Application of optical and luminescent techniques to the characterization of oxide thin films

The interaction between light and electrons in oxide compounds forms the basis for many interesting and practical effects, which are related to microstructure, energy band, traps, carrier transport and others. Thin films of oxides like WO₃, Ga₂O₃, Y₂O₃ and SrTiO₃ were investigated using various improved optical and luminescent techniques. The home-made systems for optical and luminescent measurements were described in detail. The facilities of photo-Hall and photoconductivity transients have been proven to be powerful tools in the studies, which allow us to perform photoinduced process and relaxation measurements over a wide time range from 10⁻⁸ to 10⁴ s. Furthermore, we extended the measurement capabilities of the commercial luminoscope by using an interferometer system with optical fiber and illuminance meter instead of an optical microscope. The cathodoluminescent measurements can be performed at a relative high pressure (20-60 mTorr) compared to ultra-high-vacuum condition of most commercial products. Luminescent characterization was employed as a probe to study doping ions, oxygen vacancies, trap and/or exciton levels in oxide thin films. Our results suggest that various traps and/or excitons in thin films of WO₃, Ga₂O₃ and SrTiO₃ involve in the process of photoconductivity relaxation and emission.     

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.     

Studies on growth and characterization of ternary CdS1−xSex alloy thin films deposited by chemical bath deposition technique

Ternary alloyed CdS_1−xSe_x thin films of variable composition ‘x’ were grown by the simple and economical chemical bath deposition technique. The as-grown thin films were characterized for structural, compositional, surface morphological, optical and electrical studies. The X-ray diffraction (XRD) patterns of the sample indicated that all the samples were polycrystalline in nature with hexagonal structure. Scanning electron microscopy (SEM) micrographs showed uniform morphology with spherical shaped grains distributed over entire glass substrate. EDAX studies confirmed that the CdS_1−xSe_x films were having approximately same stoichiometry initially as well as finally. Room temperature optical measurements showed that band gap engineering could be realized in CdS_1−xSe_x thin films via modulation in composition ‘x’. Electrical resistivity of CdS_1−xSe_x thin films for various compositions was found to be low. The broad and fine tunable band gap properties of ternary CdS_1−xSe_x thin films have potential applications in opto-electronic devices.     

Influence of annealing temperature on microstructure and optical properties of sol-gel derived tungsten oxide films

Tungsten oxide (WO₃) thin films have been extensively studied for their interesting physical properties and a variety of potential applications in electrochromic devices. In order to explore the possibility of using these in electrochromic devices, a preliminary and thorough study of the optical properties of the host materials is an important step. Based on this, the influence of annealing temperature on the structural, surface morphological, optical and electrochromic properties has been investigated in the present work. The host material, WO₃ films, has been prepared from an ethanolic acetylated peroxotungstic acid sol containing 5 wt.% oxalic acid dehydrate (OAD) by sol-gel technique. The monoclinic structure and textured nature change of the films with the temperature increasing have been investigated by X-ray diffraction analysis. The surface morphology evolution of the films has been characterized by SEM. The shift in absorption edge towards the higher wavelength region observed from optical studies may be due to the electron scattering effects and the optical band filling effect that reveals the crystallization of the film. The amorphous film shows better optical modulation (ΔT = 76.9% at λ = 610 nm), fast color-bleach kinetics (t_c ∼ 4 s and t_b ∼ 9 s) and good reversibility (Q_b/Q_c = 90%), thereby rendering it suitable for smart window applications.     

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.     

A comparative study of the physical properties of Sb2S3 thin films treated with N2 AC plasma and thermal annealing in N2

As-deposited antimony sulfide thin films prepared by chemical bath deposition were treated with nitrogen AC plasma and thermal annealing in nitrogen atmosphere. The as-deposited, plasma treated, and thermally annealed antimony sulfide thin films have been characterized by X-ray diffraction (XRD), energy dispersive X-ray spectroscopy, scanning electron microscopy, atomic force microscopy, UV-vis spectroscopy, and electrical measurements. The results have shown that post-deposition treatments modify the crystalline structure, the morphology, and the optoelectronic properties of Sb₂S₃ thin films. X-ray diffraction studies showed that the crystallinity of the films was improved in both cases. Atomic force microscopy studies showed that the change in the film morphology depends on the post-deposition treatment used. Optical emission spectroscopy (OES) analysis revealed the plasma etching on the surface of the film, this fact was corroborated by the energy dispersive X-ray spectroscopy analysis. The optical band gap of the films (E_g) decreased after post-deposition treatments (from 2.36 to 1.75 eV) due to the improvement in the grain sizes. The electrical resistivity of the Sb₂S₃ thin films decreased from 10⁸ to 10⁶ Ω-cm after plasma treatments.     

Optical properties of selenium-tellurium nanostructured thin film grown by thermal evaporation

Se-Te nanostructured thin films were deposited on glass substrates in the presence of oxygen and argon by thermal evaporation. The properties of Se-Te thin films strongly depend on the deposition method. During the process used, the substrate is cooled to a temperature of 77 K employing liquid nitrogen. The nanostructured thin films of Se_100−xTe_x (where x=4, 8 and 16) are deposited on glass substrate. The surface morphology of the deposited films was investigated through Scanning Electron Microscopy (SEM). The typical size of these nanostructures is in the range 40-100 nm and the length is of the order of several micrometers. The optical parameters i.e. optical gap (E_g), absorption coefficient (α), and extinction coefficient (k) are calculated in the wavelength range 190-1100 nm. It was found that the optical band gap decreased from 3.4 to 2.9 eV when Te concentration was increased in the Se_100−xTe_x nanostructured thin films. The large bandgap may be attributed to the decrease in particle size which clearly exhibits a quantum size effect. XRD analysis was performed to confirm glassy nature of the nanostructured thin films.     

Novel type of indium oxide thin films sputtering for opto-electronic applications

Transparent conductive oxide (TCO) thin films play a significant role in recent optical technologies. Displays of various types, photovoltaic systems, and opto-electronic devices use these films as transparent signal electrodes. They are used as heating surfaces and active control layers. Oxides of TCO materials such as: tin, indium, zinc, cadmium, titanium and the like, exhibit their properties. However, indium oxide and indium oxide doped with tin (ITO) coatings are the most used in this technology.In this work, we present conductive transparent indium oxide thin films which were prepared using a novel triode sputtering method. A pure In₂O₃ target of 2 in. in diameter was used in a laboratory triode sputtering system. This system provided plane plasma discharge at a relatively low pressure 0.5-5 mTorr of pure argon. The substrate temperature was varied during the experiments from room temperature up to 200 °C. The films were deposited on glass, silicon, and flexible polyimide substrates. The films were characterized for optical and electrical properties and compared with the indium oxide films deposited by magnetron sputtering.     

Third-order optical nonlinearities of lead-free (Na1−xKx)0.5Bi0.5TiO3 thin films

(Na_1−xK_x)_0.5Bi_0.5TiO₃ (NKBT) (x = 0.1, 0.2, and 0.3) thin films with good surface morphology and rhombohedral perovskite structure were fabricated on quartz substrates by a sol-gel process. The fundamental optical constants (the band gaps, linear refractive indices and absorption coefficients) of the films were obtained through optical transmittance measurements. The nonlinear optical properties were investigated by Z-scan technique performed at 532 nm with a picosecond laser. A two-photon absorption effect closely related with potassium-doping content was found in thin films, and the nonlinear refractive index n₂ increases evidently with potassium-doping. The real part of the third-order nonlinear susceptibility χ⁽³⁾ is much larger than its imaginary part, indicating that the third-order optical nonlinear response of the NKBT films is dominated by the optical nonlinear refractive behavior. These results show that NKBT thin films have potential applications in nonlinear optics.     

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.     

Nano-star formation in Al-doped ZnO thin film deposited by dip-dry method and its characterization using atomic force microscopy, electron probe microscopy, photoluminescence and laser Raman spectroscopy

Zinc oxide doped with Al (AZO) thin films were prepared on borosilicate glass substrates by dip and dry technique using sodium zincate bath. Effects of doping on the structural and optical properties of ZnO film were investigated by XRD, EPMA, AFM, optical transmittance, PL and Raman spectroscopy. The band gap for ZnO:Al (5.0 at. wt.%) film was found to be 3.29 eV compared with 3.25 eV band gap for pure ZnO film. Doping with Al introduces aggregation of crystallites to form micro-size clusters affecting the smoothness of the film surface. Al³⁺ ion was found to promote chemisorption of oxygen into the film, which in turn affects the roughness of the sample. Six photoluminescence bands were observed at 390, 419, 449, 480, 525 and 574 nm in the emission spectra. Excitation spectra of ZnO film showed bands at 200, 217, 232 and 328 nm, whereas bands at 200, 235, 257 and 267 nm were observed for ZnO:Al film. On the basis of transitions from conduction band or deep donors (CB, Zn_i or V_OZn_i) to valence band and/or deep acceptor states (VB, V_Zn or O_i or O_Zn), a tentative model has been proposed to explain the PL spectra. Doping with Al³⁺ ions reduced the polar character of the film. This has been confirmed from laser Raman studies.     

Comparative photoemission study of the electronic properties of L-CVD SnO2 thin films

In this work we present the results of comparative XPS and PYS studies of electronic properties of the space charge layer of the L-CVD SnO₂ thin films after air exposure and subsequent UHV annealing at 400 °C, with a special emphasis on the interface Fermi level position.From the centre of gravity of binding energy of the main XPS Sn 3d_5/2 line the interface Fermi level position E_F − E_v in the band gap has been determined. It was in a good correlation with the value estimated from the offset of valence band region of the XPS spectrum, as well as from the photoemission yield spectroscopy (PYS) measurements. Moreover, from the valence band region of the XPS spectrum and PYS spectrum two different types of filled electronic band gap states of the L-CVD SnO₂ thin films have been derived, located at 6 and 3 eV with respect to the Fermi level.     

Morphological, microstructural and optical properties supremacy of binary composite films—A study based on Gd2O3/SiO2 system

Composites are pragmatic choices for tailoring the material to have a desired property. Besides, such thin films have scopes to display superior optical, microstructural and morphological properties which are otherwise not possible to obtain from the pure component films. Vapor-phase-mixed binary composite Gd₂O₃/SiO₂ thin film is one such interesting system where band gap as well as refractive index superiority is observed simultaneously under certain compositional mixings. Such and similar observations in composites cannot be explained by Moss empirical rule. Our systematic study on the microstructure of this composite system based on ellipsometry and scanning probe microscopy has satisfactorily provided the information that can explain such optical properties supremacy. Morphological measurements and its derived parameters like autocorrelation and height-height correlation functions have provided several clues that represent the superior grain structures of the composites. Besides, refractive index modeling through effective single oscillator model has strongly supported such analysis results favoring the superior microstructure in composite films.     

A simplified reactive thermal evaporation method for indium tin oxide electrodes

Indium tin oxide (ITO) films approximately 120 nm thick were deposited onto unheated glass substrates by using reactive thermal evaporation (RTE) and in situ post-evaporation annealing in oxygen. We show that this simplified method can be used to produce high quality ITO thin films with low electrical resistivity (10⁻³ Ω cm) and high transmittance (approximately 80% at 550 nm). The refractive index is approximately 2.0 and the direct optical band gap of the films (above 3.0 eV) is in good agreement with previously reported values. Since this deposition method does not require heating the substrates or furnace annealing at high temperatures, it can be advantageous when it is necessary to decrease the thermal budget on underlying devices or layers.     

Structural and optical properties of sputtered ZnO thin films

Zinc oxide (ZnO) and aluminium-doped zinc oxide (ZnO:Al) thin films were prepared by RF diode sputtering at varying deposition conditions. The effects of negative bias voltage and RF power on structural and optical properties were investigated. X-ray diffraction measurements (XRD) confirmed that both un-doped and Al-doped ZnO films are polycrystalline and have hexagonal wurtzite structure. The preferential 〈0 0 1〉 orientation and surface roughness evaluated by AFM measurements showed dependence on applied bias voltage and RF power. The sputtered ZnO and ZnO:Al films had high optical transmittance (>90%) in the wavelength range of 400-800 nm, which was not influenced by bias voltage and RF power. ZnO:Al were conductive and highly transparent. Optical band gap of un-doped and Al-doped ZnO thin films depended on negative bias and RF power and in both cases showed tendency to narrowing.     

Optical parameters in SnO2 nanocrystalline textured films grown on p-InSb (111) substrates

Spectroscopic ellipsometry and photoluminescence (PL) measurements on SnO₂ nanocrystalline textured films grown on p-InSb (111) substrates by using radio-frequency magnetron sputtering at low temperature were carried out to investigate the dependence of the optical parameters on the SnO₂ thin film thickness. As the SnO₂ film thickness increases, while the energy gap of the SnO₂ film decreases, its refractive index increases. The PL spectra show that the broad peaks corresponding to the donor-acceptor pair transitions are dominant and that the peak positions change with the SnO₂ film thickness. These results can help improve understanding for the application of SnO₂ nanocrystalline thin films grown on p-InSb (111) substrates in potential optoelectronic devices based on InSb substrates.     

Characterization of Zn<Subscript>2</Subscript>SnO<Subscript>4</Subscript> Thin Films Prepared by RF Magnetron Sputtering

Zn₂SnO₄ (ZTO) is a stable semiconductor in ZnO–SnO₂ system and important transparent conducting oxide (TCO) predominantly used in optoelectronic devices. ZTO thin films were prepared by RF magnetron sputtering using Zn₂SnO₄ ceramic target in this paper. The effects of annealing temperatures and oxygen contents on characterization of ZTO thin films were studied. The results show that ZTO thin films prepared by RF magnetron sputtering are amorphous with an optical band gap of 3.22 eV. After annealing at 650°C in Ar atmosphere for 40 min, ZTO films possess a spinel structure with an optical band gap of 3.62 eV. The atomic force microscope (AFM) data of morphology reveals that the surface roughness of films is about 2 nm. The results of energy dispersive spectrometer (EDS) show that the concentration ratio of Zn to Sn is in the range from 1.44 to 1.57. The results of Hall-effect-measurement system reveal that the resistivity of films varies from 102 to 10–1 Ωcm, carrier concentration is about 10¹⁷ cm^–3, and mobility ranges from 10⁰ to 10¹ cm² v^–1 s^–1.     

Deposition of quaternary sputtered CIGS nanorods via glancing angle deposition

Nanostructured materials have become an attractive alternative to their thin film and bulk counterparts in photovoltaic and photoconductivity research. This is mainly attributed to their superior optical and electrical properties. Light trapping in vertically aligned nanostructures results in high optical absorption and provides enhanced carrier collection by utilizing a fully depleted p–n‐junction between the anode and cathode via an isolated ”capping” construction. The combination of these two features can potentially lead to the development of high efficiency nanostructured devices including solar cells, photodiodes, and photodetectors. Optical absorption proper ties of nanorod arrays of CuIn_x Ga_1–xSe₂ (CIGS), a p‐type semiconductor with a wide band gap ranging from 1.0 eV to 1.7 eV, are compared to their thin film counterpart. Utilizing an RF sputtering system, a quaternary target, and glancing angle deposition (GLAD) technique, vertical arrays of CIGS nanorods were fabricated while conventional films were fabricated by normal incidence deposition. Scanning electron microscopy (SEM) images indicated a successful growth of CIGS nanorods. Optical absorption was found to be strongly altered by the presence of the nanorod structures through spectroscopic reflectometry. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Femtosecond Z-scan measurement of third-order optical nonlinearities in anatase TiO2 thin films

Anatase phase TiO₂ films have been grown on fused silica substrate by pulsed laser deposition technique at substrate temperature of 750 °C under the oxygen pressure of 5 Pa. From the transmission spectra, the optical band gap and linear refractive index of the TiO₂ films were determined. The third-order optical nonlinearities of the films were measured by Z-scan method using a femtosecond laser (50 fs) at the wavelength of 800 nm. The real and imaginary parts of third-order nonlinear susceptibility χ⁽³⁾ were determined to be −7.1 × 10⁻¹¹esu and −4.42 × 10⁻¹²esu, respectively. The figure of merit, T, defined by T=βλ/n₂, was calculated to be 0.8, which meets the requirement of all-optical switching devices. The results show that the anatase TiO₂ films have great potential applications for nonlinear optical devices.     

Effect of energetic electron beam treatment on Ga-doped ZnO thin films

Transparent conductive zinc oxide (ZnO) thin films were synthesized by a sol–gel spin coating method with the addition of Ga(NO₃)₃ in a Zn(CH₃COO)₂ solution and exposed to electron beam treatment. The UV–Vis spectra demonstrated that all of the films had transmittances of over 85% in the visible region. When Ga(NO₃)₃ was added to the ZnO precursor solution, the resistivity of the ZnO thin film decreased and the carrier concentration increased significantly. After electron beam treatment was performed on the 0.4 at.% Ga-doped ZnO film, the optical band gap increased and the resistivity significantly decreased resulting from the increases of the carrier concentration and mobility. By combining Ga doping and electron beam treatment, the resistivity of the ZnO thin film was reduced by a factor of nine hundred.