Characterization of oxide thin films using optical techniques

Thin films of oxide materials are playing a growing role as critical elements in optoelectronic devices and nanoscale devices. In this work, thin films of some typical oxides such as WO₃, Ga₂O₃ and SrTiO₃ were investigated. We present measurements of those films, using various optical techniques like photoconductivity transients over a wide time range and photo-Hall measurements. Analysis of the photo-Hall and photoconductivity data permits the determination of the contribution to the photoconductivity made by the carrier mobility and concentration. A model for dispersive carrier transport was proposed to explain the relaxation of the photoconductivity in oxide thin films. In addition, photoluminescence characterization was used to study microstructures and energy band in oxide thin films. The broad emission from oxide host, consisting of several band peaks, was likely due to a recombination process with several possible paths. The dependence of the luminescent intensity on the annealing atmosphere was associated with the presence of oxygen vacancies. It is suggested that our optical analysis efforts have improved the understanding of oxide thin films, and this should lead to the necessary advancements in a variety of devices.     

A simple photochemical method to synthesize Ga2O3-Dy-M thin films and their evaluation as optical materials (where M=Cr or Co)

We report the photochemical method to synthesize Ga₂O₃-Dy³⁺-Co³⁺ and Ga₂O₃-Dy³⁺-Cr³⁺ thin films. X-ray photoelectron spectroscopy, X-ray diffraction and photoluminescence were used to characterize the products. These analyses revealed that as-deposited and annealed films are amorphous. The optical characterization of the films showed that these are highly transparent in the visible spectrum but decrease significantly with doped and co-doped films. Under the excitation of UV light (254 nm) the doped films (Ga₂O₃-Dy³⁺) show the characteristic emissions of Dy³⁺ at 500, 575, 594, 605 and 652 nm corresponding to ⁴F_9/2→⁶H_J ( J=15/2, 13/2 and 11/2) transitions but the emissions decrease with the co-doped films (Ga₂O₃-Dy³⁺-M³⁺, where M=Cr or Co); a possible emission mechanism and energy transfer have been proposed.     

Nonlinear optical properties in SrTiO3 thin films by pulsed laser deposition

Well-crystallized 250 nm-thick SrTiO₃ thin films on fused-quartz substrate were prepared by pulsed laser deposition. The band-gap of SrTiO₃ thin film by transmittance spectra is equal to 3.50 eV, larger than 3.22 eV for the bulk crystal. The nonlinear optical properties of the films were examined with picosecond pulses at 1.064 μm excitation. A large two-photon absorption (TPA) with absorption coefficient of 87.7 cm/GW was obtained, larger than 51.7 cm/GW for BaTiO₃ thin films. The nonlinear refractive index n₂ is equal to 5.7×10⁻¹⁰ esu with a negative sign, larger than 0.267×10⁻¹¹ esu for bulk SrTiO₃. The large TPA is attributed to intermediate energy levels introduced by the grain boundaries, and the optical limiting behaviors stemming from both TPA and negative nonlinear refraction were also discussed.     

Structural and optical properties of Ga2(1−x)In2xO3 films prepared on α-Al2O3 (0 0 0 1) by MOCVD

Ga_2(1−x)In_2xO₃ thin films with different indium content x [In/(Ga + In) atomic ratio] were prepared on α-Al₂O₃ (0 0 0 1) substrates by the metal organic chemical vapor deposition (MOCVD). The structural and optical properties of the Ga_2(1−x)In_2xO₃ films were investigated in detail. Microstructure analysis revealed that the film deposited with composition x = 0.2 was polycrystalline structure and the sample prepared with x up to 0.8 exhibited single crystalline structure of In₂O₃. The optical band gap of the films varied with increasing Ga content from 3.72 to 4.58 eV. The average transmittance for the films in the visible range was over 90%.     

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.     

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.     

Electrical and optical properties of Ga doped zinc oxide thin films deposited at room temperature by continuous composition spread

Ga doped ZnO (GZO) thin films were deposited on glass substrates at room temperature by continuous composition spread (CCS) method. CCS is thin films growth method of various Ga_xZn_1−xO(GZO) thin film compositions on a substrate, and evaluating critical properties as a function position, which is directly related to material composition. Various compositions of Ga doped ZnO deposited at room temperature were explored to find excellent electrical and optical properties. Optimized GZO thin films with a low resistivity of 1.46 × 10⁻³ Ω cm and an average transmittance above 90% in the 550 nm wavelength region were able to be formed at an Ar pressure of 2.66 Pa and a room temperature. Also, optimized composition of the GZO thin film which had the lowest resistivity and high transmittance was found at 0.8 wt.% Ga₂O₃ doped in ZnO.     

Synthesis and materials properties of transparent conducting In2O3 films prepared by sol-gel-spin coating technique

Transparent conducting indium oxide (In₂O₃) thin films have been prepared on glass substrates by the simple sol-gel-spin coating technique. These films have been characterized by X-ray diffraction, resistivity and Hall effect measurements, optical transmission, scanning electron microscopy and atomic force microscopy for their structural, electrical, optical and morphological properties. The influence of spin parameters, number of coating, process temperature on the quality of In₂O₃ films are studied. In the operating range of deposition, 400-475 °C, all the films showed predominant (2 2 2) orientation. Films deposited at optimum process conditions exhibited a resistivity of 2×10⁻² Ω cm along with the average transmittance of about 80% in the visible spectral range (400-700 nm).     

Growth of highly-oriented CaCu3Ti4O12 thin films on SrTiO3 (1 0 0) substrates by a chemical solution route

Highly-oriented CaCu₃Ti₄O₁₂ (CCTO) thin films deposited directly on SrTiO₃ (1 0 0) substrates have been developed successfully using a chemical solution coating method. X-ray diffraction (XRD), scanning electron microscopy (SEM), and atomic force microscopy (AFM) were employed to characterize the structure and the morphology. It was observed that the CCTO thin films had the 1 μm × 1 μm domain-like microstructure that consists of compact grains of about 0.1 μm in size. The cross sectional SEM image shows that the CCTO grains grow regularly close to the clear interface between the CCTO film and the SrTiO₃ substrate. The result was discussed in terms of lattice mismatch between CCTO and SrTiO₃.     

Crystallinity and morphology dependent luminescence of Li-doped Y2−xGdxO3:Eu thin film phosphors

The influence of lithium doping on the crystallization, the surface morphology, and the luminescent properties of pulsed laser deposited Y_2−xGd_xO₃:Eu³⁺ thin film phosphors was investigated. The crystallinity, the surface morphology, and the photoluminescence (PL) of films depended highly on the Li-doping and the Gd content. The relationship between the crystalline and morphological structures and the luminescent properties was studied, and Li⁺ doping was found to effectively enhance not only the crystallinity but also the luminescent brightness of Y_2−xGd_xO₃:Eu³⁺ thin films. In particular, the incorporation of Li and Gd into the Y₂O₃ lattice could induce remarkable increase in the PL. The highest emission intensity was observed Li-doped Y_1.35Gd_0.6O₃:Eu³⁺ thin films whose brightness was increased by a factor of 4.6 in comparison with that of Li-doped Y₂O₃:Eu³⁺ thin films.     

An analysis of Y2O3:Eu thin films for thermographic phosphor applications

A comparative study of the luminescent properties of Y₂O₃:Eu³⁺ phosphor powders and thin films sputtered from targets prepared from combustion synthesized powders is reported. Thin films of (Y_0.96Eu_0.04)₂O₃ were deposited on silicon substrates. Films deposited at 600 °C had both monoclinic and cubic phases of Y₂O₃, which developed to an oriented cubic phase after annealing. Films and powders showed a linear dependence of the intensity of the ⁵D₇→⁷F₂ (611 nm) transition with temperature in the range 26-660 °C with an average rate of change of 1.8×10⁻⁴ °C⁻¹. The rate of change appears to be dependent on the Eu³⁺ concentration. This work shows that these thin films can be used as thermographic phosphors for remote temperature measurements.     

Supercapacitive cobalt oxide (Co3O4) thin films by spray pyrolysis

Uniform and adherent cobalt oxide thin films have been deposited on glass substrates from aqueous cobalt chloride solution, using the solution spray pyrolysis technique. Their structural, optical and electrical properties were investigated by means of X-ray diffraction (XRD), scanning electron micrograph (SEM), optical absorption and electrical resistivity measurements. Along with this, to propose Co₃O₄ for possible application in energy storage devices, its electrochemical supercapacitor properties have been studied in aqueous KOH electrolyte. The structural analysis from XRD pattern showed the oriented growth of Co₃O₄ of cubic structure. The surface morphological studies from scanning electron micrographs revealed the nanocrystalline grains alongwith some overgrown clusters of cobalt oxide. The optical studies showed direct and indirect band gaps of 2.10 and 1.60 eV, respectively. The electrical resistivity measurement of cobalt oxide films depicted a semiconducting behavior with the room temperature electrical resistivity of the order of 1.5 × 10³ Ω cm. The supercapacitor properties depicted that spray-deposited Co₃O₄ film is capable of exhibiting specific capacitance of 74 F/g.     

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.     

Structure and electrical properties of CdIn2O4 thin films prepared by DC reactive magnetron sputtering

CdIn₂O₄ thin films were prepared by direct-current (DC) reactive magnetron sputtering. The structure, surface morphology and the chemical composition of the thin films were analyzed by X-ray diffraction (XRD), atomic force microscope (AFM) and X-ray photoelectron spectroscopy (XPS), respectively. The electrical properties of the films prepared in different oxygen concentration and annealing treatment were determined, and the effects of the preparing conditions on the structure and electrical properties were also explored. It indicates that the CdIn₂O₄ thin films with uniform and dense surface morphology contain mainly CdIn₂O₄, In₂O₃ phases, and CdO phase is also observed. The XPS analysis confirms the films are in oxygen-deficient state. The electrical properties of these films significantly depend on the preparing conditions, the resistivity of the films with the oxygen concentration of 4.29% is 2.95 × 10⁻⁴ Ω cm and the Hall mobility is as high as 60.32 cm²/V s. Annealing treatment can improve the electrical performance of the films.     

Ferromagnetism of epitaxially grown CaRu1−xMxO3 (M=Ti, Mn) films

Epitaxial thin films of CaRu_1−xM_xO₃ (M=Ti, Mn) were fabricated on a (0 0 1)-SrTiO₃ substrate by spin-coat method using organometallic solutions (metal alkoxides). Results of X-ray diffraction and transmission electron microscopy indicate that the epitaxial films were grown pseudomorphically so as to align the [0 0 l] axis of the CaRu_1−xM_xO₃ films perpendicular to the (0 0 1) plane of the SrTiO₃ substrate. Ferromagnetism and metal-insulator transition are induced by the substitution of transition metal ions. The occurrence of ferromagnetism was explained qualitatively assuming a TiRu₆ cluster model for CaRu_1−xTi_xO₃ film and a mixed valence model for CaRu_1−xMn_xO₃ film. Ferromagnetism was also observed for layered CaRuO₃/CaMnO₃ film and CaRuO₃/CaMnO₃/CaRuO₃/CaMnO₃ multilayer film and the magnetism was explained by an interfacial exchange interaction model with magnetic Mn³⁺, Mn⁴⁺, and Ru⁵⁺ ions.     

Electrochromic performance of the mixed V2O5–WO3 thin films synthesized by pulsed spray pyrolysis technique

Vanadium pentoxide (V₂O₅) mixed tungsten trioxide (WO₃) thin films have been synthesized by a novel pulsed spray pyrolysis technique (PSPT) on glass and fluorine doped tin oxide (FTO) coated glass substrates at 400 °C. Aqueous solutions of equimolar vanadium chloride and ammonium tungstate were mixed in volume proportions (5%, 10% and 15%) for the deposition of V₂O₅–WO₃ thin films. The structural, morphological, optical and electrochemical properties of V₂O₅–WO₃ thin films were investigated by FT-IR, XRD, SEM, cyclic voltammetry, chronoamperometry and chronocoulometry techniques. The results showed that the electrochemical properties of V₂O₅ were altered by mixing WO₃. All the films exhibited cathodic electrochromism in lithium containing electrolyte (0.5 M LiClO₄ + propylene carbonate (PC)). Maximum coloration efficiency (CE) of about 49 cm² C⁻¹ was observed for the V₂O₅ film mixed with 15% WO₃. The electrochemical stability of the sample was examined and it was found to be stable up to 1000 cycles.     

PLD of X7R for thin film capacitors

Thin film capacitors with a thickness of 200 nm were prepared on SrTiO₃ (1 0 0), (1 1 0) and (1 1 1) single crystal substrates at a temperature of 973 K by pulsed laser deposition (PLD) using a KrF excimer laser in an O₂-O₃ atmosphere with a gas pressure of 1 Pa using an X7R sintered target. As a result, perovskite BaTiO₃ solid solution films were obtained. In the X7R thin films on (1 0 0) and (1 1 0) SrTiO₃, only diffraction peaks with strong intensities from BaTiO₃ (1 0 0) and (1 1 0), respectively, were observed. X7R films on SrTiO₃ (1 1 1) were grown epitaxially oriented to the crystal plane direction of the substrate by inserting an initial homoepitaxial SrTiO₃ layer with a thickness of 4 nm. The X7R/SrTiO₃ film capacitors yielded a large volumetric efficiency of 50 μF/mm³ and a temperature coefficient of capacitance (TCC) of −1.3% to 1.3% which satisfies the EIA standard specifications for X7R.     

Magnetic circular and linear dichroism of iron garnets thin films

Low temperature absorption, MCD and MLD spectra are reported for pure and substituted Y₃Fe₅O₁₂ thin films in the 13000–33000 cm^?1 spectral range. The materials were obtained by liquid phase epitaxial growth on a Gd₃Ga₅O₁₂ substrate. Above 19000 cm^?1 we demonstrate that our transmission experiments on garnet films provide the same information as do reflexion measurements on bulk crystals. Below 19000 cm^?1 however, the former are much more reliable and accurate. All our data indicate that the films are of excellent optical quality. MCD and MLD spectra show a considerably increased resolution as compared to the absorption spectrum and help in sorting out most of its numerous overlapping components. Finally we prove unambiguously that Clogston's theoretical interpretation is qualitatively correct in the 13000–23000 cm^?1 region and even probably at higher wavenumbers.     

Electrochromic phenomena in transition metal oxide thin films prepared by thermal evaporation

We present an experimental study on the electrochromic properties of MoO₃, WO₃ and mixed WO₃-MoO₃ thin films prepared by thermal evaporation. We have constructed symmetric and quasi-symmetric electrochromic cells incorporating the evaporated oxide films as electrochromic layers. Li⁺ doped V₂O₅ films served as ion storage layers. The symmetric cells were found to exhibit significantly improved optical properties compared to the quasi-symmetric ones, with very low luminous transmittance values in the colored state, which makes them suitable for large-area window applications. Paper presented at the 5th Euroconference on Solid State Ionics, Benalmádena, Spain, Sept. 13–20, 1998.     

Electrochromic properties of WO3 as a single layer and in a full device: From the visible to the infrared

Most of the applications of electrochromic devices (ECDs) concern the visible whereas there is a significant need for ECDs active in the infrared (IR) region. After optimization, WO₃ thin films show significant variation in emissivity, as high as 78% and 49% in the MW (3-5 μm) band and LW (8-12 μm) band, respectively. The incorporation of the EC WO₃ layer in ECDs is discussed in terms (i) of device configuration (i.e. position of the active layer on top or bottom of the device), (ii) of the choice of materials including the transparent conductive layer, electrolyte, counter electrode, and (iii) of the thickness of each layer. Initial trends in optical modulation of the ECDs are deduced from simulation of the optical indexes (n and k). Experimental data based on half-cell assembly confirm the modulation in emissivity in the IR region for WO₃/Ta₂O₅/NiO-based devices with however lower values than the predicted ones.