Structural and optical properties of Zn doped CuInS2 thin films

Copper indium sulphide (CIS) films were deposited by spray pyrolysis onto glass substrates from aqueous solutions of copper (II) sulphate, indium chloride and thiourea using compressed air as the carrier gas. The copper/indium molar ratio (Cu/In) in the solution 1(1:1) and the sulphur/copper ratio (S/Cu) was fixed at 4. Structural properties of these films were characterized. The effects of Zn (0–5%) molecular weight compared with CuInS₂ Source and different substrate temperatures on films properties were investigated using X-ray diffraction (XRD) and optical transmission spectra. Optical characteristics of the CuInS₂ films have been analysed using spectrophotometer in the wavelength range 300–1100 nm. The absorption spectra of the films showed that this compound is a direct bandgap material and gap values varied between 1·55 and 1·57 eV, depending on the substrate temperatures. Zn-doped samples have a bandgap energy of 1·55–1·95 eV. It was observed that there is an increase in optical bandgap with increasing Zn % molecular weight. The optical constants of the deposited films were obtained from the analysis of the experimentally recorded transmission and absorption spectral data. The refractive index, n and dielectric constants, ε ₁ and ε ₂, were also discussed and calculated as a function of investigated wavelength range and found it dependent on Zn incorporation. We found that the Zn-doped CuInS₂ thin films exhibit P-type conductivity and we predict that Zn species can be considered as suitable candidates for use as doped acceptors to fabricate CuInS₂-based solar cells. The paper presents a study concerning the influence of deposition parameters (temperature of the substrate and concentration of Zn (1–5)% from 0·16 M ZnCl₂) on the quality of CuInS₂ thin films achieved by spray pyrolysis on glass substrate from solutions containing 0·02 M CuCl₂·2H₂O, 0·16 M thiourea and 0·08 M In₂Cl₃·5H₂O.     

Study of structural and optical properties of Cd1-xZnxSe thin films

Cd_1-xZn_xSe (x = 0, 0.5 and 1) thin films have been deposited onto glass substrates using thermal evaporation technique. The lattice constants, grain size, microstrain and dislocation density were studied by using X-ray diffraction. In addition the optical constants were calculated in the wavelength range 400-2500 nm. Transmittance and reflectance were used to calculate the absorption coefficient α and the optical band gap E_g. The linear relation of (αhυ)² as a function of photon energy hυ for the thin films illustrated that the films exhibit a direct band gap, which increases with increasing Zn content. This increasing of optical band gap was interpreted in accordance to the increasing in the cohesive energy. Optical constants, such as refractive index n, optical conductivity σ_opt, complex dielectric constant, relaxation time τ and dissipation factor tanδ were determined. The optical dispersion parameters E₀, E_d were determined according to Wemple and Di Domenico method.     

Third-order optical nonlinear absorption in Bi1.95La1.05TiNbO9 thin films

Single phase Bi_1.95La_1.05TiNbO₉ (LBTN-1.05) thin films with a layered aurivillius structure have been fabricated on fused silica substrates by pulsed laser deposition at 700 °C. The X-ray diffraction pattern revealed that the films are single-phase aurivillius. The band gap, linear refractive index and linear absorption coefficient were obtained by optical transmittance measurements. The film exhibits a high transmittance (> 70%) in visible-infrared region and the dispersion relation of the refractive index vs. wavelength follows the single electronic oscillator model. The nonlinear optical absorption property of the film was determined by the single beam Z-scan method using 800 nm with a duration of 100 fs. A large positive nonlinear absorption coefficient β = 5.95 × 10^− 8 m/W was determined experimentally. The results showed that the LBTN-1.05 is a promising material for applications in absorbing-type optical devices.     

Optical constants of silicone-like (Si:Ox:Cy:Hz) thin films deposited on quartz using hexamethyldisiloxane in a remote RF hollow cathode discharge plasma

Deposition of amorphous silicone-like (Si:O_x:C_y:H_z) thin films in a remote RF hollow cathode discharge plasma using hexamethyldisoloxane as monomer and Ar as feed gas has been investigated for films optical constants and plasma diagnostic as a function of RF power (100-300 W) and precursor flow rate (1-10 sccm). Plasma diagnostic has been performed using Optical Emission Spectroscopy (OES). The optical constants (refractive index, extinction coefficient and dielectric constant) have been obtained by reflection/transmission measurements in the range 300-700 nm. It is found that the refractive index increases from 1.92 to 1.97 with increasing power from 100 to 300 W, and from 1.70 to 1.92 with increasing precursor flow rate from 1 to 10 sccm. The optical energy band gap E_g and the optical-absorption tail ΔE have been estimated from optical absorption spectra, it is found that E_g decreases from 3.28 to 3.14 eV with power increase from 100 to 300 W, and from 3.54 to 3.28 eV with precursor flow rate increase from 1 to 10 sccm. ΔE is found to increase with applied RF power and precursor flow rate increase. The dependence of optical constants on deposition parameters has been correlated to plasma OES.     

Effect of intentional Na-incorporation on the structural, optical and electrical properties of CuInS2:Na thin films for solar energy conversion

Na-doped CuInS₂ material is obtained by the incorporation of the sodium of an atomic percentage in amounts of 0, 0.1, 0.5, 1, 2 and 3% with a stoechiometric mixture of the elements copper, indium and sulfur taken in the stoechiometric proportions. We have investigated in this work the effect of intentional Na-incorporation on the structural, optical and electrical properties of CuInS₂:Na-doped thin films grown by the single source thermal evaporation method. In the resulting Bridgman-grown ingots brittleness were increased with increased Na and measured hot point probe changed sign from p- to n-type in stoechiometric ingots above 0.5 at.%. The samples having a low Na atomic percentage exhibit better crystallinity that shows the effect of the sodium for the larger percentage to degrade the crystallinity of layers (atomic percentage greater than 2 at.%). The film conductivity was strongly affected by Na-doping, which increased from 10^− 6 to 10^− 3 S/cm by increasing [Na]/[CuInS₂] ratio from 0.1 to 3 at.%. Indeed for an atomic percentage Na of 1% we obtained the biggest thickness (1 μm) corresponds to the lowest refractive index value (2.08).     

Structural characterization and optical properties of Cd(1−x)MnxSe thin films

Stoichiometric bulk ingot materials of the ternary mixture Cd_(1−x)Mn_xSe (0.05 ≤ x ≤ 0.9) were prepared by direct fusion of the constituent elements in vacuum sealed silica tubes. X-ray diffraction studies indicate that the investigated samples exhibited a hexagonal structure. The lattice parameters varied linearly with Mn content, following Vegard's law. Thin films were deposited by thermal evaporation from the pre-synthesized ingot material, onto glass substrates. X-ray and electron diffraction studies on the as-deposited and annealed films revealed an amorphous-to-crystalline phase transition at T_a ≈ 423 K. EDAX studies on the prepared films show that the as-deposited films are nearly stoichiometric. The transmittance and reflectance of the deposited Cd_(1−x)Mn_xSe films were measured at normal light incident in the wavelength spectral range 500-2500 nm. Analysis of the transmittance spectra in the entire wavelength range allowed the determination of the refractive index. The dispersion parameters have been calculated, from which the static refractive index as well as static dielecric constant were calculated. Analysis of the absorption coefficient of the investigated films revealed the existence of both the allowed direct and forbidden direct optical transition mechanisms. The corresponding energies were estimated.     

Thickness dependence of structural and optical properties of indium tin oxide nanofiber thin films prepared by electron beam evaporation onto quartz substrates

Indium tin oxide (ITO) thin films, produced by electron beam evaporation technique onto quartz substrates maintained at room temperature, are grown as nanofibers. The dependence of structural and optical properties of ITO thin films on the film thickness (99-662 nm) has been reported. The crystal structure and morphology of the films are investigated by X-ray diffraction and scanning electron microscope techniques, respectively. The particle size is found to increase with increasing film thickness without changing the preferred orientation along (2 2 2) direction. The optical properties of the films are investigated in terms of the measurements of the transmittance and reflectance determined at the normal incidence of the light in the wavelength range (250-2500 nm). The absorption coefficient and refractive index are calculated and the related optical parameters are evaluated. The optical band gap is found to decrease with the increase of the film thickness, whereas the refractive index is found to increase. The optical dielectric constant and the ratio of the free carrier concentration to its effective mass are estimated for the films.     

Effect of process parameters and post deposition annealing on the optical, structural and microwave dielectric properties of RF magnetron sputtered (Ba0.5,Sr0.5)TiO3 thin films

Thin films of (Ba_0.5,Sr_0.5)TiO₃ (BST5) in the thickness range 400-800 nm have been deposited by RF magnetron sputtering on to quartz substrates at ambient temperature. All the properties investigated, i.e. structure, microstructure, optical and microwave dielectric, show a critical dependence on the processing and post processing parameters. The surface morphology as studied by atomic force microscopy reveals ultra fine grains in the case of as deposited films and coarse grain morphology on annealing. The as-deposited films are X-ray amorphous and exhibit refractive index in the range 1.9-2.04 with an optical absorption edge value between 3.8 and 4.2 eV and a maximum dielectric constant of 35 at 12 GHz. The dispersion in refractive index fits into the single effective oscillator model while the variation in the optical parameters with oxygen percentage in the sputtering gas can be explained on the basis of packing fraction changes. On annealing the films at 900 °C they crystallize in to the perovskite structure accompanied by a decrease in optical band gap, increase in refractive index and increase in the microwave dielectric constant. At 12 GHz the highest dielectric constant achieved in the annealed films is 175. It is demonstrated that with increasing oxygen-mixing percentage in the sputtering gas, the microwave dielectric loss decreases while the dielectric constant increases.     

Spectroscopic ellipsometry studies on the optical constants of Bi4Ti3O12:xNa thin films grown by metal-organic chemical vapor deposition

We have deposited undoped and Na-doped epitaxial Bi₄Ti₃O₁₂ thin films on SrTiO₃(001) substrates using the liquid-delivery spin metal-organic chemical vapor deposition technique. High resolution x-ray diffraction and Raman spectroscopy measurements were employed to investigate the structural perfection and incorporation of Na ions into the film. The ellipsometric measurements were carried out in the energy range 1.49-2.75 eV and the corresponding experimental data were fitted. Two different dispersion relations, Cauchy's absorbent and Tauc-Lorentz, have been used to determine the optical constants of the films. It is observed that there is a decrease in optical band gap for increasing sodium content. Furthermore, it has been found that the refractive index and extinction coefficient also depend on the sodium content. The refractive index dispersion data obeyed the single oscillator of the Wemple-DiDomenico model, from which the dispersion parameters were determined. The optical constants tend to decrease with increasing doping content.     

Effect of temperature on structural, optical and photoluminescence properties of antimony (Sb) doped polycrystalline CuInS2 thin films prepared by spray pyrolysis

Copper indium disulphide (CuInS₂) is an absorber material for solar cell and photovoltaic applications. By suitably doping CuInS₂ thin films with dopants such as Zn, Cd, Na, Bi, Sn, N, P and As its structural, optical, photoluminescence properties and electrical conductivities could be controlled and modified. In this work, Sb (0.01 mole (M)) doped CuInS₂ thin films are grown in the temperature range 300-400 °C on heated glass substrates. It is observed that the film growth temperature, the ion ratio (Cu/In = 1.25) and Sb-doping affects the structural, optical and photoluminescence properties of sprayed CuInS₂ films.The XRD patterns confirm that the Sb-doping suppresses the growth of CuInS₂ polycrystalline thin films along (1 1 2) preferred plane and in other characteristic planes. The EDAX results confirm the presence of Cu, In, S and Sb. About 60% of light transmission occurs in the wavelength range 350-1100 nm. The absorption coefficient (α) is found to be in the order of 10⁵ cm⁻¹. The band gap energy increases as the temperature increases from 300-400 °C (1.35-1.40 eV). SEM photographs depict that large sized crystals of Sb-doped CuInS₂ (1 μm) are formed on the surface of the films. Well defined sharp blue and green band emissions are exhibited by Sb-doped CuInS₂ thin films. Defects-related photoluminescence emissions are discussed. These Sb-doped CuInS₂ thin films are prepared by the cost effective method of spray pyrolysis from the aqueous solutions of CuCl₂, InCl₃, SC(NH₂)₂ and SbCl₃ on heated glass substrates.     

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.     

Determination of the optical constants of amorphous AsxS100−x films using effective-medium approximation and OJL model

The transmission spectra were used to obtain an efficient parameterization of the spectral dependences of the optical constants of amorphous As–S thin films by applying a suitable dielectric function model. For studying the compositional dependence of the optical constants, different compositions of As_xS_100−x (x = 10, 15, 20, 25, 30 and 40 at%) thin films were deposited by thermal evaporation technique in a base pressure of 7.5 × 10⁻⁶ Torr at room temperature. The transmission spectra (measured in the wavelength range of 0.2–0.9 μm) were analyzed by applying O’Leary, Johnson, and Lim (OJL) model based on the joint density of states (JDOS) functions. However, the best fit of the optical data was obtained by considering the two-layer configuration film; the top layer was assumed to be consisted of a bulk AsS material embedded in voids (air). Therefore, OJL model along with Bruggeman effective-medium approximation (BEMA) model was used to determine the effective optical constants of the As–S thin films. The photon energy dependence of the dielectric function, ? = ?_r − i?_i of the investigated As–S films was presented. The film thickness, absorption coefficient α, refractive index n, extinction coefficient k, static refractive index n(0) and optical band gap E_g have been deduced. It was found that with the increase in arsenic content up to the stoichiometric As₄₀S₆₀, the indirect optical energy gap decreases, while the refractive index increases.     

Influence of ultraviolet irradiation on the optical properties of amorphous Sb10Se90 thin films

Amorphous Sb₁₀Se₉₀ thin films were prepared by thermal evaporation of the bulk glass. The changes in the optical properties (transmittance, optical gap, absorption coefficient, refractive index and extinction coefficient) have been measured in the wavelength range 500-900 nm of virgin and ultraviolet (UV) illuminated films. Analysis of the optical absorption data shows that the rule of non-direct transitions predominates. It is found that the optical energy gap decreases (photo-darkening) and the refractive index increases with the increase of UV exposure time. The dispersion of the refractive index (n) has been discussed in terms of Wemple-Didomenico single oscillator model. The oscillator energy E₀ and the dispersion energy E_d have been determined and discussed in terms of UV exposure time. The photo-darkening was discussed in terms of some of the current literature models.     

Optical characterization of thin chalcogenide films by multiple-angle-of-incidence ellipsometry

Optical properties of thin chalcogenide films from the systems As-S(Se) and As-S-Se were investigated as a function of the film composition, film thickness and conditions of illumination by light using multiple-angle-of-incidence ellipsometry. Thin films were deposited by thermal evaporation and exposed to white light (halogen lamp) and to monochromatic light from Ar⁺ — (λ = 488, 514 nm) and He-Ne- (λ = 632.8 nm) lasers. The ellipsometric measurements were carried out at three different angles of light incidence in the interval 45-55°, at λ = 632.8 nm. An isotropic absorbing layer model was applied for calculation of the optical constants (refractive index, n and extinction coefficient, k) and film thickness, d. The homogeneity of the films was checked and verified by applying single-angle calculations at different angles. It was shown that the refractive index, n of As-S-Se films is independent of film thickness in the range of 50 to 1000 nm and its values varied from 2.45 to 3.05 for thin layers with composition As₂S₃ and As₂Se₃, respectively. The effect of increasing in the refractive index was observed after exposure to light which is related to the process of photodarkening in arsenic containing layers. The viability of the method for determining the optical constants of very thin chalcogenide films with a high accuracy was confirmed.     

Broad band optical characterization of sol-gel TiO2 thin film microstructure evolution with temperature

Titanium dioxide (TiO₂) thin films have been produced by spin coating a titanium isopropoxide sol on silicon wafer substrates. The structural evolution of the thin films in terms of decomposition, crystallization and densification has been monitored as a function of annealing temperature from 100 to 700 °C using optical characterization and other techniques. The effect of annealing temperature on the refractive index and extinction coefficient of these TiO₂ thin films was studied in the range of 0.62 to 4.96 eV photon energy (250-2000 nm wavelength) using spectroscopic ellipsometry. Thermal gravimetric analysis and atomic force microscopy support the ellipsometry data and provide information about structural transformations in the titania thin films with respect to different annealing temperatures. These data help construct a coherent picture of the decomposition of the sol-gel precursors and the creation of dense layers of TiO₂. It was observed that the refractive index increased from 2.02 to 2.45 at 2.48 eV (500 nm) in sol-gel spin coated titania films for annealing temperatures from 100 °C to 700 °C.     

Structural, electronic, and optical properties of nanocrystalline As-doped ZnO films on quartz substrates determined by Raman scattering and infrared to ultraviolet spectra

Nanocrystalline As-doped ZnO films with different laser power energy (40 mJ and 55 mJ) and As doping concentrations (C_As from 1% to 3%) have been grown on quartz substrates by pulsed laser deposition. The average grain size of the films was calculated from the (002) peak of x-ray diffraction patterns and is estimated to vary from 9 to 13 nm. Electronic transitions and optical properties of the films have been investigated by Raman scattering, far-infrared reflectance, and infrared-ultraviolet spectral transmittance technique. With increasing doping concentration, the A₁ longitudinal optical phonon mode shifts towards the lower energy side and can be described by (564-75C_As) cm^-1 owing to the increment of free carrier concentration. The E₁ transverse optical phonon frequency is located at about 415 cm^-1 and does not show an obvious decreasing trend with the C_As. The optical constants in the photon energy range of 0.5-6.5 eV have been extracted by fitting the experimental data with the Adachi's model. The refractive index dispersion in the transparent region can be well expressed by a Sellmeier's single oscillator function. Due to different doping concentration and hexagonal crystalline structure, the optical band gap of the films grown at 40 mJ linearly decreases with increasing As concentration. The phenomena agree well with the results from the theoretical calculations.     

Optical characterization of HfO2 thin films

Hafnia films prepared onto silicon wafers at three substrate temperatures of 40, 160 and 280 °C are optically characterized utilizing the multi-sample method. The characterization uses the combination of variable angle spectroscopic ellipsometry and spectroscopic reflectometry within the spectral region 1.24-6.5 eV (190-1000 nm). The structural model of the HfO₂ films includes boundary nanometric roughness, thickness non-uniformity and refractive index profile. Spectral dependences of the film optical constants are expressed using a recently developed parametrized joint density of states model describing the dielectric response of both interband transitions and excitations of localized states below the band gap. It is shown that the observed weak absorption below the band gap does not correspond to the Urbach tail.     

Structural and spectroscopic ellipsometry characterization for electrodeposited ZnO growth at different hydrogen peroxide concentration

This work deals with textural and optical characterization of zinc oxide (ZnO) layers obtained by potentiostatic electroplating at various hydrogen peroxide concentrations (from 0 up to 5 mM). The electrodeposition process was studied by cyclic voltametry and chronoamperometry. The [002] preferred growth orientation of hexagonal phase is obtained for the lowest hydrogen peroxide concentration (1 mM), while additionally X-ray diffraction peaks are observed for hydrogen peroxide concentration ranging from 3 to 5 mM. The optical constants and the thickness of films were determined by spectroscopic ellipsometry measurements. The refractive index of all thin films shows normal dispersion behavior. It was also found that refractive index values decrease with increasing hydrogen peroxide concentration. Further, it was revealed that the changes in the optical properties are correlated to the changes in the surface structure.     

Spectroscopic ellipsometry investigations of the optical properties of manganese doped bismuth vanadate thin films

The optical properties of Bi₂V_1−xMn_xO_5.5−x {x = 0.05, 0.1, 0.15 and 0.2 at.%} thin films fabricated by pulsed laser deposition on platinized silicon substrates were studied in UV-visible spectral region (1.51-4.17 eV) using spectroscopic ellipsometry. The optical constants and thicknesses of these films have been obtained by fitting the ellipsometric data (Ψ and Δ) using a multilayer four-phase model system and a relaxed Lorentz oscillator dispersion relation. The surface roughness and film thickness obtained by spectroscopic ellipsometry were found to be consistent with the results obtained by atomic force and scanning electron microscopy. The refractive index measured at 650 nm does not show any marginal increase with Mn content. Further, the extinction coefficient does not show much decrease with increasing Mn content. An increase in optical band gap energy from 2.52 to 2.77 eV with increasing Mn content from x = 0.05 to 0.15 was attributed to the increase in oxygen ion vacancy disorder.     

Optical properties of porous anodic aluminum oxide thin films on quartz substrates

Porous anodic aluminum oxide (AAO) thin films on quartz substrates were fabricated via evaporation of a 100-nm thick Al, followed by anodization with different durations and pore widening and Al removal by chemical etching. The transmittance and reflectance of AAO films on quartz substrates were measured by optical spectrophotometry. The microstructure and morphology were examined by scanning electron microscopy. The pore diameter of AAO films after pore widening and Al removal is 60 ± 4 nm and the interpore distance is 88 ± 5 nm. It is found that the reflectance decreases and the transmittance increases with the increase of the anodization time and pore widening. Compared to a bare substrate, the transmittance of AAO films after pore widening and Al removal is about 3.0% higher, while the reflectance is about 3.0% lower over a wide wavelength range. Additionally, after pore widening and Al removal, when AAO films are prepared on both sides of the quartz substrate, the highest transmittance is about 99.0% in the wavelength range 570-680 nm. The optical constants and thickness of AAO films after pore widening and Al removal were retrieved from normal incidence transmittance data. Results show that the refractive index is lower than 1.25 in the visible optical region and that the porosity is about 0.70.