Structural and transport properties of cubic spinel ZnCo2O4 thin films grown by reactive magnetron sputtering

We report on the growth of cubic spinel ZnCo₂O₄ thin films by reactive magnetron sputtering and bipolarity of their conduction type by tuning of oxygen partial pressure ratio in the sputtering gas mixture. Crystal structure of zinc cobalt oxide films sputtered in an oxygen partial pressure ratio of 90% was found to change from wurtzite Zn_1−xCo_xO to spinel ZnCo₂O₄ with an increase of the sputtering power ratio between the Co and Zn metal targets, D_Co/D_Zn, from 0.1 to 2.2. For a fixed D_Co/D_Zn of 2.0 yielding single-phase spinel ZnCo₂O₄ films, the conduction type was found to be dependent on the oxygen partial pressure ratio: n-type and p-type for the oxygen partial pressure ratio below ∼70% and above ∼85%, respectively. The electron and hole concentrations for the ZnCo₂O₄ films at 300 K were as high as 1.37×10²⁰ and 2.81×10²⁰ cm⁻³, respectively, with a mobility of more than 0.2 cm²/V s and a conductivity of more than 1.8 S cm⁻¹.     

Opto-electrical properties of Ti-doped In2O3 thin films grown by pulsed laser deposition

By ablating titanium containing In₂O₃ target with a KrF excimer laser, highly conducting and transparent films on quartz were obtained to investigate the effects of growth temperature and oxygen pressure on the structural, optical and electrical properties of these films. We find that the transparency of the films depends more on the growth temperature and less on the oxygen pressure. Electrical properties, however, are found to be sensitive to both the growth temperature and oxygen pressure. We report in this paper that a growth temperature of 500 °C and an oxygen pressure of 7.5 × 10⁻⁷ bar lead to titanium-doped indium oxide films which have high mobility (up to 199 cm² V⁻¹ s⁻¹), low resistivity (9.8 × 10⁻⁵ Ω cm), and relatively high transmittance (∼88%).     

Effect of incorporating nonlanthanoidal indium on optical properties of ferroelectric Bi4Ti3O12 thin films

Bi₄Ti₃O₁₂ (BTO) and Bi_3.25In_0.75Ti₃O₁₂ (BTO:In) thin films were prepared on fused quartz and LaNiO₃/Si (LNO) substrates by chemical solution deposition (CSD). Their microstructures, ferroelectric and optical properties were investigated by X-ray diffraction, scanning electron microscope, ferroelectric tester and UV-visible-NIR spectrophotometer, respectively. The optical band-gaps of the films were found to be 3.64 and 3.45 eV for the BTO and BTO:In films, respectively. Optical constants (refractive indexes and extinction coefficients) were determined from the optical transmittance spectra using the envelope method. Following the single electronic oscillator model, the single oscillator energy E₀, the dispersion energy E_d, the average interband oscillator wavelength λ₀, the average oscillator strength S₀, the refractive index dispersion parameter (E₀/S₀), the chemical bonding quantity β, and the long wavelength refractive index n_∞ were obtained and analyzed. Both the refractive index and extinction coefficient of the BTO:In films are smaller than those of the BTO films. Furthermore, the refractive index dispersion parameter (E₀/S₀) increases and the chemical bonding quantity β decreases in the BTO and BTO:In films compared with those of bulk.     

Deposition and characterization of La2Ti2O7 thin films via spray pyrolysis process

Thin films of La₂Ti₂O₇ have been deposited on fused silica and Si substrates by a spray pyrolysis method using ethylene glycol solution of La(III)-Ti(IV)-citrate complexes as starting material and O₂ as a carrier gas. The composition, crystal structure and morphology of the films are studied.     

Effect of thickness on structural, optical and electrical properties of nanostructured ZnO thin films by spray pyrolysis

Transparent conducting zinc oxide thin films were prepared by spray pyrolytic decomposition of zinc acetate onto glass substrates with different thickness. The crystallographic structure of the films was studied by X-ray diffraction (XRD). XRD measurement showed that the films were crystallized in the wurtzite phase type. The grain size, lattice constants and strain in films were calculated. The grain size increases with thickness. The studies on the optical properties show that the direct band gap value increases from 3.15 to 3.24 eV when the thickness varies from 600 to 2350 nm. The temperature dependence of the electrical conductivity during the heat treatment was studied. It was observed that heat treatment improve the electrical conductivity of the ZnO thin films. The conductivity was found to increase with film thickness.     

Structural, optical and electrical characterization of highly conducting Mo-doped In2O3 thin films

Highly conducting and transparent thin films of molybdenum-doped indium oxide were deposited on quartz by pulsed laser deposition. The effect of growth temperature and oxygen partial pressure on the structural, optical and electrical properties was studied. We find that the film transparency depends on the growth temperature. The average transmittance of the films grown at different temperatures is in range of 48-87%. The X-ray diffraction results show that the films grown at low temperature are amorphous while the films grown at higher temperature are crystalline. Electrical properties are found to be sensitive to both the growth temperature and oxygen pressure. Resistivity of the films decreases from 1.3 × 10⁻³ Ω cm to 8.9 × 10⁻⁵ Ω cm while mobility increases from 9 cm²/V s to 138 cm²/V s as the growth temperature increases from room temperature to 700 °C. However, with increase in oxygen pressure, resistivity increases but the mobility decreases after attaining a maximum. The temperature-dependent resistivity measurements show transition form semiconductor to metallic behavior. The film grown at 500 °C under an oxygen pressure of 1.0 × 10⁻³ mbar is found to exhibit high mobility (250 cm²/V s), low resistivity (6.7 × 10⁻⁵ Ω cm), and relatively high transmittance (∼90%).     

Electrochemical characterization of Mn: Co3O4 thin films prepared by spray pyrolysis via aqueous route

Present investigation reports, spray pyrolytic deposition of Mn: Co₃O₄ thin films onto the stainless steel by spray pyrolysis, at the deposition temperature 573 ± 2 K via aqueous route. Prepared electrodes were characterized structurally and morphologically by means of XRD and SEM. Also optical and electrochemical characterizations were carried out in depth. Structural characterization confirms face centered cubic and tetragonal body centered crystal structures for Co₃O₄ and Mn₃O₄ respectively. The rough granular morphology is observed form SEM. Electrochemical study reveals the pseudo capacitive as well as double layer behavior with optimum specific capacitance 485.29 F/g at the scan rate 1 mV/s in 1 M KOH electrolyte. Specific energy, specific power and columbic efficiency were calculated using chronopotentiometric technique. Electrochemical impedance spectroscopy was carried out in the frequency range 1 mHz–1 MHz. Randles equivalent circuit parameters associated with the operative cell are reported.     

Nanocrystallite formation in Pd capped PrH3−δ films

Restricting the palladium cap layer thickness to ≤9 nm on top of 170 nm Pr films during in situ hydrogen loading has been shown to result in nanocrystallite size PrH_3−δ films even though the deposited Pr films are of large crystallite size. The effect is attributed to hydrogen-induced stresses in the PrH_3−δ films, which trigger structural rearrangement. These nanocrystalline films show a blue shift of the transmittance edge with respect to PrH_3−δ films of large crystallite size. The approximate size of the nanocrystallites calculated from the blue shift using an effective mass approximation (EMA) theory is supported by XRD, TEM and AFM measurements.     

Synthesis and characterization of Gd0.1Ce0.9O1.95 thin films by spray pyrolysis technique

The Gd doped ceria (CGO) in thin layers is of great interest for low temperature operation. In the present investigation, we report on the use of spray pyrolysis technique for the synthesis of CGO thin films. The process parameters were optimized for synthesizing Gd_0.1Ce_0.9O_1.95 films. Films were characterized by XRD, EDS, SEM, and AFM and are observed to be phase pure and dense with surface roughness of the order of ∼5 nm. The d.c. conductivity was also measured and is observed to be ∼0.5 S/cm at 623 K.     

Photoluminescence in amorphous (PbLa)TiO3 thin films deposited on different substrates

Pb_1−XLa_XTiO₃ thin films, (X=0.0; 13 and 0.27 mol%) were prepared by the polymeric precursor method. Thin films were deposited on Pt/Ti/SiO₂/Si (1 1 1), Si (1 0 0) and glass substrates by spin coating, and annealed in the 200-300°C range in an O₂ atmosphere. X-ray diffraction, scanning electron microscopy and atomic force microscopy were used for the microstructural characterization of the thin films. Photoluminescence (PL) at room temperature has been observed in thin films of (PbLa)TiO₃. The films deposited on Pt/Ti/SiO₂/Si substrates present PL intensity greater than those deposited on glass and silicon substrates. The intensity of PL in these thin films was found to be dependent on the thermal treatment and lanthanum molar concentration.     

Parallel syntheses and thermoelectric properties of Ce-doped SrTiO3 thin films

Thermoelectric properties of single crystalline Ce_xSr_1−xTiO₃ films (0 ≤ x ≤ 0.5) have been studied by using combinatorial pulsed-laser deposition. Temperature gradient method was used for identifying an optimum growth temperature for SrTiO₃ homoepitaxial growth, at which both oxygen stoichiometry and persisting layer-by-layer growth mode could be accomplished. Electrical conductivity (σ) and Seebeck coefficient (S) were measured at room temperature for the composition-spread films grown at the optimized temperature and found to be considerably higher than those reported for bulk poly-crystalline compounds. Hall measurement revealed that carrier density linearly increased with increasing x, suggesting that a trivalent Ce ions substituted divalent Sr ions to supply electrons. A maximum power factor (S²σ) was obtained for the x = 0.2 film, being 7 and 14 μW/K² cm at 300 and 900 K, respectively.     

Epitaxial growth and characterization of CaVO3 thin films

Epitaxial thin films of CaVO₃ were synthesized on SrTiO₃, LaAlO₃ and (La_0.27Sr_0.73)(Al_0.65Ta_0.35)O₃ substrates by pulsed laser deposition. All CaVO₃ films, independent of epitaxial strain, exhibit metallic and Pauli paramagnetic behavior as CaVO₃ single crystals. X-ray absorption measurements confirmed the 4+ valence state for Vanadium ions. With prolonged air exposure, an increasing amount of V³⁺ is detected and is attributed to oxygen loss in the near surface region of the films.     

Optical investigation of charge-transfer transitions in spinel Co3O4

Optical transitions in normal-spinel Co₃O₄ have been identified by investigating the variation of its optical absorption spectrum with the replacement of Co by Zn. Three optical-transition structures were located at about 1.65, 2.4, and 2.8 eV from the measured dielectric function of Co₃O₄ by spectroscopic ellipsometry. The variation of the absorption structures with the Zn substitution (Zn_xCo_3−xO₄) can be explained in terms of charge-transfer transitions involving d states of Co ions. The 1.65 eV structure is assigned to a d-d charge-transfer transition between the t_2g states of octahedral Co³⁺ ion and t₂ states of tetrahedral Co²⁺ ion, t_2g(Co³⁺)→t₂(Co²⁺). The 2.4 and 2.8 eV structures are interpreted as due to charge-transfer transitions involving the p states of O²⁻ ion: p(O²⁻)→t₂(Co²⁺) for the 2.4 eV absorption and p(O²⁻)→e_g(Co³⁺) for the 2.8 eV absorption. The observed gradual reduction of the 1.65 and 2.4 eV absorption strength with the increase of the Zn composition for Zn_xCo_3−xO₄ can be explained in terms of the substitution of the tetrahedral Co²⁺ sites by Zn²⁺ ions. The crystal-field splitting Δ_Oh between the e_g and the t_2g states of the octahedral Co³⁺ ion is estimated to be 2 eV.     

Analysis of codeposited Gd2O3/SiO2 composite thin films by phase modulated spectroscopic ellipsometric technique

Tailoring of the refractive index of optical thin films has been a very fascinating as well as challenging topic for developing new generation optical coatings. In the present work a novel Gd₂O₃/SiO₂ composite system has been experimented and probed for its superior optical properties through phase modulated spectroscopic ellipsometry, spectrophotometry and atomic force microscopy. The optical parameters of the composite films have been evaluated using Tauc-Lorentz (TL) formulations. In order to derive the growth dependent refractive index profiles, each sample film has been modeled as an appropriate multilayer structure where each sub-layer was treated with the above TL parameterizations. All codeposited films demonstrated superiority with respect to the band gap and morphological measurements. At lower silica mixing compositions such as in 10-20% level, the composite films depicted superior spectral refractive index profile, band gap as well as the morphology. This aspect highlighted the fact that microstructural densifications in composite films can override the chemical compositions while deciding the refractive index and optical properties in such thin films.     

Optical and structural studies on Ba(Mg1/3Ta2/3)O3 thin films obtained by radiofrequency assisted pulsed plasma deposition

Single-phase Ba(Mg_1/3Ta_2/3)O₃ thin films were prepared by radiofrequency plasma beam assisted pulsed laser deposition (RF-PLD) starting from a bulk ceramic target synthesized by solid state reaction. Atomic force microscopy, X-ray diffraction and spectroscopic ellipsometry were used for morphological, structural and optical characterization of the BMT thin films. The X-ray diffraction spectra show that the films exhibit a polycrystalline cubic structure. From spectroscopic ellipsometry analysis, the refractive index varies with the thin films deposition parameters. By using the transmission spectra and assuming a direct band to band transition a band gap value of ≈4.72 eV has been obtained.     

Synthesis and characterization of Co3O4 nanorods by thermal decomposition of cobalt oxalate

Cobalt oxalate was used as a precursor to prepare Co₃O₄ nanorods by thermal decomposition. The combinations of triphenylphosphine and oleylamine were added as surfactants to control the morphology of the particles. The products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS). The diameters of Co₃O₄ nanorods are 20 nm and the average lengths are around 500 nm. The hysteresis loops of the obtained samples reveal the ferromagnetic behaviors, the enhanced coercivity (H_c) and decreased saturation magnetization (M_s) in contrast to their respective bulk materials. The study provides a simple and efficient route to synthesize Co₃O₄ nanorods at low temperature.     

A novel strategy to synthesize cobalt hydroxide and Co3O4 nanowires

Cobalt hydroxide ultra fine nanowires were prepared by a facile hydrothermal route using hydrogen peroxide. This method provides a simple, low cost, and large-scale route to produce β-cobalt hydroxide nanowires with an average diameter of 5 nm and a length of ca. 10 μm, which show a predominant well-crystalline hexagonal brucite-like phase. Their thermal decomposition produced highly uniform nanowires of cobalt oxide (Co₃O₄) under temperature 500 °C in the presence of oxygen gas. The produced cobalt oxide was characterized by X-ray diffraction, transmission electronic microscopy, and selected-area electron diffraction. The results indicated that cobalt oxide nanowires with an average diameter of 10 nm and a length of ca. 600 nm have been formed, which show a predominant well-crystalline cubic face-centered like phase.     

XRD and XPS characterization of mixed valence Mn3O4 hausmannite thin films prepared by chemical spray pyrolysis technique

Spray pyrolysis technique has been employed successfully for the synthesis of single phase mixed valence spinel hausmannite (Mn₃O₄) thin films using alcoholic start solution of manganese acetate (Mn(CH₃COO)₂·4H₂O) on pyrex glass substrates at atmospheric pressure using air as a carrier gas. Thermal decomposition of the precursor in the temperature range 320-490 °C led to the formation of Mn₃O₄ phase as revealed from the thermogravimetry analysis. Prepared samples are characterized by X-ray diffraction that shows spinel structure with space group I4₁/amd. Pure and well crystallized specimen is subjected to X-ray photoelectron spectroscopy for the surface chemistry investigation of these systems at a molecular level. Surface Mn/O ratio is compared to the bulk composition of the sample. Atomic force micrographs revealed that the morphology and the surface grains of the films largely influenced by the substrate temperature.     

Preparation of transparent conductive TiO2:Nb thin films by pulsed laser deposition

This study investigated the optical and electrical properties of Nb-doped TiO₂ thin films prepared by pulsed laser deposition (PLD). The PLD conditions were optimized to fabricate Nb-doped TiO₂ thin films with an improved electrical conductivity and crystalline structure. XRD analyses revealed that the deposition at room temperature in 0.92 Pa O₂ was suitable to produce anatase-type TiO₂. A Nb-doped TiO₂ thin film attained a resistivity as low as 6.7 × 10⁻⁴ Ω cm after annealing at 350 °C in vacuum (<10⁻⁵ Pa), thereby maintaining the transmittance as high as 60% in the UV-vis region.     

High mobility W-doped In2O3 thin films: Effect of growth temperature and oxygen pressure on structural, electrical and optical properties

Highly conducting and transparent thin films of tungsten (W)-doped indium oxide were obtained using pulsed laser deposition to study the effect of growth temperature and oxygen pressure on structural, optical and electrical properties. The transparency of the films is seen to largely depend on the growth temperature. The electrical properties, however, are found to depend strongly on both the growth temperature and the oxygen pressure. High mobility (up to 358 cm² V⁻¹ s⁻¹), low resistivity (1.1 × 10⁻⁴ Ω cm), and relatively high transmittance (∼90%) tungsten-doped indium oxide films have been prepared at a growth temperature of 500 °C and an oxygen pressure of 1 × 10⁻⁶ bar.