Development of structural and optical properties of WOx films upon increasing oxygen partial pressure during reactive sputtering

WO_x films were prepared by reactive dc magnetron sputtering using tungsten target. Sputtering was carried out at a total pressure of 1.2 Pa using a mixture of argon plus oxygen in an effort to determine the influence of the oxygen partial pressure on structural and optical properties of the films. The deposition rate decreases significantly as the surface of the target is oxidized. X-Ray diffraction revealed the amorphous nature of all the films prepared at oxygen partial pressures higher than 1.71×10⁻³ Pa. For higher oxygen partial pressures, fully transparent films were deposited, which showed a slight increase in optical band gap with increasing oxygen partial pressure, while the refractive index was simultaneously decreased.     

Dynamics of a pulsed laser generated tin plasma expanding in an oxygen atmosphere

Semiconducting tin oxide can be successfully deposited by means of the laser ablation technique. In particular by ablating metallic tin in a controlled oxygen atmosphere, thin films of SnO _x have been deposited. The partial oxygen pressure at which the films are deposited strongly influences both the stoichiometry and the structural properties of the films. In this work, we present a study of the expansion dynamics of the plasma generated by ablating a tin target by means of a pulsed laser using time and space resolved optical emission spectroscopy and fast photography imaging of the expanding plasma. Both Sn I and Sn II optical emission lines have been observed from the time-integrated spectroscopy. Time resolved-measurements revealed the dynamics of the expanding plasma in the ambient oxygen atmosphere. Stoichiometry of the films has been determined by means of X-ray photoelectron spectroscopy and correlated to the expansion dynamics of the plasma.     

Structural, optical and morphological studies on laser ablated nanostructured WO3 thin films

Thin films of tungsten trioxide (WO₃) are prepared by reactive pulsed laser deposition (PLD) technique on glass substrates at three different substrate temperatures (T_s). The structural, morphological and optical properties of the deposited films are systematically studied using X-ray diffraction (XRD), grazing incidence X-ray diffraction (GIXRD), micro-Raman spectroscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM) and UV-VIS spectrophotometry techniques. X-ray diffraction analysis reveals that crystalline WO₃ films can grow effectively even at 300 K at an oxygen pressure of 0.12 mbar. All the films deposited at various T_s exhibit mixed oxide phase consisting of orthorhombic and triclinic phase of tungsten oxide with a preferred orientation along (0 0 1) lattice plane reflection. Micro-Raman results are consistent with X-ray diffraction findings. The SEM analysis shows that deposited films are porous and crystalline grains are of nano-metric dimension. The effect of T_s on mean surface roughness studied by AFM analysis reveals that mean surface roughness decreases with increase in T_s. The optical response of WO₃ layers measured using UV-VIS spectrophotometry is used to extract the optical constants such as refractive index (n), extinction coefficient (k) and optical band gap (E_g), following the method of Swanepoel.     

The relationship between refractive index-energy gap and the film thickness effect on the characteristic parameters of CdSe thin films

CdSe thin films were deposited on glass substrates using Successive Ionic Layer Adsorption and Reaction (SILAR) method at room temperature and ambient pressure. The relationship between refractive index and energy bandgap was investigated. The film thickness effect on the structural, morphological, optical and electrical properties of CdSe thin films was investigated. The X-ray diffraction (XRD) and scanning electron microscopy (SEM) studies showed that all the films exhibit polycrystalline nature with hexagonal structure and are covered well with glass substrates. The crystalline and surface properties of the films improved with increasing film thickness. The optical absorption studies revealed that the films are found to be a direct allowed transition. The energy bandgap values were changed from 1.93 to 1.87 eV depending on the film thickness. The electron effective mass (m_e^?/m_o), refractive index (n), optical static and high frequency dielectric constant (ε_o, ε_∞) values were calculated by using the energy bandgap values as a function of the film thickness. The resistivity of the films changed between 10⁶ and 10² Ω-cm with increasing film thickness at room temperature.     

Optimization of F-doped SnO2 electrodes for organic photovoltaic devices

Fluorine-doped tin oxide (FTO) thin films have been investigated as an alternative to indium tin oxide anodes in organic photovoltaic devices. The structural, electrical, and optical properties of the FTO films grown by pulsed laser deposition were studied as a function of oxygen deposition pressure. For 400 nm thick FTO films deposited at 300°C and 6.7 Pa of oxygen, an electrical resistivity of 5×10⁻⁴ Ω-cm, sheet resistance of 12.5 Ω/□, average transmittance of 87% in the visible range, and optical band gap of 4.25 eV were obtained. Organic photovoltaic (OPV) cells based on poly(3-hexylthiophene)/[6,6]-phenyl-C₆₁-butyric acid methyl ester bulk heterojunctions were prepared on FTO/glass electrodes and the device performance was investigated as a function of FTO film thickness. OPV cells fabricated on the optimum FTO anodes (∼300–600 nm thick) exhibited power conversion efficiencies of ∼3%, which is comparable to the same device made on commercial ITO/glass electrodes (3.4%).     

Effect of substrate temperature on structural, optical and electrical properties of pulsed laser ablated nanostructured indium oxide films

Nanocrystalline indium oxide (INO) films are deposited in a back ground oxygen pressure at 0.02 mbar on quartz substrates at different substrate temperatures (T_s) ranging from 300 to 573 K using pulsed laser deposition technique. The films are characterized using GIXRD, XPS, AFM and UV-visible spectroscopy to study the effect of substrate temperature on the structural and optical properties of films. The XRD patterns suggest that the films deposited at room temperature are amorphous in nature and the crystalline nature of the films increases with increase in substrate temperature. Films prepared at T_s ≥ 473 K are polycrystalline in nature (cubic phase). Crystalline grain size calculation based on Debye Scherrer formula indicates that the particle size enhances with the increase in substrate temperature. Lattice constant of the films are calculated from the XRD data. XPS studies suggest that all the INO films consist of both crystalline and amorphous phases. XPS results show an increase in oxygen content with increase in substrate temperature and reveals that the films deposited at higher substrate temperatures exhibit better stoichiometry. The thickness measurements using interferometric techniques show that the film thickness decreases with increase in substrate temperature. Analysis of the optical transmittance data of the films shows a blue shift in the values of optical band gap energy for the films compared to that of the bulk material owing to the quantum confinement effect due to the presence of quantum dots in the films. Refractive index and porosity of the films are also investigated. Room temperature DC electrical measurements shows that the INO films investigated are having relatively high electrical resistivity in the range of 0.80-1.90 Ωm. Low temperature electrical conductivity measurements in the temperature range of 50-300 K for the film deposited at 300 K give a linear Arrhenius plot suggesting thermally activated conduction. Surface morphology studies of the films using AFM reveal the formation of nanostructured indium oxide thin films.     

Effect of post annealing temperature on structural and optical properties of ZnCdO thin films deposited by sol–gel method

Ternary ZnCdO thin films oriented along c-axis have been successfully deposited on p-Si (1 0 0) substrates using sol–gel spin coating route. To optimize most suitable annealing temperature for the Zn_1−xCd_xO thin films; these films with selected cadmium content x = 0.10 were treated at annealing temperatures from 300 °C up to 800 °C in oxygen ambient after deposition. The structural and optical properties of deposited thin films have been characterized by X-ray diffraction, energy dispersive spectroscopy, atomic force microscopy, UV–Vis spectroscopy, and photoluminescence spectra. The results show that the obtained films possess high crystallinity with wurtzite structure. The crystallite size, lattice parameters, lattice strain and stress in the deposited films are determined from X-ray diffraction analysis. The band gap energy increased as a function of annealing temperatures as observed from optical reflectance spectra of samples. The presence of Cd in the deposited films is confirmed by energy dispersive spectrum and it is observed that Cd re-evaporate from the lattice with annealing. The photoluminescence measurements as performed at room temperature did not exhibit any luminescence related to oxygen vacancies defects for lower annealing temperatures, as normally displayed by ZnO films. The green yellow luminescence associated to these defects was observed at higher annealing temperatures (≥700 °C).     

Effect of oxygen partial pressure and VO<Subscript>2</Subscript> content on hexagonal WO<Subscript>3</Subscript> thin films synthesized by pulsed laser deposition technique

We report on the effect of oxygen partial pressure and vacuum annealing on structural and optical properties of pulsed laser-deposited nanocrystalline WO₃ thin films. XRD results show the hexagonal phase of deposited WO₃ thin films. The crystallite size was observed to increase with increase in oxygen partial pressure. Vacuum annealing changed the transparent as-deposited WO₃ thin film to deep shade of blue color which increases the optical absorption of the film. The origin of this blue color could be due to the presence of oxygen vacancies associated with tungsten ions in lower oxidation states. In addition, the effects of VO₂ content on structural, electrochemical, and optical properties of (WO₃)_1−x (VO₂) _x nanocomposite thin films have also been systematically investigated. Cyclic voltammogram exhibits a modification with the appearance of an extra cathodic peak for VO₂–WO₃ thin film electrode with higher VO₂ content (x ≥ 0.2). Increase of VO₂ content in (WO₃)_1−x (VO₂) _x films leads to red shift in optical band gap.     

An extreme change in structural and optical properties of indium oxynitride deposited by reactive gas-timing RF magnetron sputtering

The indium oxynitride (InON) films were achieved by reactive RF magnetron sputtering indium target which has the purity of 99.999% with a novel reactive gas-timing technique. The structural, optical and electrical properties in a series of polycrystalline InON films affected by gas-timing of reactive N₂ and O₂ gases introduced to the chamber were observed. The X-ray photoelectron spectroscopy revealed that the oxygen content in thin films that compounded to indium and nitrogen, which increased from 10% in indium nitride (InN) to 66% in indium oxide (In₂O₃) films. The X-ray diffraction peaks show that the phase of deposited films changes from InN to InON and to In₂O₃ with an increasing oxygen timing. The hexagonal structure of InN films with predominant (0 0 2) and (0 0 4) orientation was observed when pure nitrogen is only used as sputtering gas, while InON and In₂O₃ seem to demonstrate body-center cubic polycrystalline structures depending on gas-timing. The surface morphologies investigated from atomic force microscope of deposited films with varying gas-timing of O₂:N₂ show indifferent. The numerical algorithm method was used to define the optical bandgap of films from transmittance results. The increasing oxygen gas-timing affects extremely to the change of crystallinity phase from InN to InON and to In₂O₃, the increase of optical bandgap from 1.4 to 3.4 eV and the rise of sheet resistance from 15 Ω/□ to insulator.     

Structural,electrical and optical studies on spray-deposited aluminium-doped ZnO thin films

Thin films of zinc oxide (ZnO) were deposited on cleaned glass substrates by chemical spray pyrolysis technique using Zn(CH₃COO)₂ as precursor solution. Also, aluminium-doped thin films of ZnO were prepared by using AlCl₃ as doping solution for aluminium. The dopant concentration [Al/Zn atomic percentage (at%)] was varied from 0 to 1.5 at% in thin films of ZnO prepared in different depositions. Structural characterization of the deposited films was performed with X-ray diffraction (XRD) studies. It confirmed that all the films were of zinc oxide having polycrystalline nature and possessing typical hexagonal wurtzite structure with crystallite size varying between 100.7 and 268.6 nm. The films exhibited changes in relative intensities and crystallite size with changes in the doping concentration of Al. The electrical studies established that 1 at% of Al-doping was the optimum for enhancing electrical conduction in ZnO thin films and beyond that the distortion caused in the lattice lowered the conductivity. The films also exhibited distinct changes in their optical properties at different doping concentrations, including a blue shift and slight widening of bandgap with increasing Al dopant concentration.     

Structural and luminescent characteristics of pulsed laser deposited Eu3+-doped Y2O3 thin films

Thin films of Eu-doped Y₂O₃ were deposited using the pulsed laser ablation technique on amorphous fused silica substrates. The effect of oxygen partial pressure (pO₂) and substrate temperature on the structural and optical characteristics of the deposited films were investigated. All the deposited films were crystalline, showing preferred orientation along the (111) plane, irrespective of oxygen partial pressure and substrate temperature. The film deposited at 0.005?mbar pO₂ exhibited better crystallinity with minimum FWHM at a substrate temperature of 600°C. All the films deposited at various substrate temperatures and different partial pressure (at 600°C) exhibited a red luminescence peak at 615?nm corresponding to the ⁵D₀–⁷F₁ transition in Eu³⁺. Photoluminescence excitation spectra exhibited two bands, one corresponding to band to band excitation (212?nm) of the host and the other to charge transfer band excitation (245?nm). A microstructure analysis revealed that surface roughness of the as-deposited films increases with increase in oxygen partial pressure.     

Influence of oxygen on structural and optoelectronic properties of CdS thin film deposited by magnetron sputtering technique

In this study, CdS thin films with thicknesses of approximately 100 nm were deposited at a substrate temperature of 100 °C by a sputtering technique under two different ambient conditions—pure Ar ambient and Ar/O₂ (99:1) ambient—at deposition power densities of 1.0 and 2.0 W/cm², respectively The films were polycrystalline with a preferential orientation along the (002) crystal plane; however, the films deposited in the Ar/O₂ ambient exhibited reduced crystallinity. Furthermore, the crystallite sizes, micro-strains, and dislocation densities of the films were significantly affected by oxygen diffusion into the films’ crystal structures. The CdS films deposited in the Ar/O₂ ambient demonstrated higher optical transmittance and higher bandgaps. Morphologies observed from scanning electron microscopy images revealed that the grains of the films were also significantly affected by the oxygen present in the deposition ambient. Additionally, photoluminescence analysis revealed that the sulfur vacancies in the CdS films were partially filled by oxygen atoms, causing significant variations in the electrical properties of the films.     

SnO2 thin films grown by pulsed Nd:YAG laser deposition

SnO₂ thin films have been deposited on glass substrates by pulsed Nd:YAG laser at different oxygen pressures, and the effects of oxygen pressure on the physical properties of SnO₂ films have been investigated. The films were deposited at substrate temperature of 500°C in oxygen partial pressure between 5.0 and 125 mTorr. The thin films deposited between 5.0 to 50 mTorr showed evidence of diffraction peaks, but increasing the oxygen pressure up to 100 mTorr, three diffraction peaks (110), (101) and (211) were observed containing the SnO₂ tetragonal structure. The electrical resistivity was very sensitive to the oxygen pressure. At 100 mTorr the films showed electrical resistivity of 4×10⁻² Ω cm, free carrier density of 1.03×10¹⁹ cm⁻³, mobility of 10.26 cm² V⁻¹ s⁻¹ with average visible transmittance of ∼87%, and optical band gap of 3.6 eV.     

Hydrogen gas-sensing properties of Pt/WO<Subscript>3</Subscript> thin film in various measurement conditions

A well-known gasochromic material is Pt particle-dispersed tungsten trioxide (Pt/WO₃). Its optical properties could make it effective as a hydrogen gas sensor. In this study, Pt nanoparticle-dispersed WO₃ thin films were prepared using the sol–gel process, and their optical and electrical properties dependent on the working environment (i.e., temperature, hydrogen gas concentration, oxygen partial pressure, etc.) were investigated. The Pt/WO₃ thin films prepared at 400 °C showed the largest change in optical transmittance and electrical conductivity when exposed to hydrogen gas compared with the films prepared at other temperatures. The optical absorbance and electrical conductivity were found to be dependent on the hydrogen and oxygen gas concentration in the atmosphere because generation and disappearance of W⁵⁺ in the thin films depend on the equilibrium reaction between injection and rejection of H⁺ into and from the thin films. In addition, the equilibrium reaction depends on the hydrogen and oxygen gas concentrations.     

Thin ZnO films prepared by chemical solution deposition on glass and flexible conducting substrate

Thin films of zinc oxide (ZnO) are deposited by a simple method of successive immersion of substrate in (NH₄)₂ZnO₂(0.1 M) chemical solution and in boiling water. Films of a thickness ≈ 500 nm could be deposited on stainless steel and glass by 40 immersions. The composition, structure, optical bandgap and the charge transport mechanism were determined and the results are presented. Films are stoichiometric and have the same hexagonal lattice parameters as for powder samples. Films are formed from grains with a mean size of a few 100 nm. Grains consist of crystallites of mean size 20–30 nm. For films deposited on stainless steel, the crystallites are highly oriented along their c-axis perpendicular to the substrate. Films have a high optical transparency (above 80%) in the visible region and bandgap energy in the range 3.38–3.42 eV. Films are intrinsically n-type and the charge transport across the films is controlled by a shallow trapping level in accordance with the Poole–Frenkel mechanism. The doubly-ionized trapping level has a concentration of 4×10¹¹ cm^-3 and zero-field ionization energy of 110 meV. Adsorption of oxygen by annealing the films in air yields a singly-ionized trap. PACS 81.15.Lm; 81.05.Dz; 68.37.Hk; 73.61.Ga     

Influence of post-deposition annealing on the structural,optical and electrical properties of Li and Mg co-doped ZnO thin films deposited by sol–gel technique

Lithium (Li) and magnesium (Mg) co-doped zinc oxide (ZnO) thin films were deposited by sol–gel method using spin coating technique. The films were deposited on glass substrates and annealed at different temperatures. The effects of annealing temperature on the structural, optical and electrical properties of the deposited films were investigated using X-ray diffraction (XRD), Ultraviolet–Visible absorption spectra (UV–VIS), photoluminescence spectra (PL), X-ray photo electron spectroscopy (XPS) and Hall measurements. XRD patterns indicated that the deposited films had a polycrystalline hexagonal wurtzite structure with preferred (0 0 0 2) orientation. All films were found to exhibit a good transparency in the visible range. Analysis of the absorption edge revealed that the optical band gap energies of the films annealed at different temperatures varies between 3.49 eV and 3.69 eV. Room temperature PL spectra of the deposited films annealed at various temperatures consist of a near band edge emission and visible emission due to the electronic defects, which are related to deep level emissions, such as oxide antisite (O_Zn), interstitial zinc (Zn_i), interstitial oxygen (O_i) and zinc vacancy (V_Zn) which are generated during annealing process. The influence of annealing temperature on the chemical state of the dopants in the film was analysed by XPS spectra. Ion beam analysis (Rutherford back scattering) experiments were performed to evaluate the content of Li and Mg in the films. Hall measurements confirmed the p-type nature of the deposited films.     

Structural and optical evaluation of WOxNy films deposited by reactive magnetron sputtering

Thin films of tungsten oxynitrides were deposited on substrates preheated at 300 °C from metallic tungsten target using reactive pulsed d.c. magnetron sputtering. The deposition was carried out at different nitrogen to total reactive gas partial pressures ratios. The energy dispersive analysis of X-ray showed that significant incorporation of nitrogen occurred only when the nitrogen partial pressure exceeded 74% of the total reactive gas pressure. X-ray diffraction analysis revealed that the formation of a specific crystalline phase is affected by the composition and the possibility of competitive growth of different phases. The increase of nitrogen content into the films increases the optical absorption and decreases the optical band gap. The refractive index was determined from the transmittance spectra using Swanepoel's method. It was found that the refractive index increases with increasing nitrogen content over the entire spectral range. The values of the tungsten effective coordination number, N_c, was estimated from the analysis of the dispersion of the refractive index, and an increase in N_c with increasing nitrogen content was observed.     

Influence of annealing atmosphere on ZnO thin films grown by MOCVD

ZnO films were deposited on c-plane sapphire substrates by metal-organic chemical vapor deposition (MOCVD). Annealing treatments for as-deposited samples were performed in different atmosphere under various pressures in the same chamber just after growth. The effect of annealing atmosphere on the electrical, structural, and optical properties of the deposited films has been investigated by means of X-ray diffraction (XRD), atomic force microscope (AFM), Hall effect, and optical absorption measurements. The results indicated that the electrical and structural properties of the films were highly influenced by annealing atmosphere, which was more pronounced for the films annealed in oxygen ambient. The most significant improvements for structural and electrical properties were obtained for the film annealed in oxygen under the pressure of 60 Pa. Under the optimum annealing condition, the lowest resistivity of 0.28 Ω cm and the highest mobility of 19.6 cm² v⁻¹ s⁻¹ were obtained. Meanwhile, the absorbance spectra turned steeper and the optical band gap red shifted back to the single-crystal value.     

Investigation of the microstructure and optical properties of hydrogenated polymorphous silicon films prepared with pure silane

The dependences of microstructure and optical properties of hydrogenated polymorphous silicon (pm-Si:H) films on total gas pressure were studied. Instead of using high diluted silane in H₂, pure silane was used as the source gas. The films were grown by the radio-frequency plasma-enhanced chemical vapour deposition method. Fourier-transform infrared spectrometry was used to characterize the presence of Si _m H _n clusters in pm-Si:H film deposited on KBr substrate. Atomic force microscopy (AFM) analysis characterized the morphology of the pm-Si:H films and X-ray diffraction at grazing incidence angle (XRDGI) microstructure analysis also confirmed the existence of Si _m H _n nanocrystalline clusters in pm-Si:H. The thickness and optical constants of the films were measured by spectra ellipsometry as well as scanning electron microscopy. Derived using the Tauc relation, the dependence of optical bandgap, E_g , and coefficient, B, on the pressure during deposition process is discussed. The influence of inter-electrode distance on growth rate and surface smooth was analyzed using AFM.     

Effects of H2 ambient annealing in fully 0 0 2-textured ZnO:Ga thin films grown on glass substrates using RF magnetron co-sputter deposition

Gallium doped zinc oxide (ZnO:Ga) thin films were grown on glass substrates using RF magnetron co-sputtering, followed by H₂ ambient annealing at 623 K to explore a possibility of steady and low-cost process for fabricating transparent electrodes. While it was observed that the ZnO:Ga thin films were densely packed c-axis oriented self-textured structures, in the as-deposited state, the films contained Ga₂O₃ and ZnGa₂O₄ which had adverse effect on the electrical properties. On the other hand, post-annealing in H₂ ambient improved the electrical properties significantly via reduction of Ga₂O₃ and ZnGa₂O₄ to release elemental Ga which subsequently acted as substitutional dopant increasing the carrier concentration by two orders of magnitude. Transmittance of the ZnO:Ga thin films were all over 90% that of glass while the optical band gap varied in accordance with the carrier concentrations due to changes in Fermi level. Experimental observation in this study suggests that transparent conductive oxide (TCO) films based on Ga doped ZnO with good electrical and optical properties can be realized via simple low-cost process.