Structural, electrical and optical properties of TiO2 doped WO3 thin films

TiO₂ doped WO₃ thin films were deposited onto glass substrates and fluorine doped tin oxide (FTO) coated conducting glass substrates, maintained at 500 °C by pyrolytic decomposition of adequate precursor solution. Equimolar ammonium tungstate ((NH₄)₂WO₄) and titanyl acetyl acetonate (TiAcAc) solutions were mixed together at pH 9 in volume proportions and used as a precursor solution for the deposition of TiO₂ doped WO₃ thin films. Doping concentrations were varied between 4 and 38%. The effect of TiO₂ doping concentration on structural, electrical and optical properties of TiO₂ doped WO₃ thin films were studied. Values of room temperature electrical resistivity, thermoelectric power and band gap energy (E_g) were estimated. The films with 38% TiO₂ doping in WO₃ exhibited lowest resistivity, n-type electrical conductivity and improved electrochromic performance among all the samples. The values of thermoelectric power (TEP) were in the range of 23-56 μV/K and the direct band gap energy varied between 2.72 and 2.86 eV.     

Preparation of WO3 nanoparticles and application to NO2 sensor

WO₃ nanoparticles were prepared by evaporating tungsten filament under a low pressure of oxygen gas, namely, by a gas evaporation method. The crystal structure, morphology, and NO₂ gas sensing properties of WO₃ nanoparticles deposited under various oxygen pressures and annealed at different temperatures were investigated. The particles obtained were identified as monoclinic WO₃. The particle size increased with increasing oxygen pressure and with increasing annealing temperature. The sensitivity increased with decreasing particle size, irrespective of the oxygen pressure during deposition and annealing temperature. The highest sensitivity of 4700 to NO₂ at 1 ppm observed in this study was measured at a relatively low operating temperature of 50 °C; this sensitivity was observed for a sensor made of particles as small as 36 nm.     

VO2-WO3 nanocomposite thin films synthesized by pulsed laser deposition technique

Pure VO₂ and VO₂-WO₃ composite thin films were grown on quartz substrate by pulsed laser deposition (PLD) technique. The influence of varying WO₃ molar concentration in the range from x = 0.0 to x = 0.4 on structural, electrical and optical properties of VO₂-WO₃ nanocomposite thin films has been systematically investigated. X-ray diffraction studies reveal the single crystalline monoclinic VO₂ phase (m-VO₂) up to 10% of WO₃ content whereas both m-VO₂ as well as h-WO₃ (hexagonal WO₃) phases were present at higher WO₃ content (0.2 ≤ x ≤ 0.4). Optical transmittance spectra of the films showed blue shift in the absorption edge with increase in WO₃ content. Temperature dependence of resistivity (R-T) measurements indicates significant variation in metal-insulator transition temperature, width of the hysteresis, and shape of the hysteresis curve. Cyclic Voltammetry measurements were performed on VO₂-WO₃ thin films. A direct correlation between V/W ratio and structure-property relationship was established. The present investigations reveal that doping of WO₃ in VO₂ is effective to increase the optical transmittance and to reduce the semiconductor to metal phase transition temperature close to room temperature.     

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.     

Density functional theory study of NO2-sensing mechanisms of pure and Ti-dopedWO3 （002） surfaces

Density functional theory (DFT) calculations are employed to explore the NO₂-sensing mechanisms of pure and Ti-doped WO₃ (002) surfaces. When Ti is doped into the WO₃ surface, two substitution models are considered: substitution of Ti for W_6c and substitution of Ti for W_5c. The results reveal that substitution of Ti for 5-fold W forms a stable doping structure, and doping induces some new electronic states in the band gap, which may lead to changes in the surface properties. Four top adsorption models of NO₂ on pure and Ti-doped WO₃ (002) surfaces are investigated: adsorptions on 5-fold W (Ti), on 6-fold W, on bridging oxygen, and on plane oxygen. The most stable and likely NO₂ adsorption structures are both N-end oriented to the surface bridge oxygen O_1c site. By comparing the adsorption energy and the electronic population, it is found that Ti doping can enhance the adsorption of NO₂, which theoretically proves the experimental observation that Ti doping can greatly increase the WO₃ gas sensor sensitivity to NO₂ gas.     

Influence of postdeposition annealing on structural properties and electrical characteristics of thin Tm2O3 and Tm2Ti2O7 dielectrics

We describe the structural properties and electrical characteristics of thin thulium oxide (Tm₂O₃) and thulium titanium oxide (Tm₂Ti₂O₇) as gate dielectrics deposited on silicon substrates through reactive sputtering. The structural and morphological features of these films were explored by X-ray diffraction, X-ray photoelectron spectroscopy, secondary ion mass spectrometry, and atomic force microscopy, measurements. It is found that the Tm₂Ti₂O₇ film annealed at 800 °C exhibited a thinner capacitance equivalent thickness of 19.8 Å, a lower interface trap density of 8.37 × 10¹¹ eV⁻¹ cm⁻², and a smaller hysteresis voltage of ∼4 mV than the other conditions. We attribute this behavior to the Ti incorporated into the Tm₂O₃ film improving the interfacial layer and the surface roughness. This film also shows negligible degrees of charge trapping at high electric field stress.     

Effect of complexing agent on the properties of electrochemically deposited Cu2ZnSnS4 (CZTS) thin films

The Cu₂ZnSnS₄ (CZTS) thin films have been electrochemically deposited on Mo-coated glass substrate from weak acidic medium (pH 4.5-5) at room temperature. The effect of complexing agent (tri-sodium citrate) on the structural, morphological and compositional properties of CZTS thin films has been investigated. The as-deposited and annealed thin films were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM),EDAX and X-ray photoelectron spectroscopy (XPS) techniques for their structural, morphological, compositional and chemical properties, respectively. XRD studies reveal that the amorphous nature of as-deposited thin film changes into polycrystalline with kesterite crystal structure after annealing in Ar atmosphere. The film prepared without complexing agent showed well-covered surface morphology on the substrate with some cracks on the surface of the film whereas those prepared using complexing agent, exhibited uneven and slightly porous and some overgrown particles on the surface of the films. After annealing, morphology changes into the flat grains, uniformly distributed over the entire surface of the substrate. The EDAX and XPS study reveals that the films deposited using 0.2 M tri-sodium citrate are nearly stoichiometric.     

Structural and optical properties of Er, Yb co-doped Y2O3 thin films

Thin Er³⁺, Yb³⁺ co-doped Y₂O₃ films were grown on (1 0 0) YAG substrates by pulsed laser deposition. Ceramic targets having different active ion concentration were used for ablation. The influence of the rare-earth content and oxygen pressure applied during the deposition on the structural, morphological and optical properties of the films were investigated. The films deposited at the lower pressure, 1 Pa, and at 1/10 Er to Yb doping ratio are highly textured along the (1 1 1) direction of the Y₂O₃ cubic phase. In addition to the crystalline structure, these films possess smoother surface compared to those prepared at the higher pressure, 10 Pa. All other films are polycrystalline, consisting of cubic and monoclinic phases of Y₂O₃. The rougher surface of the films produced at the higher-pressure leads to higher scattering losses and different behavior of the reflectivity spectra. Optical anisotropy in the films of less than 0.004 was measured regardless of the monoclinic structure obtained. Waveguide losses of about 1 dB/cm at 633 nm were obtained for the films produced at the lower oxygen pressure.     

Luminescence of ZnWO4 and CdWO4 thin films prepared by spray pyrolysis

Thin films of ZnWO₄ and CdWO₄ were prepared by spray pyrolysis and the structural, optical, and luminescence properties were investigated. Both ZnWO₄ and CdWO₄ thin films showed a broad blue-green emission band. The broad band of ZnWO₄ films was centered at 495 nm (2.51 eV) consisted of three bands at 444 nm (2.80 eV), 495 nm (2.51 eV) and 540 nm (2.30 eV). The broad band of CdWO₄ films at 495 nm (2.51 eV) could be decomposed to three bands at 444 nm (2.80 eV), 495 nm (2.51 eV) and 545 nm (2.28 eV). These results are consistent with emission from the WO₆⁶⁻ molecular complex. The luminance and efficiency for ZnWO₄ film at 5 kV and 57 μA/cm² were 48 cd/m² and 0.22 lm/w, respectively, and for CdWO₄ film the values were 420 cd/m² and 1.9 lm/w.     

Preparation of Bi2S3 thin films with a nanoleaf structure by electrodeposition method

Nanoleaf-like Bi₂S₃ thin films were deposited on indium tin oxide (ITO) glass using Bi(NO₃)₃ and Na₂S₂O₃ as precursors by a cathodic electrodeposition process. The as-deposited thin films were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and photoluminescence spectrum (PL). The influence of precursor solution mole concentration ratios [Bi(NO₃)₃]/[Na₂S₂O₃] on the phase compositions, morphologies and photoluminescence properties of the obtained thin films were investigated. Results show that a uniform Bi₂S₃ thin film with nanoleaf structure can be obtained with the precursor solution concentration ratio [Bi(NO₃)₃]/[Na₂S₂O₃] = 1:7. The as-prepared thin films exhibit blue-green photoluminescence properties under ultraviolet light excitation. With the increase of concentration ratios [Bi(NO₃)₃]/[Na₂S₂O₃] in the deposition solution, the crystallizations and PL properties of Bi₂S₃ thin films are obviously improved.     

Effect of WO3 on structural and optical properties of CeO2-PbO-B2O3 glasses

Pure and WO₃ doped CeO₂-PbO-B₂O₃ glasses are prepared by the melt-quench technique. The structural and optical analyses of glasses are carried out by XRD, FTIR, density and UV-vis spectroscopic measurement techniques. FTIR analysis indicates the transformation of structural units of BO₃ into BO₄ with W-O-W vibration and the presence of WO₄ and WO₆ units observed with increase in WO₃ contents. Decrease in band gap for CeO₂-PbO-B₂O₃ glasses from 2.89 to 2.30 eV and for WO₃ doped glasses from 2.89 to 1.95 eV has been observed and discussed. This decrease in band gap with WO₃ doping approaches to semiconductor behavior. It shows that the presence of WO₃ in the glass samples causes more compaction of the borate network due to the formation of BO₄ groups and the presence of WO₄ and WO₆ groups, which result in a decrease in the optical band gap energy and increase in the density.     

Structural properties and electrical characteristics of high-k Dy2O3 gate dielectrics

This paper describes the structural properties and electrical characteristics of thin Dy₂O₃ dielectrics deposited on silicon substrates by means of reactive sputtering. The structural and morphological features of these films after postdeposition annealing were studied by X-ray diffraction and X-ray photoelectron spectroscopy. It is found that Dy₂O₃ dielectrics annealed at 700 °C exhibit a thinner capacitance equivalent thickness and better electrical properties, including the interface trap density and the hysteresis in the capacitance-voltage curves. Under constant current stress, the Weibull slope of the charge-to-breakdown of the 700 °C-annealed films is about 1.6. These results are attributed to the formation of well-crystallized Dy₂O₃ structure and the reduction of the interfacial SiO₂ layer.     

Structural transition and blue emission in textured and highly transparent spray deposited Li doped WO3 thin films

The effect of Li (0-5 wt%) doping on the properties of WO₃ thin films deposited using an automated homemade spray pyrolysis unit is studied. Change in structural and optical properties is observed on doping with Li. The XRD patterns shows that undoped WO₃ film has an orthorhombic phase while the Li (1-5 wt%) doped WO₃ films have tetragonal phase. The SEM and AFM images confirm relatively smooth surface of Li doped WO₃ films compared to undoped WO₃ film. Transmission spectra reveal that the transparency of the Li-doped films is much greater than that of undoped film. From the transmission data, the direct, indirect bandgap and phonon energies were calculated. Room temperature photoluminescence spectra showed pronounced blue emission on doping with Li.     

Effect of solution concentration on physicochemical and gas sensing properties of sprayed WO3 thin films

Sub-stoichiometric tungsten trioxide (WO₃) thin films are deposited onto the glass substrates by spray pyrolysis technique using ammonium metatungstate. Effect of solution concentration on structural, morphological, optical, electrical and NO₂ sensing properties of WO₃ thin films is studied. Films are polycrystalline with monoclinic crystal structure and sub-stoichiometric as observed form the XRD and XPS studies, respectively. The SEM and AFM images show micro grained structure and surface roughness increases with increase in solution concentration. The PL studies revealed that the majority of the defects are the oxygen vacancies. From XPS and PL studies it is observed that, oxygen vacancies decrease with increase in solution concentration. The dielectric constant of the films as a function of frequency is in concurrence with resistivity measurements. Films show reproducible and reversible gas response at various operating temperatures and gas concentrations. Highest sensor response (38%) towards 200 ppm NO₂ concentration is observed for the film with 15 mM solution concentration at moderate operating temperature (200 °C). Pd sensitization enhanced gas response to 68% and improved kinetics of the sensor. Films are highly selective towards NO₂ as compared with the various gases such as SO₂, LPG, NH₃ and H₂S.     

A novel chemical synthesis and characterization of Mn3O4 thin films for supercapacitor application

Mn₃O₄ thin films have been prepared by novel chemical successive ionic layer adsorption and reaction (SILAR) method. Further these films were characterized for their structural, morphological and optical properties by means of X-ray diffraction (XRD), Fourier transform infrared spectrum (FTIR), field emission scanning electron microscopy (FESEM), wettability test and optical absorption studies. The XRD pattern showed that the Mn₃O₄ films exhibit tetragonal hausmannite structure. Formation of manganese oxide compound was confirmed from FTIR studies. The optical absorption showed existence of direct optical band gap of energy 2.30 eV. Mn₃O₄ film surface showed hydrophilic nature with water contact angle of 55°. The supercapacitive properties of Mn₃O₄ thin film investigated in 1 M Na₂SO₄ electrolyte showed maximum supercapacitance of 314 F g⁻¹ at scan rate 5 mV s⁻¹.     

Chemical synthesis of spinel nickel ferrite (NiFe2O4) nano-sheets

The present investigation is related to the deposition of single-phase nano-sheets spinel nickel ferrite (NiFe₂O₄) thin films onto glass substrates using a chemical method. Nano-sheets nickel ferrite films were deposited from an alkaline bath containing Ni²⁺ and Fe²⁺ ions. The films were characterized for their structural, surface morphological and electrical properties by means of X-ray diffraction (XRD), transmission electron microscope (TEM), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and two-point probe electrical resistivity techniques. The X-ray diffraction pattern showed that NiFe₂O₄ nano-sheets are oriented along (3 1 1) plane. The FT-IR spectra of NiFe₂O₄ films showed strong absorption peaks around 600 and 400 cm⁻¹ which are typical for cubic spinel crystal structure. Microstructural study of NiFe₂O₄ film revealed nano-sheet like morphology with average sheet thickness of 30 nm. The room temperature electrical resistivity of the NiFe₂O₄ nano-sheets was 10⁷ Ω cm.     

Structural, morphological and optical properties of CuAlS2 films deposited by spray pyrolysis method

The structural, morphological and optical properties of CuAlS₂ films deposited by spray pyrolysis method have been investigated. CuAlS₂ in the form of films is prepared at different deposition conditions by a simple and economical spray pyrolysis method. The structural, surface morphology and optical properties of the films were analyzed by X-ray diffraction (XRD), scanning electron microscope (SEM), atomic force microscope (AFM) and absorbance spectra, respectively. The films were polycrystalline, crystallized in a tetragonal structure, and are preferentially orientated along the (1 1 2) direction. Grain size values, dislocation density, and d% error of CuAlS₂ films were calculated. The optical band gap of the CuAlS₂ film was found to be 3.45 eV. The optical constants such as refractive index, extinction coefficient and dielectric constants of the CuAlS₂ film were determined. The refractive index dispersion curve of the film obeys the single oscillator model. Optical dispersion parameters E_o and E_d developed by Wemple-DiDomenico were calculated and found to be 3.562 and 12.590 eV.     

The effect of Si surface nitridation on the interfacial structure and electrical properties of (La2O3)0.5(SiO2)0.5 high-k gate dielectric films

Thermal stability, interfacial structures and electrical properties of amorphous (La₂O₃)_0.5(SiO₂)_0.5 (LSO) films deposited by using pulsed laser deposition (PLD) on Si (1 0 0) and NH₃ nitrided Si (1 0 0) substrates were comparatively investigated. The LSO films keep the amorphous state up to a high annealing temperature of 900 °C. HRTEM observations and XPS analyses showed that the surface nitridation of silicon wafer using NH₃ can result in the formation of the passivation layer, which effectively suppresses the excessive growth of the interfacial layer between LSO film and silicon wafer after high-temperature annealing process. The Pt/LSO/nitrided Si capacitors annealed at high temperature exhibit smaller CET and EOT, a less flatband voltage shift, a negligible hysteresis loop, a smaller equivalent dielectric charge density, and a much lower gate leakage current density as compared with that of the Pt/LSO/Si capacitors without Si surface nitridation.     

Studies on sprayed lanthanum sulphide (La2S3) thin films from non-aqueous medium

Thin films of lanthanum sulphide (La₂S₃) have been deposited onto glass substrates by spray pyrolysis technique from non-aqueous (methanol) medium. The structural, morphological, optical, dielectric, electric and thermoemf properties were studied. The films were polycrystalline with an irregular shaped particles present over the porous structure within a fibrous network structure. The optical band gap was estimated to be 2.50 eV. The dielectric properties were measured in the range 100 Hz-1 MHz. The electrical resistivity was of the order of 10⁴ to 10⁵ Ω cm. Thermoemf study revealed that the La₂S₃ films exhibit p-type electrical conductivity.     

In-situ bridging of SnO2 nanowires between the electrodes and their NO2 gas sensing characteristics

A simple and efficient way of making highly sensitive SnO₂ nanowire-based gas sensors without an individual lithography process was studied. The SnO₂ nanowires network was floated upon the Si substrate by separating the Au catalyst layer from the substrate. As the electric current is transported along the networks of the nanowires, not along the surface layer on the substrate, the gas sensitivities could be maximized in this networked and floated structures. The sensitivity was 5-30 when the NO₂ concentration was 1-10 ppm. The response time was ca. 20-60 s.