Influence of temperature annealing on optical properties of SrTiO3/BaTiO3 multilayered films on indium tin oxide

We have prepared SrTiO₃/BaTiO₃ thin films with multilayered structures deposited on indium tin oxide (ITO) coated glass by a sol-gel deposition and heating at 300-650 °C. The optical properties were obtained by UV-vis spectroscopy. The films show a high transmittance (approximately 85%) in the visible region. The optical band gap of the films is tunable in the 3.64-4.19 eV range by varying the annealing temperature. An abrupt decrease towards the bulk band gap value is observed at annealing temperatures above 600 °C. The multilayered film annealed at 650 ° C exhibited the maximum refractive index of 2.09-1.91 in the 450-750 nm wavelength range. The XRD and AFM results indicate that the films annealed above 600 ° C are substantially more crystalline than the films prepared at lower temperatures which were used to change their optical band gap and complex refractive index to an extent that depended on the annealing temperature.     

Optical constants and thermocoloration of pulsed laser deposited molybdenum oxide thin films

Molybdenum oxide thin films were prepared by pulsed laser deposition. The as-deposited films were dark. Annealing the films in air at 400 °C resulted in transparent films. These films were further annealed in vacuum at 300 and 400 °C to investigate thermocoloration. The structural, chemical, and optical properties of the films were determined. All films were predominantly amorphous. The air-annealed films were nearly stoichiometric. However, after annealing in vacuum at 400 °C, the films became oxygen-deficient. The transmittance of the films progressively decreased as the vacuum-annealing temperature increased, indicating stronger coloration of the films. The optical constants were determined from the transmittance measurements. Both the refractive index and extinction coefficient increased upon vacuum annealing. However, the band gap slightly decreased after vacuum annealing.     

Derivation of the optical constants of spin coated CeO2-TiO2-ZrO2 thin films prepared by sol-gel route

Ternary thin films of cerium titanium zirconium mixed oxide were prepared by the sol-gel process and deposited by a spin coating technique at different spin speeds (1000-4000 rpm). Ceric ammonium nitrate, Ce(NO₃)₆(NH₄)₂, titanium butoxide, Ti[O(CH₂)₃CH₃]₄, and zirconium propoxide, Zr(OCH₂CH₂CH₃)₄, were used as starting materials. Differential calorimetric analysis (DSC) and thermogravimetric analysis (TGA) were carried out on the CeO₂-TiO₂-ZrO₂ gel to study the decomposition and phase transition of the gel. For molecular, structural, elemental, and morphological characterization of the films, Fourier Transform Infrared (FTIR) spectral analysis, X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS), cross-sectional scanning electron microscopy (SEM), and atomic force microscopy (AFM) were carried out. All the ternary oxide thin films were amorphous. The optical constants (refractive index, extinction coefficient, band gap) and thickness of the films were determined in the 350-1000 nm wavelength range by using an nkd spectrophotometer. The refractive index, extinction coefficient, and thickness of the films were changed by varying the spin speed. The oscillator and dispersion energies were obtained using the Wemple-DiDomenico dispersion relationship. The optical band gap is independent of the spin speed and has a value of about E_g≈2.82±0.04 eV for indirect transition.     

Investigation of thin TiO2 films cosputtered with Si species

Titanium dioxide (TiO₂) films were fabricated by cosputtering titanium (Ti) target and SiO₂ or Si slice with ion-beam-sputtering deposition (IBSD) technique and were postannealed at 450 °C for 6 h. The variations of oxygen bonding, which included high-binding-energy oxygen (HBO), bridging oxygen (BO), low-binding-energy oxygen (LBO), and three chemical states of titanium (Ti⁴⁺, Ti³⁺ and Ti²⁺) were analyzed by X-ray photoelectron spectroscopy (XPS). The enhancement of HBO and reduction of BO in O 1s spectra as functions of SiO₂ or Si amount in cosputtered film imply the formation of Si-O-Ti linkage. Corresponding increase of Ti³⁺ in Ti 2p spectra further confirmed the property modification of the cosputtered film resulting from the variation of the chemical bonding. An observed correlation between the chemical structure and optical properties, refractive index and extinction coefficient, of the SiO₂ or Si cosputtered films demonstrated that the change of chemical bonding in the film results in the modification of optical properties. Furthermore, it was found that the optical properties of the cosputtered films were strongly depended on the cosputtering targets. In case of the Si cosputtered films both the refractive indices and extinction coefficients were reduced after postannealing, however, the opposite trend was observed in SiO₂ cosputtered films.     

Effects of thermally induced anatase-to-rutile phase transition in MOCVD-grown TiO2 films on structural and optical properties

Titanium dioxide (TiO₂) films with a thickness of 550 nm were deposited on quartz glass at 300 °C by metalorganic chemical vapor deposition. The effects of post-annealing between 600 °C and 1000 °C were investigated on the structural and optical properties of the films. X-ray diffraction patterns revealed that the anatase phase of as-grown TiO₂ films began to be transformed into rutile at the annealing temperature of 900 °C. The TiO₂ films were entirely changed to the rutile phase at 1000 °C. From scanning electron spectroscopy and atomic force microscopy images, it was confirmed that the microstructure of as-deposited films changed from narrow columnar grains into wide columnar ones. The surface composition of the TiO₂ films, which was analyzed by X-ray photoelectron spectroscopy data, was nearly constant although the films were annealed at different temperatures. When the annealing temperature increased, the transmittance of the films decreased, whereas the refractive index and the extinction coefficient calculated by the envelope method increased at high temperature. The values of optical band gap decreased from 3.5 eV to 3.25 eV at 900 °C. This abrupt decrease was consistent with the anatase-to-rutile phase transition. Received: 4 October 2000 / Accepted: 4 December 2000 / Published online: 23 May 2001     

Thermal annealing effect of on optical constants of vacuum evaporated Se75S25−xCdx chalcogenide thin films

Chalcogenide glasses are interesting materials due to their infrared transmitting properties and photo induced effects exhibited by them. Thin films with thickness of 3000 Å of the glasses Se₇₅S_25−xCd_x with x=6, 8 and 10 at% prepared by melt quench technique were evaporated by thermal evaporation onto glass substrates under a vacuum of 10⁻⁶ Torr. The optical constants (absorption coefficient, refractive index and extinction coefficient) of as-prepared and annealed films have been studied as a function of photon energy in the wave length region 400-1000 nm. Analysis of the optical absorption data shows that the rule of non-direct transitions predominates. It has been found that the absorption coefficient and optical band gap increase with increasing annealing temperatures. The refractive index (n) and the extinction coefficient (k) were observed to decrease with increasing annealing temperature.     

Preparation of ZnO-doped Al films by spray pyrolysis technique

Al-doped zinc oxide (AZO) thin films have been prepared by spray pyrolysis (SP) technique of zinc acetate and aluminium nitrate, and the effect of thickness on structural and optical properties has been investigated. The structural and optical characteristics of the AZO films were examined by X-ray diffraction (XRD) and double-beam spectrophotometry. These films, deposited on glass substrates at an optimal substrate temperature (T_S = 450 °C), have a polycrystalline texture with a hexagonal structure. Transmission measurements showed that for visible wavelengths, the AZO films have an average transmission of over 90%. The optical parameters have been calculated. The dependence of the refractive index, n, and extinction coefficient, k, on the wavelength for the sprayed films is also reported. Optical band gap of AZO is 3.30 and 3.55 eV, respectively, depending on the film thicknesses.     

Effect of post-annealing on the properties of copper oxide thin films obtained from the oxidation of evaporated metallic copper

Thin films of copper oxide were obtained through thermal oxidation (100-450 °C) of evaporated metallic copper (Cu) films on glass substrates. The X-ray diffraction (XRD) studies confirmed the cubic Cu phase of the as-deposited films. The films annealed at 100 °C showed mixed Cu-Cu₂O phase, whereas those annealed between 200 and 300 °C showed a single cubic Cu₂O phase. A single monoclinic CuO phase was obtained from the films annealed between 350 and 450 °C. The positive sign of the Hall coefficient confirmed the p-type conductivity in the films with Cu₂O phase. However, a relatively poor crystallinity of these films limited the p-type characteristics. The films with Cu and CuO phases show n-type conductivity. The surface of the as-deposited is smooth (RMS roughness of 1.47 nm) and comprised of uniformly distributed grains (AFM and SEM analysis). The post-annealing is found to be effective on the distribution of grains and their sizes. The poor transmittance of the as-deposited films (<1%) is increased to a maximum of ∼80% (800 nm) on annealing at 200 °C. The direct allowed band gap is varied between 2.03 and 3.02 eV.     

Influence of crystallization on the spectral features of nano-sized ferroelectric barium strontium titanate (Ba0.7Sr0.3Tio3) thin films

Ferroelectric barium strontium titanate (Ba_0.7Sr_0.3TiO₃)(BST) thin films have been prepared from barium 2-ethylhexanoate [Ba[CH₃(CH₂)₃CH(C₂H₅)CO₂]₂]_, strontium 2-ethylhexanoate [Sr[CH₃(CH₂)₃CH(C₂H₅)CO₂]₂] and titanium(IV) isopropoxide [TiOCH(CH₃)₂]₄ precursors using a modified sol-gel technique. The precursor except [TiOCH(CH₃)₂]₄ were synthesized in the laboratory. Transparent and crack-free films were fabricated on pre-cleaned quartz substrates by spin coating. The structural and optical properties of films annealed at different temperatures have been investigated. The as-fired films were found to be amorphous that crystallized to the tetragonal phase after annealing at 550 °C for 1 h in air. The lattice constants “a” and “c” were found to be 3.974 A and 3.990 A, respectively. The grain sizes of the films annealed at 450, 500 and 550 °C were found to be 30.8, 36.0 and 39.8 nm respectively. The amorphous film showed very high transparency (∼95%), which decreases slightly after crystallization (∼90%). The band gap and refractive index of the amorphous and crystalline films were estimated. The optical dispersion data are also analyzed in the light of the single oscillator model and are discussed.     

Effect of annealing temperature on the optical constants of zinc oxide films

In this paper, the effect of annealing temperature on optical constants was studied. The ZnO films were deposited on microscopic glass substrates using the sol-gel method for various annealing temperatures. The deposited zinc oxide (ZnO) films were characterized by an X-ray diffractometer (XRD), a spectrophotometer and scanning electron microscopy (SEM). The transmittance spectra recorded through the spectrophotometer exhibits 90% transmittance. The XRD spectra showed polycrystalline nature of ZnO film. Optical constants were determined through transmittance spectra using an envelope method. It was found that there was a significant effect of annealing temperature on the refractive index and extinction coefficient of deposited ZnO films. In this experiment, the optimum refractive index value of 1.97 was obtained at 350 °C annealing temperature at visible (vis) wavelength. The optical energy gap was found to be of ∼3.2 eV for all the samples. The top view of SEM showed the ZnO grain growth on the glass substrates.     

Fabrication of hydrophobic surface of titanium dioxide films by successive ionic layer adsorption and reaction (SILAR) method

Titanium dioxide (TiO₂) films were fabricated on fluorine doped tin oxide (FTO) coated glass substrate using successive ionic layer adsorption and reaction (SILAR) method. The X-ray diffraction, scanning electron microscopy, transmission electron microscopy, optical absorption and contact angle measurement were applied to study the structural, surface morphological, optical and surface wettability properties of the as-deposited and annealed TiO₂ films. The X-ray diffraction studies revealed both as-deposited and annealed TiO₂ films are amorphous. Irregular shaped spherical grains of random size and well covered to the fluorine doped tin oxide coated glass substrates were observed from SEM studies with some cracks after annealing. The optical band gap values of virgin TiO_2, annealed, methyl violet and rose bengal sensitized TiO₂ were found to be 3.6, 3.5, 2.87 and 2.95 eV, respectively. Surface wettability studied in contact with liquid interface, showed hydrophobic nature as water contact angles were greater than 90°. The adsorption of dyes, as confirmed by the photographs, is one of the prime requirements for dye sensitized solar cells (DSSC).     

Determination of optical properties in nanostructured thin films using the Swanepoel method

We present the methodological framework of the Swanepoel method for the spectrophotometric determination of optical properties in thin films using transmittance data. As an illustrative case study, we determined the refractive index, thickness, absorption index, and extinction coefficient of a nanostructured 3 mol% Y₂O₃-doped ZrO₂ (yttria stabilized zirconia, 3YSZ) thin film prepared by the sol-gel method and deposited by dipping onto a soda-lime glass substrate. In addition, using the absorption index obtained with the Swanepoel method, we calculated the optical band gap of the film. The refractive index was found to increase, then decrease, and finally stabilize with increasing wavelength of the radiation, while the absorption index and extinction coefficient decreased monotonically to zero. These trends are explained in terms of the location of the absorption bands. We also deduced that this 3YSZ thin film has a direct optical band gap of 4.6 eV. All these results compared well with those given in the literature for similar thin films. This suggests that the Swanepoel method has an important role to play in the optical characterization of ceramic thin films.     

The effect of heat treatment on the physical properties of sol-gel derived ZnO thin films

Zinc oxide (ZnO) thin films were deposited on microscope glass substrates by sol-gel spin coating method. Zinc acetate (ZnAc) dehydrate was used as the starting salt material source. A homogeneous and stable solution was prepared by dissolving ZnAc in the solution of monoethanolamine (MEA). ZnO thin films were obtained after preheating the spin coated thin films at 250 °C for 5 min after each coating. The films, after the deposition of the eighth layer, were annealed in air at temperatures of 300 °C, 400 °C and 500 °C for 1 h. The effect of thermal annealing in air on the physical properties of the sol-gel derived ZnO thin films are studied. The powder and its thin film were characterized by X-ray diffractometer (XRD) method. XRD analysis revealed that the annealed ZnO thin films consist of single phase ZnO with wurtzite structure (JCPDS 36-1451) and show the c-axis grain orientation. Increasing annealing temperature increased the c-axis orientation and the crystallite size of the film. The annealed films are highly transparent with average transmission exceeding 80% in the visible range (400-700 nm). The measured optical band gap values of the ZnO thin films were between 3.26 eV and 3.28 eV, which were in the range of band gap values of intrinsic ZnO (3.2-3.3 eV). SEM analysis of annealed thin films has shown a completely different surface morphology behavior.     

Structural, electrical and optical properties of ZnS films deposited by close-spaced evaporation

ZnS films have been deposited on glass substrates by close-spaced evaporation (CSE) technique. The films were grown at different temperatures in the range, 200-350 °C. The layers have been characterized with X-ray diffractometer (XRD), atomic force microscope (AFM), energy dispersive analysis of X-rays (EDAX) and optical spectrophotometer to evaluate the quality of the layers for photovoltaic applications. The studies showed that the optimum substrate temperature for the growth of ZnS layers was 300 °C. The films grown at these temperatures exhibited cubic structure with nearly stoichiometric composition. The AFM data revealed that the films had nano-sized grains with a grain size of ∼40 nm. The optical studies exhibited direct allowed transition with an energy band gap of 3.61 eV. The other structural and optical parameters such as lattice stress, dislocation density, refractive index and extinction coefficient were also evaluated. The temperature-dependent conductivity measured in the range, 303-523 K showed a change in the conduction mechanism at 120 °C. The activation energy values evaluated using the temperature dependence of electrical conductivity are 7 and 29 meV at low and high temperature regions, respectively.     

Optical and electrical properties of plasma-oxidation derived HfO2 gate dielectric films

High-k gate dielectric HfO₂ thin films have been deposited on Si(1 0 0) by using plasma oxidation of sputtered metallic Hf thin films. The optical and electrical properties in relation to postdeposition annealing temperatures are investigated by spectroscopic ellipsometry (SE) and capacitance-voltage (C-V) characteristics in detail. X-ray diffraction (XRD) measurement shows that the as-deposited HfO₂ films are basically amorphous. Based on a parameterized Tauc-Lorentz dispersion mode, excellent agreement has been found between the experimental and the simulated spectra, and the optical constants of the as-deposited and annealed films related to the annealing temperature are systematically extracted. Increases in the refractive index n and extinction coefficient k, with increasing annealing temperature are observed due to the formation of more closely packed thin films and the enhancement of scattering effect in the targeted HfO₂ film. Change of the complex dielectric function and reduction of optical band gap with an increase in annealing temperature are discussed. The extracted direct band gap related to the structure varies from 5.77, 5.65, and 5.56 eV for the as-deposited and annealed thin films at 700 and 800 °C, respectively. It has been found from the C-V measurement the decrease of accumulation capacitance values upon annealing, which can be contributed to the growth of the interfacial layer with lower dielectric constant upon postannealing. The flat-band voltage shifts negatively due to positive charge generated during postannealing.     

Optical constants of vacuum annealed radio frequency (RF) magnetron sputtered zinc oxide thin films

Zinc oxide thin films were deposited by radio frequency magnetron sputtering. The films were annealed in vacuum at temperatures of 400, 600, and 800 °C. The influence of annealing on the structural, chemical, and optical properties of the films was investigated. From a structural point of view, the films were highly oriented, with columnar microstructure. Chemical analysis indicated that the films were sub-stoichiometric, and that the concentration of oxygen vacancies was enhanced upon annealing. The films were highly transparent in the visible and near-infrared spectral regions. Transparency was reduced as the annealing temperature was increased. The refractive index and extinction coefficient, in the transparent regions of the films, were derived from transmittance measurements. The refractive index manifested variation that was affected by crystallite size, roughness and defect concentration. The extinction coefficient of the as-deposited films and those annealed at 400 °C was negligible. However, the films annealed at 600 or 800 °C had much larger values of the extinction coefficient due to increased absorption or scattering. The absorption coefficient and optical band gap of the films were derived from spectrophotometric measurements. The absorption coefficient showed progressive increase with the annealing temperature. However, the band gap did not show significant variation.     

Optimization of the optical and electrical properties of electron beam evaporated aluminum-doped zinc oxide films for opto-electronic applications

Aluminum-doped zinc oxide (AZO) thin films have been deposited by electron beam evaporation technique on glass substrates. The structural, electrical and optical properties of AZO films have been investigated as a function of annealing temperature. It was observed that the optical properties such as transmittance, reflectance, optical band gap and refractive index of AZO films were strongly affected by annealing temperature. The transmittance values of 84% in the visible region and 97% in the NIR region were obtained for AZO film annealed at 475 °C. The room temperature electrical resistivity of 4.6×10⁻³ Ω cm has been obtained at the same temperature of annealing. It was found that the calculated refractive index has been affected by the packing density of the thin films, whereas, the high annealing temperature gave rise to improve the homogeneity of the films. The single-oscillator model was used to analyze the optical parameters such as the oscillator and dispersion energies.     

Effect of annealing on optical and structural properties of ZnS/MnS and MnS/ZnS superlattices thin films for solar energy application

ZnS/MnS super lattice thin films were grown on glass substrates by Chemical Bath Deposition technique. Equimolar aqueous solutions of ZnCl₂:thiourea and MnCl₂·2H₂O:thiourea were taken separately. The substrates were placed vertically in the beakers containing the precursor described above, and the films are deposited at 85 °C for an hour. The as deposited films are annealed at 200 °C for about two hours. X-ray diffractometry method was used to obtain structural characterization. The UV–vis absorption spectrometry was employed to find the optical properties. The refractive-index, dielectric constant, optical conductivity, electrical conductivity and extinction coefficient were determined by various equations based on the data. The valence band and conduction band offset voltages for ZnS/MnS were determined as 0.7 eV and 0.1 eV respectively and for MnS/ZnS were 0.4 eV and 0.3 eV respectively. The band alignment of both superlattice was found to be as Type I.     

Formation of CdO films from chemically deposited Cd(OH)2 films as a precursor

Formation of cadmium hydroxide at room temperature onto glass substrates from an aqueous alkaline cadmium nitrate solution using a simple soft chemical method and its conversion to cadmium oxide (CdO) by thermal annealing treatment has been studied in this paper. The as-deposited film was given thermal annealing treatment in oxygen atmosphere at 450 °C for 2 h for conversion into cadmium oxide. The structural, surface morphological and optical studies were performed for as-deposited and the annealed films. The structural analyses revealed that as-deposited films consists of mixture of Cd(OH)₂ and CdO, while annealed films exhibited crystalline CdO. From surface morphological studies, conversion of clusters to grains after annealing was observed. The band gap energy was changed from 3.21 to 2.58 eV after annealing treatment. The determination of elementals on surface composition of the core-shell nanoparticles of annealed films was carried out using X-ray photoelectron spectroscopy (XPS).     

Effect of indium incorporation on properties of SnS thin films prepared by spray pyrolysis

Tin sulphide (SnS) thin films were deposited on glass substrate at different substrate temperature (T_s = 325 °C, 350 °C and 375 °C) by pyrolytic decomposition using stannous chloride and thiourea as precursor solutions. Also, indium-doped SnS thin films were prepared by using InCl₃ as dopant source. The dopant concentration [In/Sn] was varied from 2 at% to 6 at%. The XRD analysis revealed that the films were polycrystalline in nature having orthorhombic crystal structure with a preferred grain orientation along (1 1 1) plane. Due to In doping, the orientation of the grains in the (1 1 1) plane was found to be deteriorated. Atomic force microscopy (AFM) measurements revealed that the surface roughness of the films decreased due to indium doping. The optical properties were investigated by measuring the transmittance characteristics which were used to find the optical band gap energy, refractive index and extinction coefficient. The energy band gap value was decreased from 1.60 to 1.43 eV with increasing In concentration. The photoluminescence (PL) measurements of thin films showed strong emission band centered at 760 nm. Using Hall Effect measurements electrical resistivity, carrier concentration and Hall mobility have been determined.