Growth and characterization of indium oxide thin films prepared by spray pyrolysis

Highly transparent and conducting indium oxide thin films are prepared on glass substrates from precursor solution of indium chloride. These films are characterized by X-ray diffraction, scanning electron microscopy and optical transmission. The preferential orientation of these films is found to be sensitive to deposition parameters. A comparative study has been made on the dependence on the thickness of the film on substrate temperatures with aqueous solution and 1:1 C₂H₅OH and H₂O as precursors. Films deposited at optimum conditions have 167 nm thickness and exhibited a resistivity of 2.94 × 10⁻⁴ Ω m along with transmittance better than 82% at 550 nm. The analytical expressions enabling the derivation of the optical constants of these films from their transmission spectrum only have successfully been applied. Finally, the refractive index dispersion is discussed in terms of the single-oscillator Wemple and Didomenico model.     

Wide bandgap Mg-doped ZnAlO thin films for optoelectronic applications

Magnesium-doped ZnAlO thin films were grown on quartz substrate by ablating the sintered target with a KrF excimer laser. The effect of growth temperature from 30 °C to 700 °C on structural, optical, and electrical properties has been studied. These films are highly transparent in visible spectrum with average transmittance of 82%. The films grown at low temperature are amorphous while films grown at high temperature are crystalline in nature. These films are highly oriented along (0 0 2) direction. The electrical conductivity, carrier concentration, and electron mobility is found to increase with increase in temperature and then decreases with further increase in temperature. The bandgap is found to vary from 3.86 eV to 4.00 eV for various films.     

Investigation of structural,optical and micro-mechanical properties of (NdyTi1 − y)Ox thin films deposited by magnetron sputtering

TiO₂ and (Nd_yTi_1 − y)O_x thin films were deposited by reactive magnetron sputtering process from mosaic Ti–Nd targets and characterised by X-ray diffraction (XRD), Raman optical spectroscopy and nanoindentation technique. XRD measurements revealed that as-prepared titanium dioxide and TiO₂ thin films with 4 and 7 at.% of Nd had nanocrystalline rutile structure, while coatings with larger amount of Nd were amorphous. Raman spectroscopy investigations showed that the increase of the neodymium concentration caused amorphisation of the coatings and hindered their crystal growth. All as-prepared coatings were transparent in the visible wavelength range with a transmittance of approximately 80%. The refractive index and extinction coefficient of the thin films gradually decreased with the increase of the neodymium concentration. Micro-mechanical properties, i.e. hardness and elastic modulus, were determined using traditional load-controlled nanoindentation testing and continuous stiffness measurements. The highest hardness and elastic modulus values were obtained for thin films with 7 at.% of Nd and were approximately 14.8 GPa and 166.3 GPa, respectively.     

Preparation of ZnO:Al thin film on transparent TPT substrate at room temperature by RF magnetron sputtering technique

Aluminum doped ZnO thin films (ZnO:Al) deposited on flexible substrates are suitable to be used as transparent conductive oxide (TCO) thin films in solar cells because of the excellent optical and electrical properties. TPT films are a kind of composite materials and are usually used as encapsulation material of solar panels. In this paper, ZnO:Al film was firstly deposited on transparent TPT substrate by RF magnetron sputtering. The structural, optical, and electrical properties of the film were investigated by X-ray diffractometry (XRD), scanning electron microscope (SEM), UV–visible spectrophotometer, as well as Hall Effect Measurement System. Results revealed that the obtained film had a hexagonal structure and a highly preferred orientation with the c-axis perpendicular to the substrate. Also, the film showed a high optical transmittance over 80% in the visible region and a resistivity of about 3.03 × 10^? 1 Ω·cm.     

Structural,optical and electrical characterization of ZnO:Ga thin films for organic photovoltaic applications

Gallium-doped zinc oxide (ZnO:Ga) films were prepared on glass substrates by RF magnetron sputtering. The effect of growth temperature on microstructure, optical and electrical properties of the films was investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), UV–visible spectrophotometer and four-point probe. The results show that all the films are polycrystalline and (002) oriented, and that the growth temperature significantly affects the microstructure and optoelectrical properties of the films. The film deposited at 670 K has the largest grain size of 71.9 nm, the lowest resistivity of 8.3 × 10^? 4 Ω?cm and the highest figure of merit of 2.1 × 10^? 2 Ω^? 1. Furthermore, the optical energy gaps and optical constants were determined by optical characterization methods. The dispersion behavior of the refractive index was also studied using the Sellmeir's dispersion model and the oscillator parameters of the films were obtained.     

Transparent amorphous zinc oxide thin films for NLO applications

This review focuses on the growth and optical properties of amorphous zinc oxide (ZnO) thin films. A high quality ZnO films fabricated by dip-coating (sol–gel) method were grown on quartz and glass substrates at temperature equal to 350 K. The amorphous nature of the films was verified by X-ray diffraction. Atomic Force Microscopy was used to evaluate the surface morphology of the films. The optical characteristics of amorphous thin films have been investigated in the spectral range 190–1100 nm. Measurement of the polarized optical properties was shows a high transmissivity (80–99%) and low absorptivity (<5%) in the visible and near infrared regions at different angles of incidence. Linear optical properties were investigated by classic and Time-Resolved Photoluminescence (TRPL) measurements. Photoluminescence spectrum exhibits a strong ultraviolet emission while the visible emission is very weak. An innovative TRPL technique has enabled the measurement of the photoluminescence decay time as a function of temperature. TRPL measurements reveal a multiexponential decay behavior typical for amorphous thin films. Second and third harmonic generation measurements were performed by means of the rotational Maker fringe technique using Nd:YAG laser at 1064 nm in picosecond regime for investigations of the nonlinear optical properties. The obtained values of second and third order nonlinear susceptibilities were found to be high enough for the potential applications in the optical switching devices based on refractive index changes. Presented spectra confirm high structural and optical quality of the investigated zinc oxide thin films.     

Spectroscopic ellipsometry study of thin film thermo-optical properties

Spectroscopic ellipsometry (SE) was employed to realize in-situ monitoring and the determination of thermo-optic coefficients (TOC) of thin films by integrating a temperature controlled hot stage to the ellipsometer and applying the empirical relationship of Cauchy between the refractive index and wavelength in the data analysis. Magnetron sputtered titanium oxide thin films of 350 nm thick both as-deposited and post-deposition annealed were prepared on silicon wafers for this investigation. Results of ellipsometric analysis show that as-deposited TiO₂ films have a negative TOC of ? 1.21 × 10^? 4 K^? 1 at 630 nm over the test temperature range 304–378 K. The post-deposition annealing at 923 K for 2 hours leads an increase in film refractive index to 2.29 from 2.17 for as-deposited TiO₂ films, and an enhancement in TOC up to ? 2.14 × 10^? 4 K^? 1. X-ray diffraction (XRD) and scanning electron microscopy (SEM) cross-sectional analysis were performed for film structure characterization.     

Study of annealing time on sol–gel indium tin oxide films on glass

Indium and tin salt-based precursors maintaining In:Sn atomic ratio as 90:10 were utilized for the development of sol–gel dip coated indium tin oxide films (ITO) on SiO₂ coated (∼ 200 nm thickness) soda lime silica glass substrate. The gel films were initially cured in air at ∼ 450 °C to obtain oxide films of physical thickness ∼ 250 nm. These were then annealed in 95% Ar–5% H₂ atmosphere at ∼ 500 °C. The annealing time was varied from 0.5 h to 5 h. Variation of annealing time did not show any considerable change of transmittance in the visible region. Thermal emissivity (ε_d, 0.67–0.79) of the films were evaluated from their hemispherical spectral reflectance. These passed through a minima with increasing annealing time as the reflectivity of the films in the mid-IR passed through a maxima. The microstructure of the films revealed systematic growth of the ITO grains. XRD and XPS studies revealed the presence of both In and Sn metals in addition to the metal oxides. The energy dispersive X-ray (EDX) analysis showed little lowering of tin content in the films with increasing annealing time.     

Effect of sputtering pressure and annealing temperature on the properties of indium tin oxide thin films

Indium tin oxide (ITO) thin films were deposited on glass substrates by RF sputtering system at different sputtering pressure (SP) (20–34 mTorr) and room temperature. The sputtering pressure effects on the deposition rate, electro-optical and structural properties of the as-deposited films were systematically investigated. The optimum sputtering pressure of 27 mTorr, giving a good compromise between electrical conductivity and optical transmittance was found to deposit films. The films were heat-treated in vacuum (200–450 °C) and their electro-optical and structural properties investigated with temperature. A criterion factor Q, which is the ratio between the normalized average transmission to normalized resistivity was defined. It has been observed that Q has its maximum value for heat treatment at 400 °C and the X-ray diffraction (XRD) and scanning electron microscopy (SEM) analysis proves the films have preferred crystal growth towards (2 2 2) direction and average size of grains are 35–40 nm.     

Optical and electrical properties of ink-jet printed indium–tin-oxide nanoparticle films

In this work, spherical indium tin oxide (ITO) nanoparticles (~ 15 nm) synthesized by co-precipitation method were successfully applied for direct ink-jet printing of transparent conducting patterns on polyethylene terephthalate substrates. The printed ITO nanoparticle patterns with various thicknesses were investigated for understanding fundamental properties and potentials for soft electronics. It has been found that the optical transmittance in the visible region as well as the band-gap absorption edge of the printed ITO films significantly varies with thickness, which is related to the huge nanoparticle scattering effect as evidenced. The electrical resistivity can be effectively improved by increasing the pattern thickness, indicating that the present printed ITO films are of great potential for optoelectronic applications.     

Effect of oxygen partial pressure on microstructural and optical properties of titanium oxide thin films prepared by pulsed laser deposition

Nanocrystalline titanium oxide (TiO₂) thin films were deposited on silicon (1 0 0) and quartz substrates at various oxygen partial pressures (1 × 10⁻⁵ to 3.5 × 10⁻¹ mbar) with a substrate temperature of 973 K by pulsed laser deposition. The microstructural and optical properties were characterized using Grazing incidence X-ray diffraction, atomic force microscopy, UV–visible spectroscopy and photoluminescence. The X-ray diffraction studies indicated the formation of mixed phases (anatase and rutile) at higher oxygen partial pressures (3.5 × 10⁻² to 3.5 × 10⁻¹ mbar) and strong rutile phase at lower oxygen partial pressures (1 × 10⁻⁵ to 3.5 × 10⁻³ mbar). The atomic force microscopy studies showed the dense and uniform distribution of nanocrystallites. The root mean square surface roughness of the films increased with increasing oxygen partial pressures. The UV–visible studies showed that the bandgap of the films increased from 3.20 eV to 3.60 eV with the increase of oxygen partial pressures. The refractive index was found to decrease from 2.73 to 2.06 (at 550 nm) as the oxygen partial pressure increased from 1.5 × 10⁻⁴ mbar to 3.5 × 10⁻¹ mbar. The photoluminescence peaks were fitted to Gaussian function and the bandgap was found to be in the range ∼3.28–3.40 eV for anatase and 2.98–3.13 eV for rutile phases with increasing oxygen partial pressure from 1 × 10⁻⁵ to 3.5 × 10⁻¹ mbar.     

Influence of thermal annealing on optical properties and structure of aluminium oxide thin films by filtered cathodic vacuum arc

Optical and structural properties of aluminium oxide thin films are investigated in the annealing temperature range of 200–900 °C. The changes in optical properties and film structure show the great dependence on the temperature. For the film annealed at low temperatures (from 200 °C to 600 °C), the film optical properties, such as transmittance and optical constants, could be improved by thermal annealing with amorphous structure and smooth surface. However, for the film annealed at higher temperature (e.g. 900 °C), the poor performance of optical properties indicates undesirable application for precise use in optics due to significant changes in both structure and surface roughness. At optimum annealing temperature of 600 °C, the transmittance could reach as high as that of substrate and the film possesses better optical constants (refractive index was 1.73 and extinction coefficient was ∼10⁻⁴ at 550 nm) with remaining amorphous structure and smooth surface.     

Phase change and optical band gap behavior of Se0.8S0.2 chalcogenide glass films

Se_0.8S_0.2 chalcogenide glass films have been prepared by thermal vacuum evaporation technique with thickness 583 nm. Annealing process at T ≥ 333 K crystallizes the films and nanostructured films are formed. The crystallite size was increased to 24 nm as the annealing temperature increased to 373 K. Orthorhombic crystalline system was identified for the annealed films. SEM micrographs show that films consist of two parallel surfaces and the thickness was determined by cross section imaging. The optical transmittance is characterized by interference patterns as a result of these two parallel surfaces, besides their average value at longer wavelength decreases as a result of annealing process. The band gap, E_g is red shifted due to crystallization by annealing. As the phase of the films changes from amorphous to crystalline in the annealing temperature range 333–363 K, a non sharp change of the band gap (E_g) is observed. This change was explained by Brus’s model of the energy gap confinement behavior of the nanostructured films. The optical refractive index increases suddenly when the system starts to be crystallized by annealing.     

Effect of aluminum oxide doping on the structural,electrical, and optical properties of zinc oxide (AOZO) nanofibers synthesized by electrospinning

Zinc oxide nanofibers doped with aluminum oxide were prepared by sol–gel processing and electrospinning techniques using polyvinylpyrrolidone (PVP), zinc acetate and aluminum acetate as precursors. The resulting nanofibers were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), UV–Vis spectroscopy, and current–voltage (I–V) properties. The nanofibers had diameters in the range of 60–150 nm. The incorporation of aluminum oxide resulted in a decrease in the crystallite sizes of the zinc oxide nanofibers. Aluminum oxide doped zinc oxide (AOZO) nanofibers exhibited lower bandgap energies compared to undoped zinc oxide nanofibers. However, as the aluminum content (Al/(Al + Zn) × 100%) was increased from 1.70 at.% to 3.20 at.% in the electrospinning solution, the bandgap energy increased resulting in lower conductivity. The electrical conductivity of the AOZO samples was found to depend on the amount of aluminum dopant in the matrix as reflected in the changes in oxidation state elucidated from XPS data. Electrospinning was found to be a productive, simple, and easy method for tuning the bandgap energy and conductivity of zinc oxide semiconducting nanofibers.     

Effects of intermediate metal layer on the properties of Ga–Al doped ZnO/metal/Ga–Al doped ZnO multilayers deposited on polymer substrate

Ga–Al doped ZnO/metal/Ga–Al doped ZnO multilayer films were deposited on polyethersulfone (PES) substrate at room temperature. The multilayer films consisted of intermediate Ag metal layers, top and bottom Ga–Al doped ZnO layer. The multilayer with PES substrate had advantages such as low sheet resistance, high optical transmittance in visible range and stable mechanical properties. From the results, sheet resistances of multilayer showed 9 Ω/sq with 12 nm of Ag metal layer thickness. Average optical transmittance of multilayer film showed 84% in visible range (380–770 nm) with 12 nm of Ag metal layer thickness. Moreover the multilayers showed stable mechanical properties than single-layered Ga–Al doped ZnO sample during the bending test due to the existence of ductile Ag metal layer.     

Flexible polyarylene ether nitrile containing pendant carboxyl groups/Eu(III) fluorescent films with high thermal stability and mechanical strength

A series of flexible and transparent polyarylene ether nitrile with pendant carboxyl groups/Eu(III) fluorescent films were successfully prepared, and characterized by scanning electron microscopy, energy-dispersive spectroscopy, thermogravimetric analysis, tensile test, ultraviolet–visible absorption and fluorescence spectroscopy. The results showed that the films possess high thermal stability (5% weight loss temperatures over 425 °C) and high mechanical strength (tensile strengths exceeding 90 MPa). Furthermore, all the films exhibit a relatively high transmittance in the visible region, and also show an excellent macroscopic flexibility, so that they can be easily bent and curled. This is mainly attributed to the superior performance of the polymer matrix. The photoluminescence results indicated that the films emit an intense red light at 617 nm under ultraviolet excitation, which is attributed to the ⁵D₀ → ⁷F₂ transitions of Eu(III) ions.     

Formation of F-doped ZnO transparent conductive films by sputtering of ZnF2

Fluorine-doped ZnO transparent conductive thin films were successfully deposited on glass substrate by radio frequency magnetron sputtering of ZnF₂. The effects of rapid thermal annealing in vacuum on the optical and electrical properties of fluorine-doped ZnO thin films have been investigated. X-ray diffraction spectra indicate that no fluorine compounds, such as ZnF₂, except ZnO were observed. The specimen annealed at 500 °C has the lowest resistivity of 6.65 × 10^? 4 Ω cm, the highest carrier concentration of 1.95 × 10²¹ cm^? 3, and the highest energy band gap of 3.46 eV. The average transmittance in the visible region of the F-doped ZnO thin films as-deposited and annealed is over 90%.     

Tantalum oxide film prepared by reactive magnetron sputtering deposition for all-solid-state electrochromic device

Inorganic-solid-state electrolyte tantalum oxide thin films were deposited by reactive DC magnetron sputtering to improve the leakage and deterioration of traditional liquid electrolytes in electrochromic devices. O₂ at 1–20 sccm flow rates was used to deposit the tantalum oxide films with various compositions and microstructures. The results indicate that the tantalum oxide thin films were amorphous, near-stoichiometric, porous with a loose fibrous structure, and highly transparent. The maximum charge capacity was obtained at an oxygen flow rate of 3 sccm and 50 W. The transmission change of the Ta₂O₅ film deposited on a WO₃/ITO/glass substrate between colored and bleached states at a wavelength of 550 nm was 56.7%. The all-solid-state electrochromic device was fabricated as a multilayer structure of glass/ITO/WO₃/Ta₂O₅/NiO_x/ITO/glass. The optical transmittance difference of the device increased with increasing applied voltage. The maximum change was 66.5% at an applied voltage of ± 5 V.     

Morphological characterization of TiO2 thin films

Films prepared by reactive magnetron sputtering always present some structural and morphological heterogeneities.In this work, optical parameters, n(λ), k(λ) and E₀, of TiO₂ thin films were obtained, using only optical transmittance measurements. Films were described according to Abèles's model. Using a mono-oscillator type dispersion curve for the refractive index and a Lorentzian type curve for the absorption coefficient, we were able to demonstrate that the films were optically equivalent to a porous layer, with some dispersion in film thickness.The detailed analysis of the experimental transmittance data, fitted between 330 nm to 2200 nm, also enabled us to correlate the effective refractive index of each film with its deposition conditions.     

Reflectance spectra and refractive index of a Nd:YAG laser-oxidized Si surface

The reflectance spectra and refractive index of Nd:YAG laser-oxidized SiO₂ layers with thicknesses from 15 to 75 nm have been investigated with respect to the laser beam energy density and substrate temperature. Thickness and refractive index of films have been determined from reflectance measurements at normal light incidence in the spectral range 300–800 nm. It was found that the oxide-growth conditions at higher substrate temperatures and laser powers greater than 3.36 J cm⁻² provides a better film quality in terms of both optical thickness and refractive index. However, the refractive indices of the films are smaller in the whole spectral range studied as compared to that of conventional thermally grown SiO₂. This might be due to the porous structure formed during the laser-assisted oxidation. The results suggest the need of post-oxidation annealing to improve the refractive indices of the films, suitable for Si-device applications.