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.     

Structural and optical properties of thermally evaporated zinc phthalocyanine thin films

Thermally evaporated zinc phthalocyanine (ZnPc) films in the as deposited condition were identified to be as-amorphous. It undergoes structural transformation upon annealing up to 613 K. The optical properties and spectral behavior of as deposited and annealed thin films of ZnPc were studied using spectrophotometric measurements of the transmissivity and reflectivity at normal incidence of light in the wavelength range 200–2500 nm. The refractive index, n, and absorption index, k, were calculated and it was found that they are independent of film thickness in the thickness range 205–530 nm. Annealing at 613 K increases absorbance of films by 5–6 times in comparison with absorbance of as deposited ones and shifts peak positions of all bands towards low energy side of spectra except the peak position of N-band is shifted towards high energy side of spectra. The absorption spectra in the UV–VIS. region has been analyzed in terms of both molecular orbital and band theories. Indirect allowed transitions near the onset and fundamental absorption edges were observed. The energy at the onset was obtained and equals to 1.45 and 1.51 eV for as deposited and annealed films, respectively. The fundamental energy gap was obtained and equals to 2.94 and 2.88 eV for as deposited and annealed films, respectively. The absorption spectra shows four absorption bands. The oscillator strength, f, the electric dipole strength, q², the molar extinction coefficient, ζ_molar, were calculated for as deposited and annealed ZnPc thin films.     

Optical constants and band gap determination of Pb0.95La0.05Zr0.54Ti0.46O3 thin films using spectroscopic ellipsometry and UV–visible spectroscopy

We report the structural evolution and optical properties of lanthanum doped lead zirconate titanate (PLZT) thin films prepared on Pt/TiO₂/SiO₂/Si substrates by chemical solution deposition. X-ray diffraction demonstrates the post-deposition annealing induced crystallization for PLZT films annealed in a temperature (T_a) range of 550–750 °C. PLZT films annealed at higher temperature exhibit polycrystalline structure along with larger grain size. Optical band gap (E_g) values determined from UV–visible spectroscopy and spectroscopic ellipsometry (SE) for PLZT films were found to be in the range of 3.5–3.8 eV. E_g decreases with increasing T_a. The optical constants and their dispersion profiles for PLZT films were also determined from SE analyses. PLZT films show an index of refraction in the range of 2.46–2.50 (λ = 632.8 nm) with increase in T_a. The increase in refractive index at higher T_a is attributed to the improved packing density and crystallinity with the temperature.     

Optical constants of thermally evaporated Se–Sb–Te films using only their transmission spectra

Amorphous Se_82 ? xTe₁₈Sb_x thin films with different compositions (x = 0, 3, 6 and 9 at.%) were deposited onto glass substrates by thermal evaporation. The transmission spectra, T(λ), of the films at normal incidence were obtained in the spectral region from 400 to 2500 nm. Based on the use of the maxima and minima of the interference fringes, a straightforward analysis proposed by Swanepoel has been applied to derive the optical constants and the film thickness. The dispersion of the refractive index is discussed in terms of the single-oscillator Wemple and DiDomenico model. Tauc relation for the allowed non-direct transition describes the optical transition in the studied films. With increasing antimony content the refractive index increases while the optical band gap decreases. The optical band gap decreases from 1.62 to 1.26 eV with increasing antimony content from 0 to 9 at.%. The chemical-bond approach has been applied successfully to interpret the decrease of the optical gap with increasing antimony content.     

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.     

Optical and dielectric properties of double helix DNA thin films

In this work, the thin film of wheat DNA was deposited by spin-coating technique onto glass substrate, and the optical and dielectric properties of the double helix DNA thin film were investigated. The optical constants such as refractive index, extinction coefficient, dielectric constant, dissipation factor, relaxation time, and optical conductivity were determined from the measured transmittance spectra in the wavelength range 190–1100 nm. Meanwhile, the dispersion behavior of the refractive index was studied in terms of the single oscillator Wemple–DiDomenico (W–D) model, and the physical parameters of the average oscillator strength, average oscillator wavelength, average oscillator energy, the refractive index dispersion parameter and the dispersion energy were achieved. Furthermore, the optical band gap values were calculated by W–D model and Tauc model, respectively, and the values obtained from W–D model are in agreement with those determined from the Tauc model. The analysis of the optical absorption data indicates that the optical band gap E_g was indirect transitions. These results provide some useful references for the potential application of the DNA thin films in fiber optic, solar cell and optoelectronic devices.     

Depth dependent properties of ITO thin films grown by pulsed DC sputtering

A systematically prepared set of ITO layers for solar cell applications has been analyzed by spectroscopic variable angle ellipsometry in order to trace the dependence of free carriers’ distribution along the film depth as a function of film thickness as well as its change upon annealing. Samples were deposited on silicon substrates with various thicknesses in steps of approximately 10–20 nm. This set was duplicated and these samples were annealed, so that for each thickness an as-deposited and an annealed sample is available. Conventionally measured electrical conductivity and morphological properties (AFM measurements) of the films have been compared with the optical constants’ inhomogeneity, i.e. material properties along the film thickness modelled by variable-angle spectroscopic ellipsometry. The obtained results show that the optical as well as electrical properties of thin ITO films prepared by pulsed DC sputtering are depth dependent. For the deposition conditions used a well-determined reproducible non-uniform distribution of free carriers within the film thickness was determined. In particular it has been found that the majority of free carriers in as-deposited ultra-thin ITO films is concentrated at sample half-depth, while their distribution becomes asymmetric for the thicker films, with a maximum located at approximately 40 nm depth. The distribution of free carriers in annealed samples is qualitatively different from that of as-deposited layers.     

Effect of composition and deposition parameters on optical properties of Ge25Sb15−xBixS60 thin films

The optical constants of the Ge₂₅Sb_15−xBi_xS₆₀ (0?x?15) chalcogenide films, either as-deposited or after being annealed at various temperatures have been computed in the spectral wavelength range 400-2400 nm from the transmittance and reflectance measurements of normally-incident light. With the increase in bismuth content, the optical energy gap (which is indirect) decreases, while the refractive index increases. The effects of film thickness, substrate type, deposition rate and γ-radiation on optical properties have been studied. The effect of thermal annealing on the growth characteristics and stability of the films has been studied using X-ray diffraction and scanning electron microscopy. The dispersion of the refractive index is discussed in terms of the single-oscillator Wemple-DiDomenico model.     

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.     

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.     

Optical characterization of vacuum evaporated CdZnTe thin films deposited by a multilayer method

CdZnTe thin films of thickness 450–1400 nm have been evaporated under vacuum onto unheated glass substrates, using a multilayer method. During film deposition, the two evaporation sources, separated by two glass cylinders, were maintained at temperatures of 720 K for Zn and at 925–1200 K for CdTe, respectively. After deposition, the samples were annealed in air up to 775 K. The structural and optical properties of both as-deposited and heat-treated samples were investigated. Depending on the preparation conditions and the annealing temperature, the value of the optical band gap, E_g, of respective films varied between 1.16 and 1.63 eV. The obtained results are discussed in correlation with the structure of the films and the role of Zn atoms in CdTe films.     

Spectroscopic ellipsometry and magneto-transport investigations of Mn-doped ZnO nanocrystalline films deposited by a non-vacuum sol–gel spin-coating method

Nanocrystalline Zn_1?xMn_xO films (x = 0, 0.05, 0.1, 0.15, and 0.2) were deposited onto corning glass substrates by a non-vacuum sol–gel spin coating method. All of the films were annealed at 450 °C for 2 h. The structural, optical and magneto-transport properties were investigated by X-ray diffraction, spectroscopic ellipsometry and a system for the measurement of the physical properties. X-ray diffraction analysis of the films reveals that the Mn-doped ZnO films crystallize in the form of a hexagonal wurtzite-type structure with a crystallite size decreases with an increase of the Mn concentration. It was also found that the microstrain increases with the increase of the Mn content. Evidence of nanocrystalline nature of the films was observed from the investigation of surface morphology using transmission, scanning electron microscopy and atomic force microscopy. The optical constants and film thicknesses of nanocrystalline Zn_1?xMn_xO films were obtained by fitting the spectroscopic ellipsometric data (ψ and Δ) using a three-layer model system in the wavelength range from 300 to 1200 nm. The refractive index was observed to increase with increasing Mn concentration. This increase in the refractive index with increasing Mn content may be attributed to the increase in the polarizability due to the large ionic radius of Mn²⁺ compared to the ionic radius of Zn²⁺. The optical band gap of the nanocrystalline Mn–ZnO films was determined by an analysis of the absorption coefficient. The direct transition of the series of films was observed to have energies increasing linearly from 3.17 eV (x = 0) to 3.55 eV (x = 0.2). Magnetoresistance (MR) was measured from 5 K to 300 K in a magnetic field of up to 6 T. Low-field positive MR and high-field negative MR were detected in Mn-doped ZnO at 5 K. Only negative MR was observed for temperatures above 200 K. The positive MR in Mn-doped ZnO films was observed to decrease drastically when the temperature increased from 5 K to 100 K. The isothermal MR of Zn_1?xMn_xO films with different Mn concentrations at 5 K reveals that the increase of the Mn content induces a giant positive MR above x = 0.05 and reaches up to 55% at an applied field of 30 kOe for x = 0.2.     

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.     

Effect of thickness on structural,optical, electrical and morphological properties of nanocrystalline CdSe thin films for optoelectronic applications

This paper presents effect of thickness on the physical properties of thermally evaporated cadmium selenide thin films. The films of thickness 445 nm, 631 nm and 810 nm were deposited employing thermal evaporation technique on glass and ITO coated glass substrates followed by thermal annealing in air atmosphere at temperature 300 °C. The as-deposited and annealed films were subjected to the XRD, UV–Vis spectrophotometer, source meter, SEM and EDS to find the structural, optical, electrical, morphological and compositional analysis respectively. The structural analysis shows that the films have cubic phase with preferred orientation (1 1 1) and nanocrystalline nature. The structural parameters like inter-planner spacing, lattice constant, grain size, number of crystallites per unit area, internal strain, dislocation density and texture coefficient are calculated. The optical band gap is found in the range 1.69–1.84 eV and observed to decrease with thickness. The electrical resistivity is found to increase with thickness for as-deposited films and decrease for annealed films. The morphological studies show that the as-deposited and annealed films are homogeneous, smooth, fully covered and free from crystal defects like pin holes and voids. The grains in the as-deposited films are densely packed, well defined and found to be increased with thickness.     

On the optical constants of amorphous GexSe1−x thin films of non-uniform thickness prepared by plasma-enhanced chemical vapour deposition

The preparation of layers of amorphous Ge_xSe_1−x (with Ge atomic concentrations x=0, 0.17, 0.25 and 0.34) by plasma-enhanced chemical vapour deposition (PECVD) using the hydrides, GeH₄ and H₂Se, as precursor gases is described in detail. Information concerning the structure of the films was obtained from Raman spectroscopy. The optical transmission was measured over the 300 to 2500 nm spectral region in order to derive the refractive index and extinction coefficient of these PECVD films. The expressions proposed by Swanepoel, enabling the calculation of the optical constants of a thin film with non-uniform thickness, have successfully been applied. The refractive-index dispersion data were analysed using the Wemple–DiDomenico single-oscillator fit. The optical-absorption edges have been all of them described using the `non-direct transition' model proposed by Tauc. The optical gaps were calculated using Tauc's extrapolation, resulting in values ranging from 1.93 eV for a-Se to 2.26 eV for a-GeSe₂.     

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.     

Preparation and optical characterization of e-beam deposited cerium oxide films

Cerium oxide films, of 0.3–1 μm thickness, were reactively deposited in the oxygen atmosphere onto quartz plates by the PVD method. An electron gun was used as an evaporation source. Films were characterized with the AFM method, Raman spectroscopy and spectrophotometrically. Optical properties of these films were examined for the wavelength range 0.2–2.5 μm. Films were characterized by high transparency, between 0.38 and 2.5 μm. The complex refractive index, n^*=n − jk, was evaluated. The dispersion characteristics for n(λ) and k(λ) were presented. We found that the refractive index strongly depends on the temperature of substrates (300 K ⩽ T_s ⩽ 673 K) during film deposition. Estimated values of the refractive index (at λ = 0.55 μm) were in the range 1.91–2.34.     

Origin of photoluminescence peaks in Ge–SiO2 thin films

Ge–SiO₂ thin films were prepared by the RF magnetron sputtering technique on p-Si substrates from a Ge–SiO₂ composite target. The as-deposited films were annealed in the temperature range of 300–1000 °C under nitrogen ambience. The structure of films was evaluated by X-ray diffraction, X-ray photoemission spectroscopy and Fourier transform infrared absorption spectroscopy. Results show that the content of Ge and its oxides in the films change with increasing annealing temperature (T_a), the photoluminescence (PL) characteristics are closely dependent on the contents of Ge and its oxides in SiO₂ matrix. The dependence observed strongly suggests that the PL peak at 394 nm is related to the existence of GeO and 580 nm to that of Ge nanocrystal (nc-Ge) in the films.     

Study of the properties of CuInSe2 materials prepared from nanoparticle powder

This work studies the properties of CuInSe₂ (CIS) thin films obtained from nanoparticle powder. The samples were prepared by direct thermal evaporation of ball milled powder from a tungsten crucible onto precleaned glass substrates, using a BALZERS coating unit. The as deposited films were annealed in a vacuum at different temperatures. The composition, structure, morphology and optical properties of these samples have been investigated. X-ray diffraction (XRD) results showed that the CuInSe₂ phase may be prepared by mechanical alloying method. The crystallites of the CIS powder were found to be partially copper-rich. The as-deposited film was polycrystalline in nature having chalcopyrite structure as a mainly phase. The surface morphology is homogeneous across the surface. Expected optical properties (E_g = 1.04 eV, α ≈ 10⁴ cm^? 1) and near stoichiometric composition (Cu: 23.62 at.%, In: 24.35 at.% and Se: 52.03 at.%) were determined.     

Influence of W5+ ions on the optical properties of doped Bi12TiO20

There have been studied single crystals of undoped and doped Bi₁₂TiO₂₀ with two concentrations of W⁵⁺ (2.62 × 10¹⁷ cm⁻³ and 2.62 × 10¹⁸ cm⁻³). There have been obtained absorption spectra in the energy range of 10,482–15,408 cm⁻¹ by classical measurements. There have been determined the cross-section (σ_a) of the impurity absorption and the oscillator strength of d–d transitions. There have been calculated the refractive index of doped crystals and the concentration of Ti³⁺ ions in an undoped sample through an experiment.