The study of optical properties of In2O3 and of mixed oxides In2O3−MoO3 system deposited by coevaporation

A discussion of the optical properties of two systems of dielectric films i.e. In₂O₃ and of mixed oxides In₂O₃−MoO₃ system is presented. Film thickness, substrate temperature, annealing and composition (in molar%) have a profound effect on the structure and optical properties of these films. The decrease in optical band gap with the increase in film thickness of In₂O₃ is interpreted in terms of incorporation of oxygen vacancies in the In₂O₃ lattice. The decrease in optical band gap with the increase in substrate temperature and annealing of In₂O₃ thin films is ascribed to the release of trapped electrons by thermal energy or by the outward diffusion of the oxygen-ion vacancies, which are quite mobile even at low temperature. For the mixed oxides In₂O₃−MoO₃ system the results are found to be compatible with the reduction in the value of optical band gap of these materials as the molar fraction of MoO₃ increases in the In₂O₃ thin films and is attributed to the incorporation of Mo(VI) ions in an In₂O₃lattice that causes the indium orbital to become a little less tightly bound. The decrease in optical band gap of mixed oxides In₂O₃−MoO₃ system, with increasing film thickness is interpreted in terms of incorporation of oxygen vacancies in both In₂O₃ and MoO₃ lattice which are also believed to be the source of conduction electrons in In₂O₃–MoO₃ complex. The decrease in optical band gap with increasing substrate temperature and annealing of mixed oxides In₂O₃−MoO₃ system is due to the increasing concentration of oxygen vacancies, formation of indium and molybdenum species of lower oxidation state and indium interstitials. The blue colouration of mixed oxides In₂O₃–MoO₃ samples is due to the inter-electron transfer from oxygen 2p to molybdenum 4d level due to which Mo species of lower oxidation states are formed.     

Ellipsometry and optical measurements on amorphous thin films of As2Se3

Thin films of amorphous AsSe_3/2 have been prepared by thermal evaporation of the material under a vacuum of 1.33×10^?3 Pa. Reflectivity, transmission and ellipsometric measurements of the films have been carried out. The optical energy gap and the absorption coefficient as a function of wavelength were obtained. Two absorption bands were observed and interpreted in terms of defects in the AsSe_3/2 system (homopolar bonds). Analysis of reflection and transmission spectra shows that the electron density at band tails of both conduction and valency bands follows N(E)?E^1/2 (Taue plots). No considerable variations were observed on changing the film thickness.     

Effect of post-deposition annealing on microstructural and optical properties of barium strontium titanate thin films deposited by r.f. magnetron sputtering

The effect of post-deposition annealing on the structural and optical properties of barium strontium titanate, Ba_0.8Sr_0.2TiO₃ film has been investigated. The films have been deposited on oxidized p-silicon substrates by r.f. magnetron sputtering followed by annealing in O₂ atmosphere at different temperatures. In situ deposition has also been carried out at 550 °C for comparison. The nature of the variation of refractive index and extinction coefficient with annealing temperature and wavelength has been studied. Absorption band edges shift towards lower photon energy values as the temperature is increased causing a reduction in the optical band gap energy. Infrared absorption bands show a cubic symmetry at lower frequency and are found to be broadened and even split at higher frequency.     

The correlation of various properties of thin films of MoO3 and of the mixed oxide systems MoO3-In2O3 and MoO3-SiO

A discussion of the general properties of three systems of dielectric films i.e. MoO₃ and the mixed oxide systems MoO₃-In₂O₃ and MoO₃-SiO is presented. Composition, film thickness, substrate deposition temperature and annealing all have a substantial effect on the structure and various properties of the films. The general properties of these three systems of dielectric films include analysis by X-ray photoelectron spectroscopy, UV-visible and infrared spectroscopy including the Fourier transform technique, electrical properties both d.c. and a.c. at both low and high fields and electron spin resonance. An attempt is made to show how the variations of properties depend on many disposable parameters. In particular the use of X-ray photoelectron spectroscopy shows how the local atomic and molecular bonding changes as a result of varying preparation parameters and this feature is a recent facility in the field of thin dielectric-semiconducting films. It is expected that the general discussion in this paper may help in the interpretation of results on other thin dielectric and semiconducting films.     

A.c. conduction in evaporated MoO3/SiO amorphous thin films

The dielectric properties of vacuum-deposited MoO₃/SiO films of different compositions studied in the frequency range 10² to 10⁶ Hz at various temperatures (193 to 393 K) are reported. The properties of the film capacitor are found to be temperature and frequency dependent. The decrease in a.c. conductance with increasing concentration of SiO in MoO₃ may be attributed to the increasing number of trapping centres generated in MoO₃/SiO films during the evaporation process.     

Thermal modification of MoO3 nanofilms

Optical spectroscopy results demonstrate that heat treatment of 2- to 60-nm-thick MoO₃ films for 1 s to 120 min in the temperature range 573–873 K reduces their absorbance in the range λ = 300–480 nm (λ_max = 350 nm) and increases it in the range λ = 480-1100 nm (λ_max = 870 nm). The degree of conversion of the MoO₃ films increases with increasing heat-treatment time and temperature and with decreasing film thickness. A mechanism is proposed for the thermal modification of MoO₃ films, which involves the formation of a [(V _a)⁺⁺ e] center during the preparation of the MoO₃ film and a thermally activated electron transition from the valence band to the level of the [(V _a)⁺⁺ e] center, resulting in the formation of an [e (V _a)⁺⁺ e] center.     

Effects of annealing temperatures on optical and electrical properties of vacuum evaporated Ga15Se77In8 chalcogenide thin films

The optical constants (absorption coefficient, optical band gap, refractive index, extinction coefficient, real and imaginary parts of dielectric constants) of amorphous and thermally annealed thin films of Ga₁₅Se₇₇In₈ chalcogenide glasses with thickness 4000 Å have been investigated from absorption and reflection spectra as a function of photon energy in the wave length region 400-800 nm. Thin films of Ga₁₅Se₇₇In₈ chalcogenide glasses were thermally annealed for 2 h at three different annealing temperatures 333 K, 348 K and 363 K, which are in between the glass transition and crystallization temperature of Ga₁₅Se₇₇In₈ glasses. Analysis of the optical absorption data shows that the rule of non-direct transitions predominates. It was found that the optical band gap decreases with increasing annealing temperature. It has been observed that the value of absorption coefficient and extinction coefficient increases while the values of refractive index decrease with increasing annealing temperature. The decrease in optical band gap is explained on the basis of the change in nature of films, from amorphous to crystalline state. The dc conductivity of amorphous and thermally annealed thin films of Ga₁₅Se₇₇In₈ chalcogenide glasses is also reported for the temperature range 298-393 K. It has been observed that the conduction is due to thermally assisted tunneling of the carriers in the localized states near the band edges. The dc conductivity was observed to increase with the corresponding decrease in activation energy on increasing annealing temperature in the present system. These results were analyzed in terms of the Davis-Mott model.     

Electrical and optical properties of reactive sputtered TiO x thin films for uncooled IR detector applications

Nanostructured titanium oxide (nano-TiO _x ) thin films for uncooled IR detectors were fabricated by dc reactive magnetron sputtering and post-deposition annealed in oxygen atmosphere. The crystalline structure and surface morphology were characterized by glancing incidence X-ray diffraction (GIXRD) and field emission scanning microscopy. The results of GIXRD measurements indicate that TiO _x thin film deposited at room temperature is amorphous. A mixture of anatase and rutile nanocrystalline structure phase were present in oxygen annealed TiO _x thin film. A weak absorption peak around 438 cm^?1 corresponding to Ti–O stretching vibration is observed by Fourier transform infrared spectroscopy with annealed TiO _x thin film. The X-ray photoelectron spectra reveals Ti³⁺ and Ti⁴⁺ ions are coexisting in TiO _x films. The optical spectra of the films indicate that the optical absorption edge of the nano-TiO _x film exhibits a red shift compared to the as-deposited film. Furthermore, compared to bulk TiO _x , a blue shift was observed in both of the deposited and annealed films due to quantum size effect. The dependence of resistivity on temperature reveals both the absolute value of temperature coefficient of resistivity (TCR) and activation energy of TiO _x thin film increase significantly after annealing in oxygen.     

The optical absorption edge in amorphous thin films of MoO3-In2O3

A study of the effects of changes in composition, film thickness, substrate deposition temperature and annealing on the optical properties of MoO₃-In₂O₃ is presented. The results are found to be compatible with the reduction in the value of optical energy gap of these materials as the molar fraction of In₂O₃ in the MoO₃ thin film increases. This decrease of optical gap may be attributed to the incorporation of In(III) ions in an MoO₃ lattice. The decrease in optical band gap with increasing thickness may be interpreted in terms of the incorporation of oxygen vacancies which are also believed to be the source of conduction electrons in the MoO₃-In₂O₃ complex. The decrease of band gap with increasing substrate temperature may be attributed to the enhanced ordering of the samples and the decrease of band gap with annealing may be attributed to a reduction in the concentration of lattice imperfections.     

Annealing effect on the structural and optical properties of embedded Au nanoparticles in silicon suboxide films

Au/SiO_x nanocomposite films have been fabricated by co-sputtering Au wires and SiO₂ target using an RF magnetron co-sputtering system before the thermal annealing process at different temperatures. The structural and optical properties of the samples were characterized using X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM), Fourier transform infrared spectroscopy (FTIR), optical transmission, and reflection spectroscopy. XPS analysis confirms that the as-prepared SiO_x films are silicon-rich suboxide films. FESEM images reveal that with an increase in annealing temperature, the embedded Au NPs tend to diffuse toward the surface of the SiO_x films. In IR spectra, the intensity of the Si-O-Si absorption band increases with the annealing temperature. Optical spectra reveal that the position and intensity of the surface plasmon resonance (SPR) peak are dominated by the effect of the inter-particle distance and size of the Au NPs embedded in the SiO_x films, respectively. The SPR absorption peak shows the blue-shift from 672 to 600 nm with an increase in annealing temperature. The growth of silica nanowires (SiO_x NWs) is observed in the film prepared on a c-Si substrate instead of a quartz substrate and annealed at temperatures of 1000 °C.     

Sol-gel synthesis, structure and photoluminescence properties of nanocrystalline Lu2MoO6:Eu

In this paper, we reported the obtention of Eu³⁺ ion doped Lu₂MoO₆ powders synthesized by a sol-gel method, and followed by annealing at different temperatures. The structure and photoluminescence properties of these powders were investigated. The X-ray diffraction pattern suggests that Lu₂MoO₆ powder has a monoclinic structure. It was observed that the UV-visible and photoluminescence spectra of Lu₂MoO₆:Eu nanocrystallines varied systematically with the calcination temperature. The near-UV absorption edge shifts to long wavelength direction with the decreasing of the calcination temperature, while the peak of MoO₅ excitation band shifts in an opposite way. The decline of the crystallinity and the introduced lattice defect were considered to respond for these variations. Additionally, due to the efficient red light emission under near-UV light excitation, the powder can be a candidate as red phosphor for white-light-emitting diodes.     

Effect of substrate temperature and film thickness on the surface structure of some thin amorphous films of MoO3 studied by X-ray photoelectron spectroscopy (ESCA)

X-ray photoelectron spectroscopy (XPS) core level spectra of MoO₃ substoichiometric amorphous thin films in the thickness range 100 to 670 nm were studied as a function of thickness. Some samples 500 nm thick were studied for different substrate temperatures in the range 293 to 543 K. It was observed that with the increase of thickness of the samples no change in the electron spectrum was observed in the material. Under vacuum conditions, MoO₃ turned blue when the substrate temperature was higher than 373 K. XPS spectra supported the formation of the Mo⁵⁺ oxidation state in the blue samples. Blue coloration was observed after heating in vacuum and this was attributed to an internal electron transfer from oxygen to metallic orbitals by thermal ionization creating an Mo⁵⁺ oxidation state.     

Influence of sputtering power on the physical properties of magnetron sputtered molybdenum oxide films

Thin films of molybdenum oxide were formed on glass and silicon substrates by sputtering of molybdenum target under various sputtering powers in the range 2.3–6.8 W/cm², at a constant oxygen partial pressure of 2 × 10⁻⁴ mbar and substrate temperature 523 K employing DC magnetron sputtering technique. The effect of sputtering power on the core level binding energies, chemical binding configurations, crystallographic structure, surface morphology and electrical and optical properties was systematically studied. X-ray photoelectron spectroscopic studies revealed that the films formed at sputtering powers less than 5.7 W/cm² were mixed oxidation states of Mo⁵⁺ and Mo⁶⁺. The films formed at 5.7 W/cm² contained the oxidation state Mo⁶⁺ of MoO₃. Fourier transform infrared spectra contained the characteristic optical vibrations. The presence of a sharp absorption band at 1,000 cm⁻¹ in the case of the films formed at 5.7 W/cm² was also conformed the existence of α-phase MoO₃. X-ray diffraction studies also confirmed that the films formed at sputtering powers less than 5.7 W/cm² showed the mixed phase of α-and β-phase of MoO₃ where as at sputtering power of 5.7 W/cm² showed single phase α-MoO₃. The electrical conductivity of the films increased from 8 × 10⁻⁶ to 1.2 × 10⁻⁴ Ω⁻¹ cm⁻¹, the optical band gap decreased from 3.28 to 3.12 eV and the refractive index decreased from 2.12 to 1.94 with the increase of sputtering power from 2.3 to 6.8 W/cm², respectively.     

Electrical and optical properties of MoO3-V2O5 mixed oxide films

Vacuum deposited MoO₃-V₂O₅ films of different molar concentrations have been used for DC electrical conductivity studies at different temperatures. The optical absorption spectra of MoO₃-V₂O₅ films of different molar concentrations have been measured. From these measurements it is found that optical band gap and activation energy vary with molar concentration of MoO₃-V₂O₅ films.     

A study of the infrared absorption spectra of thin amorphous films of molybdenum trioxide

The spectra of thin amorphous films of MoO₃ deposited by vacuum evaporation have been studied within the spectral range 4000–400 cm^–1 by the Fourier transform infrared technique. Some samples in the thickness range 100 to 400 nm were investigated at room temperature. Four samples were investigated in the substrate deposition temperature range 293 to 543 K. Some samples were annealed in vacuum in the temperature range 473 to 673 K and their IR spectra were recorded as soon as the samples were cooled to room temperature. It has been observed that annealing of the samples at 473 K or above and also heating the substrates in the temperature range 473 K or above, results in the formation of molybdenum species of lower oxidation state than the normal Mo(VI), i.e. Mo(V). This new oxidation state is formed by electron transfer from the oxygen 2p to the molybdenum 4d level.     

Temperature effects on the optoelectronic properties of AgIn5S8 thin films

Polycrystalline AgIn₅S₈ thin films are obtained by the thermal evaporation of AgIn₅S₈ crystals onto ultrasonically cleaned glass substrates under a pressure of ~ 1.3 × 10⁻³ Pa. The temperature dependence of the optical band gap and photoconductivity of these films was studied in the temperature regions of 300-450 K and 40-300 K, respectively. The heat treatment effect at annealing temperatures of 350, 450 and 550 K on the temperature dependent photoconductivity is also investigated. The absorption coefficient, which was studied in the incidence photon energy range of 1.65-2.55 eV, increased with increasing temperature. Consistently, the absorption edge shifts to lower energy values as temperature increases. The fundamental absorption edge which corresponds to a direct allowed transition energy band gap of 1.78 eV exhibited a temperature coefficient of −3.56 × 10⁻⁴ eV/K. The 0 K energy band gap is estimated as 1.89 eV. AgIn₅S₈ films are observed to be photoconductive. The highest and most stable temperature invariant photocurrent was obtained at an annealing temperature of 550 K. The photoconductivity kinetics was attributed to the structural modifications caused by annealing and due to the trapping-recombination centers' exchange.     

Annealing dependence of optical properties of Ga20S75Sb5 and Ga20S40Sb40 thin films

Amorphous Ga₂₀S₇₅Sb₅ and Ga₂₀S₄₀Sb₄₀ thin films were prepared onto glass substrates by using thermal evaporation method. The effect of annealing (under vacuum) at different temperatures on the optical parameters was investigated in the temperature range 373-593 K. The optical absorption coefficient (α) for the as-deposited and annealed films were calculated from the reflectance and transmittance measurements in the range 190-900 nm. X-Ray diffraction indicates that the as-deposited films and those annealed up to the glass transition temperature (T_g) exhibit amorphous state. On annealing above the glass transition temperature these films show a polycrystalline structure. Analysis of the optical absorption data indicates that the optical band gap E_g^opt of these films obeys Tauc's relation for the allowed non-direct transition. It was found that the optical band gap E_g^opt increases with annealing temperature up to T_g, whereas above T_g there is a remarkable decrease. The obtained results were interpreted on the basis of amorphous- crystalline transformation.     

Structural and optical properties of In doped Se–Te phase-change thin films: A material for optical data storage

Se_75−xTe₂₅In_x (x = 0, 3, 6, & 9) bulk glasses were obtained by melt quench technique. Thin films of thickness 400 nm were prepared by thermal evaporation technique at a base pressure of 10⁻⁶ Torr onto well cleaned glass substrate. a-Se_75−xTe₂₅In_x thin films were annealed at different temperatures for 2 h. As prepared and annealed films were characterized by X-ray diffraction and UV–Vis spectroscopy. The X-ray diffraction results show that the as-prepared films are of amorphous nature while it shows some poly-crystalline structure in amorphous phases after annealing. The optical absorption spectra of these films were measured in the wavelength range 400–1100 nm in order to derive the extinction and absorption coefficient of these films. It was found that the mechanism of optical absorption follows the rule of allowed non-direct transition. The optical band gap of as prepared and annealed films as a function of photon energy has been studied. The optical band gap is found to decrease with increase in annealing temperature in the present glassy system. It happens due to crystallization of amorphous films. The decrease in optical band gap due to annealing is an interesting behavior for a material to be used in optical storage. The optical band gap has been observed to decrease with the increase of In content in Se–Te glassy system.     

Direct Measurement of Polaron Binding Energy in AMnO3 as a Function of the A Site Ionic Size by Photoinduced IR Absorption

Photoinduced IR absorption was measured in undoped (LaMn)_1?δO₃ and (NdMn)_1?δO₃. We observe broadening and a ～44% increase of the midinfrared anti-Jahn–Teller polaron peak energy when La³⁺ is replaced with smaller Nd³⁺. The absence of any concurent large frequency shifts of the observed PI phonon bleaching peaks and the Brillouin-zone-center internal perovskite phonon modes measured by Raman and infrared spectroscopy indicate that the polaron peak energy shift is mainly a consequence of an increase of the electron phonon coupling constant with decreasing ionic radius 〈r _A〉 on the perovskite A site. This indicates that the dynamical lattice effects strongly contribute to the electronic band narrowing with decreasing 〈r _A〉 in doped giant magnetoresistance manganites.     

An XPS study of amorphous MoO3/SiO films deposited by co-evaporation

X-ray photoelectron spectroscopic (XPS) core-level spectra of MoO₃/SiO thin films are presented. The effects of changes in composition, substrate temperature during deposition and annealing on the binding energy of Mo(3d) and Si(2p) core lines in mixed films are compared with those of MoO₃ and SiO. Appreciable changes in Mo(3d) peak positions and slight changes in Si(2p) peak positions are observed. The change in binding energy of the Mo(3d) doublet may be attributed to the effective incorporation of silicon ions in an MoO₃ lattice which may cause the molybdenum orbital to be a little less tightly bound. This helps in the internal electron transfer from the oxygen (2p) to the molybdenum (4d) level as a result of which the molybdenum is readily changed to lower oxidation states during heat treatment. XPS spectra show that the position of the Si(2p) core state shifts monotonically with increasing oxygen concentration from the value of 101.8 to 102.6 eV.