solar cell. The highest efficiency (10.5%) of CIGS solar cell was obtained using a dense and homogenous Cd_0.68Zn_0.32S thin film as the buffer layer.     

Preparation and characterization of chemically deposited PbSnS3 thin films

High-quality and well-reproducible PbSnS₃ thin films have been prepared by a simple and inexpensive chemical-bath deposition method from an aqueous medium, using thioacetamide as a sulphide ion source. X-ray diffraction analysis of the deposited films revealed that the as-deposited films were amorphous, however, an amorphous-to-crystalline phase transition was observed as the result of thermal annealing at 425 K for 1 h. The X-ray structure analysis of the collected powder from the bath annealed at 425 K for 1.5 h revealed an orthorhombic phase.

Analysis of the optical absorption data of crystalline PbSnS₃ films revealed that both direct and indirect optical transitions exist in the photon energy range 1.24–2.48 eV with optical band gaps of 1.68 and 1.42 eV, respectively. However, a forbidden direct optical transition with a band gap value of 1.038 eV dominates at low energy (<1.24 eV). The refractive index changes from 3.38 to 2.16 in the range 500–1300 nm. The high frequency dielectric constant and the carrier concentration to the effective mass ratio calculated from the refractive index analysis were found to be 4.79 and 2.3×10²⁰ cm⁻³, respectively. The temperature dependence of the electrical resistivity of the deposited films follows the semiconductor behaviour with extrinsic and intrinsic conduction. The determined activation energies range are 0.35–0.42 and 0.76–85 eV, respectively.     

Synthesis and physicochemical characterization of copolymers of 3-octylthiophene and thiophene functionalized with azo chromophore

Polythiophene derivatives with azo chromophore were synthesized via copolymerization of 3-octylthiophene (3OT) and 2-[N-ethyl-N-[4-[(4-nitrophenyl)azo]phenyl]amino]ethyl 3-thienylacetate (3-DRT). This copolymer has interesting optoelectronic properties and a variety of applications such as electrochromic and electronic devices. The polymerization process of 3OT and the functionalized thiophene was carried out via FeCl₃ oxidative polymerization. Thin films of poly(3OT-co-3-DRT) copolymer were prepared by spin-coating technique from toluene. FTIR and ¹H NMR spectroscopy revealed the presence of chromophore groups in the copolymer chain. Molecular weight and polydispersity of the polymers were measured by size exclusion chromatography. Changes in the surface topography of copolymers were analyzed by atomic force microscopy; the results showed that the copolymers presented some protuberances of variable size unlike the homogeneous granular morphology of P3OT. It is believed that these changes appeared by the incorporation of 3-DRT in the polymer. P3ATs are electrochromic materials that show color change upon oxidation-reduction process. We report that electrochemical characterization of poly(3OT-co-3-DRT) copolymer films synthesized chemically on indium-tin oxide (ITO) glass substrates showed an additional color to the P3OT homopolymer. Optical absorption properties of the polymer films were analyzed in the undoped and doped states and as a function of 3-DRT concentration in the copolymer. The nonlinear optical properties of the copolymers in the undoped and doped states were analyzed by Z-scan technique. The copolymers showed a change of non-linearity sign when the film was doped and results showed that the copolymers have a positive (self-focusing) and negative (self-defocusing) nonlinear optical properties which make them interesting for application as optoelectronic devices. We determined that the nonlinearity of the polymer films was a Kerr type.     

Optical properties of tungsten oxide thin films by non-reactive sputtering

Tungsten oxide thin films were grown on glass substrates by RF sputtering at room temperature using a tungsten trioxide target for several values of the argon pressure (P_Ar). The structural and morphological properties of these films were studied using X-ray diffraction and atomic force microscopy. The as-deposited films were amorphous irrespective of the argon pressure, and crystallized in a mixture of hexagonal and monoclinic phases after annealing at a temperature of 350 °C in air. Surface-roughness increased by an order of magnitude (from 1 nm to 20 nm) after thermal treatment. The argon pressure, however, had a strong influence on the optical properties of the films. Three different regions are clearly identified: deep blue films for P_Ar ≤ 2.67 Pa with low transmittance values, light blue films for 2.67 Pa < P_Ar < 6 Pa with intermediate transmittance values and transparent films for P_Ar ≥ 6 Pa with high transmittance values. We suggest that the observed changes in optical properties are due to an increasing number of oxygen vacancies as the growth argon pressure decreases.     

Optical properties of NiO thin films fabricated by electron beam evaporation

Nickel oxide (NiO) thin films were deposited onto quartz substrates by the electron beam deposition technique, and obtained high crystal quality after annealing at 1173 K. The structural and microstructural properties of the films were studied by X-ray diffraction (XRD) and atomic force microscope (AFM), respectively. We focus on the optical characterization of the films, indicating the enhancement of the crystal quality, which was confirmed by the photoluminescence and Raman spectrum. Furthermore, PL studies exhibited room temperature emission at 377 nm, and also shown high ultraviolet/visible rejection ratio (>100).     

Structural, morphological and optical properties of thermal annealed TiO thin films

Structural, morphological and optical properties of TiO thin films grown by single source thermal evaporation method were studied. The films were annealed from 300 to 520 °C in air after evaporation. Qualitative film analysis was performed with X-ray diffraction, atomic force microscopy and optical transmittance and reflectance spectra. A correlation was established between the optical properties, surface roughness and growth morphology of the evaporated TiO thin films. The X-ray diffraction spectra indicated the presence of the TiO₂ phase for the annealing temperature above 400 °C.     

Optical properties of pyrene doped polymer thin films

Thin films of pyrene in polystyrene matrix have been prepared by spin coating technique. The concentration of polystyrene is kept constant to 1 wt.% while that of pyrene dopant varied in the range 2.30×10⁻⁴-2.30×10⁻¹ wt.%. Thickness of the films was found to depend upon concentration of pyrene and varies from 90 to 782 nm. The results of X-ray diffraction analysis reveal the crystalline nature of the films. The optical properties were studied by absorption, excitation and fluorescence spectroscopy. The band gap energy of pyrene in polymer films was calculated from absorption results. A transition from monomer to excimer is observed with thickness variation of the films. The structured part of the spectrum is assigned to the monomer emission while the broad emission band is attributed to well known pyrene excimer-like emission.     

Optical properties of vapour chopped and nonchopped tin oxide thin films

The optical properties of vapour chopped and nonchopped undoped tin oxide thin films (1000 Å) have been studied. The films were prepared by thermal oxidation (in air) of vacuum evaporated vapour chopped and nonchopped tin thin films. Effect of varied oxidation temperature and duration was also studied. As revealed by X ray diffraction studies, polycrystalline (both tetragonal and orthorhombic) films were obtained. The refractive indices ranged from 1.575 to 1.667 and 1.600 to 1.810 for nonchopped and vapour chopped tin oxide films respectively. Refractive index was found to increase after ageing. The effect was found lower in vapour chopped films. The direct band gap values ranged from 2.18 to 2.51 and 2.95 to 3.08 for nonchopped and vapour chopped tin oxide films respectively. The films showed high optical transmittance in the visible range of the spectrum. It was observed that the heat treatment process strongly affects the properties of the films. The vapour chopped tin oxide thin films showed higher packing density, optical band gap and refractive index with lower ageing effect.     

Optical and structural properties of sol-gel prepared MgZnO alloy thin films

Mg_xZn_1−xO (x = 0-0.5) alloy thin films were prepared by a sol-gel dip-coating method. Mg_0.1Zn_0.9O and Mg_0.5Zn_0.5O films prepared were annealed in the range of 400-900 °C to investigate their thermal stability and temperature-dependent optical properties. The Mg_0.1Zn_0.9O films were thermally stable in the investigated annealing temperature range and exhibited the maximum ultraviolet emission at 800 °C. The segregation of MgO occurred in the Mg_0.5Zn_0.5O films, and the near-band-edge ultraviolet emission of this alloy was enhanced with increasing annealing temperature. The Mg saturation content in the sol-gel prepared MgZnO alloys was found to be about 0.23 where the band gap extended to 3.48 eV.     

Synthesis and characterization of WO3 thin films by surfactant assisted spray pyrolysis for electrochromic applications

Thin films of WO₃ were prepared by surfactant assisted spray pyrolysis on F-doped SnO₂ (FTO) conductive glass by using hexadecyltrimethylammonium bromide (HTAB) and polyethylene glycol (PEG400):HTAB as growth controlling agents. The surface tension of the spraying solutions was experimentally evaluated and was correlated with the deposition processes (nucleation and growth) of very smooth and homogenous films. The effect of the surfactant, alone and associated with PEG, on the structure (XRD), morphology (AFM), surface composition (XPS), FTIR and hydrophilicity (contact angle) were investigated and their influence on the electrochromic activity was discussed. Using surfactants and PEG, the coloration efficiency, transmission modulation and cycling stability of the WO₃ thin films can be enhanced.     

Optical and structural properties of chemically deposited CdS thin films on polyethylene naphthalate substrates

CdS thin films were deposited on polyethylene naphthalate substrates by means of the chemical bath deposition technique in an ammonia-free cadmium-sodium citrate system. Three sets of CdS films were grown in precursor solutions with different contents of Cd and thiourea maintaining constant the concentration ratios [Cd]/[thiourea] and [Cd]/[sodium citrate] at 0.2 and 0.1 M/M, respectively. The concentrations of cadmium in the reaction solutions were 0.01, 7.5 × 10⁻³ and 6.8 × 10⁻³ M, respectively. The three sets of CdS films were homogeneous, hard, specularly reflecting, yellowish and adhered very well to the plastic substrates, quite similar to those deposited on glass substrates. The structural and optical properties of the CdS films were determined from X-ray diffraction, optical transmission and reflection spectroscopy and atomic force microscopy measurements. We found that the properties of the films depend on both the amount of Cd in the growth solutions and on the deposition time. The increasing of Cd concentration in the reaction solution yield to thicker CdS films with smaller grain size, shorter lattice constant, and higher energy band gap. The energy band gap of the CdS films varied in the range 2.42-2.54 eV depending on the precursor solution. The properties of the films were analyzed in terms of the growth mechanisms during the chemical deposition of CdS layers.     

Optical properties of erbium oxide thin films deposited by electron beam evaporation

Erbium oxide thin films were deposited by electron beam evaporation on substrates heated to 300 °C. The effect of the introduction of oxygen on the structural, chemical and optical properties of the films was investigated. The films were characterized using X-ray diffraction, X-ray photoelectron spectroscopy and normal-incidence transmittance and reflectance. The films had microcrystallites embedded in an amorphous matrix, and their stoichiometry was dependent on the oxygen partial pressure. The transmittance spectra of the films revealed that they were optically inhomogeneous. A model based on an inhomogeneous layer was applied to extract the refractive index and extinction coefficient from the transmittance and reflectance spectra.     

Optical and surface morphological properties of triethylamine passivated lead sulphide nanoparticles

The triethylamine capped lead sulphide (PbS) nanoparticles were successfully synthesized by simple wet chemical method. The synthesized product has been characterized by powder X-ray diffraction (XRD), UV–vis spectrophotometry, FTIR spectroscopy, atomic force microscopy (AFM), transmission electron microscopy (TEM) and photoluminescence studies. The size of the PbS nanoparticles was determined from AFM, TEM, XRD and from these studies it is found that the size of the particles of the order of 10–15 nm. Significant “blue shift” from bulk material was observed on the PbS nanoparticles using UV–vis and photoluminescence spectrum.     

Growth and characterization of electrosynthesised zinc oxide thin films

Zinc oxide (ZnO) films have been electrodeposited from an aqueous solution containing 0.1 M zinc nitrate as the electrolyte with pH around 5±0.1. The deposition was carried out by galvanostatic reduction with an applied cathodic current density in the range between 5 and 20 mA cm⁻². The influence of bath composition on the preparation of ZnO films is studied. The effects of zinc nitrate concentration and cathodic current density on the deposition rate of ZnO films were also studied. An optimum current density of 10 mA cm⁻² is identified for the growth of ZnO film with improved crystallinity and optical transmittance. The crystalline structure of the deposits studied by X-ray diffraction reveals the possibility of growing hexagonal ZnO films under suitable electrochemical conditions. The surface morphological studies by scanning electron micrographs revealed the presence of nodular appearance for films deposited at 800 °C bath temperatures.     

Structural and optical properties of CdS thin films grown by chemical bath deposition

Cubic cadmium sulphide (CdS) thin films with (111) preferential orientation were prepared by chemical bath deposition (CBD) technique, using the reaction between NH₄OH, CdSO₄ and CS(NH₂)₂. The films properties have been investigated as a function of bath temperature and deposition time. Structural properties of the obtained films were studied by X-ray diffraction analysis. The structural parameters such as crystallite size have been evaluated. The transmission spectra, recorded in the UV visible range reveal a relatively high transmission coefficient (70%) in the obtained films. The transmittance data analysis indicates that the optical band gap is closely related to the deposition conditions, a direct band gap ranging from 2.0 eV to 2.34 eV was deduced. The electrical characterization shows that CdS films' dark conductivities can be controlled either by the deposition time or the bath temperature.     

Ellipsometry study of poly(o-methoxyaniline) thin films

Spin-coated poly(o-methoxyaniline) (POMA) thin films on various substrates were investigated using spectroscopic ellipsometry (SE) in the 1.5–4.5 eV photon energy range. Spin-coating process parameters are reported (spin speed and concentration). Substrates with higher surface energy were found to increase polymer film thickness and decrease roughness. An optical model was developed using SE data along with complementary data from atomic force microscopy and UV–vis spectroscopy to obtain optical properties—refractive index n and extinction coefficient k for POMA. The model includes Lorentz oscillators for the POMA film and a Bruggeman effective medium approximation for roughness. In-plane film optical anisotropy was not observed, but a small out of plane anisotropy was detected for the polymer.