Optical constants of Zn-doped CuInS2 thin films

Optical properties of Zn-doped CuInS₂ thin films grown by double source thermal evaporation method have been studied. The amount of the Zn source was determined to be 0%-4% molecular weight compared with CuInS₂ source. After that, samples were annealed in vacuum at the temperature of 450 °C in quartz tube. The optical constants of the deposited films were obtained from the analysis of the experimental recorded transmission and reflexion spectral data over the wavelength range 300-1800 nm. It is observed that there is an increase in optical band gap with increasing Zn % molecular weight. It has been found that the refractive index and extinction coefficient are dependent on Zn incorporation. The complex dielectric constants of Zn-doped CuInS₂ films have been calculated in the investigated wavelength range. It was found that the refractive index dispersion data obeyed the single oscillator of the Wemple-DiDomenico model, from which the dispersion parameters and the high-frequency dielectric constant were determined. The electric free carrier susceptibility and the carrier concentration on the effective mass ratio were estimated according to the model of Spitzer and Fan.     

Phase determination of filtered vacuum arc deposited TiO2 thin films by optical modeling

Thin films of TiO₂ were produced using filtered vacuum arc deposition. Arc currents were 275, 300, 325 A, and the oxygen pressure during deposition was 0.93 Pa. The substrates were glass microscope slides, at temperatures of 25 °C (RT), 200 °C, and 400 °C. Film thickness was in the range 100 to 250 nm, depending on the deposition conditions. Film structure and chemical composition were determined using XRD and XPS analyses, respectively. As-deposited films were amorphous, except to two samples that were found to be crystalline (deposited with 300 A, 325 A at 400 °C), and the crystalline phase was close to that of anatase. All of the films were partially crystallized by annealing in air at 450 °C for 1 h. The O:Ti atomic concentration ratio was in the range 1.6:1-2:1, independent of deposition conditions. The optical parameters, refractive index and the extinction coefficient of the films were determined using variable angle spectroscopic ellipsometry. In addition, the optical transmission of the films were determined in the UV-VIS and IR regions. The average optical transmission in the VIS spectrum was 70-85%, affected by the interference in the film with 90% maxima and 60% minima. The refractive index at λ = 550 nm was in the range 2.4 to 2.7, depending on the deposition conditions and annealing. Using the semi-empirical model of Wemple and DiDomenico for the dielectric function below the interband absorption edge of ionic and covalent solids, the dispersion energy parameters of TiO₂ (E_o, E_d) were calculated. The underlying structural order of the amorphous films was inferred by comparing the dispersion energy parameters of the amorphous films with those of crystalline TiO₂. As expected, the refractive index of the amorphous films depended on the underlying phase of the film. The optical analyses indicated that the underlying phase of the amorphous films deposited on RT substrates was close to anatase, whereas the underlying phase of the amorphous films deposited on 400 °C substrates and annealed at 450 °C for 1 h consisted of both anatase and rutile. Thus, although the XRD analyses could not indicate the underlying phase of the amorphous films, it could be determined by the optical analyses.     

Scaling behavior and structure transition of ZrO2 films deposited by RF magnetron sputtering

ZrO₂ thin films were deposited onto Si wafers and glass slides by reactive rf magnetron sputtering with varying conditions of substrate temperature (T_s). Structural analysis was carried out using high-resolution transmission electron microscopy (HRTEM) and atomic force microscopy (AFM). The scaling behavior of the AFM topographical profiles was analyzed using one-dimensional power spectral density method (1DPSD). Morphological and structural evolution of ZrO₂ films have been studied in relation to T_s. With substrate temperatures ranging from RT to 550 °C, the structural transition of the films is a-ZrO₂ (below 250 °C) → m-ZrO₂ with a little a-ZrO₂ (450 °C) → m-ZrO₂ with a little t-ZrO₂ (550 °C). The roughness exponent α is 1.53 ± 0.02, 1.04 ± 0.01, 1.06 ± 0.05, 1.20 ± 0.03 for ZrO₂ thin films deposited at RT, 250 °C, 450 °C, and 550 °C, respectively. Quantitative surface characterization by spatially resolved 1DPSD analyses identified three different growth mechanisms of surface morphology for ZrO₂ thin films deposited at RT, 250∼450 °C and 550 °C. The evolution and interactions of surface roughness and microstructure are discussed in terms of surface diffusion, grain growth, and flux shadowing mechanisms.     

Effect of thermal annealing time on optical and structural properties of TeO2 thin films

TeO₂ thin films were deposited on quartz substrates by rf reactive sputtering technique from a Te metal target. The obtained samples were annealed in an argon atmosphere at 450 °C for different annealing times up to 90 min. X-ray diffraction studies revealed that the as-grown samples were amorphous and there was no appreciable change in structure for a short annealing time. Thin films became polycrystalline with the tetragonal (α-phase) structure of tellurium dioxide crystal with the increase of the thermal annealing time. The refractive index and optical energy gap of the films were calculated by modelling transmittance spectra. The optical energy gap decreased continuously from 3.83 eV to 3.71 eV with increasing thermal annealing time.     

Structural, thermal and optical characterization of TiO2:ZrO2 thin films prepared by sol-gel method

We have studied the structural and optical properties of thin films of TiO₂, doped with 5% ZrO₂ and deposited on glass substrate (by the sol-gel method). The dip-coated thin films have been examined at different annealing temperatures (350 to 450 °C) and for various layer thicknesses (63-286 nm). Refractive index and porosity were calculated from the measured transmittance spectrum. The values of the index of refraction are in the range of 1.62-2.29 and the porosity is in the range of 0.21-0.70. The coefficient of transmission varies from 50 to 90%. In the case of the powder of TiO₂, doped with 5% ZrO₂, and aged for 3 months in ambient temperature, we have noticed the formation of the anatase phase (tetragonal structure with 14.8 nm grains). However, the undoped TiO₂ exhibits an amorphous phase. After heat treatments of thin films, titanium oxide starts to crystallize at the annealing temperature 350 °C. The obtained structures are anatase and brookite. The calculated grain size, depending on the annealing temperature and the layer thickness, is in the range (8.58-20.56 nm).     

Growth and vacuum post-annealing effect on the properties of the new absorber CuSbS2 thin films

Post-growth treatments in vacuum atmosphere were performed on CuSbS₂ films prepared by the single-source thermal evaporation method on glass substrates. The films were annealed in vacuum atmosphere for 2 h in temperature range 130-200 °C. The effect of this thermal treatment on the structural, optical and electrical properties of the films was studied. X-ray diffraction (XRD) patterns indicated that the films exhibited an amorphous structure for annealing temperature below 200 °C and a polycrystalline structure with CuSbS₂ principal phase. For the films annealed at temperatures below 200 °C one direct optical transition in range 1.8-2 eV was found. For the films annealed at 200 °C, two optical direct transitions emerged at 1.3 and 1.79 eV corresponding to the CuSbS₂ and Sb₂S₃ values respectively. The electrical measurements showed a conversion from low resistivities (3.10^− 2-9.10^− 2) Ω cm for the samples annealed at temperatures below 200 °C to relatively high resistivities (2 Ω cm) for the samples annealed at 200 °C. In all cases the samples exhibited p-Ztype conductivity.     

Structural and optical studies of nanocrystalline V2O5 thin films

We report the structural and optical properties of nanocrystalline thin films of vanadium oxide prepared via evaporation technique on amorphous glass substrates. The crystallinity of the films was studied using X-ray diffraction and surface morphology of the films was studied using scanning electron microscopy and atomic force microscopy. Deposition temperature was found to have a great impact on the optical and structural properties of these films. The films deposited at room temperature show homogeneous, uniform and smooth texture but were amorphous in nature. These films remain amorphous even after postannealing at 300 °C. On the other hand the films deposited at substrate temperature T_S > 200 °C were well textured and c-axis oriented with good crystalline properties. Moreover colour of the films changes from pale yellow to light brown to black corresponding to deposition at room temperature, 300 °C and 500 °C respectively. The investigation revealed that nanocrystalline V₂O₅ films with preferred 001 orientation and with crystalline size of 17.67 nm can be grown with a layered structure onto amorphous glass substrates at temperature as low as 300 °C. The photograph of V₂O₅ films deposited at room temperature taken by scanning electron microscopy shows regular dot like features of nm size.     

Overview about the optical properties and mechanical stress of different dielectric thin films produced by reactive-low-voltage-ion-plating

Thin films of Ta₂O₅, Nb₂O₅, and HfO₂ were deposited by reactive-low-voltage-ion-plating (RLVIP) on unheated glass and silicon substrates. The film thickness was about 200 nm. Optical properties as well as mechanical film stress of these layers were investigated in dependence of various deposition parameters, i.e. arc current and oxygen partial pressure. For an arc current in the range between 40 and 50 A and an oxygen partial pressure of at least 11 · 10^− 4 mbar good results were obtained. The refractive index and film thickness were calculated from spectrophotometric transmission data using the Swanepoel theory. For example at 550 nm wavelength the refractive index for thin RLVIP-Nb₂O₅-films was found to be n₅₅₀ = 2.40. The optical absorption was obtained by photo-thermal deflection spectrometry. For the investigated materials absorption coefficients in the range of k = 5 · 10^− 4 at 515 nm wavelength were measured. The mechanical film stress was determined by measuring the difference in bending of silicon substrates before and after the deposition process. For dense films, i.e. no water vapour sorption on atmosphere, the mechanical film stress was always compressive with values of some hundred MPa. In case of films deposited with higher arc currents (I_arc > 60A) and lower oxygen pressure (< 15 · 10^− 4 mbar) the influence of a post deposition heat treatment at 350 °C for 4 h on air was also investigated. For these films the properties could clearly be improved by such treatment. However, by using lower arc currents and higher oxygen partial pressure during the ion plating process, immediately dense and environmental stable films with good optical as well as mechanical properties could be achieved without post deposition heat treatment. All the results obtained will be presented in graphs and diagrams.     

Investigation of the substrate effect for Zr doped ZnO thin film deposition by thermionic vacuum arc technique

ZnO is a fundamental wide band gap semiconductor. Especially, doped elements change the optical properties of the ZnO thin film, drastically. Doped ZnO semiconductor is a promising materials for the transparent conductive oxide layer. Especially, Zr doped ZnO is a potential material for the high performance TCO. In this paper, ZnO semiconductors were doped with Zr element and microstructural, surface and optical properties of the Zr doped ZnO thin films were investigated. Zr doped ZnO thin films were deposited thermionic vacuum arc (TVA) technique. TVA is a rapid and high vacuum deposition method. A glass, polyethylene terephthalate and Si wafer (111) were used as a substrate material. Zr doped ZnO thin films deposited by TVA technique and their substrate effect investigated. As a results, deposited thin films has a high transparency. The crystal orientation of the films are in polycrystal formation. Especially, substrate crystal orientation strongly change the crystal formation of the films. Substrate crystal structure can change the optical band gap, microstructural properties and deposited layer formation. According to the atomic force microscopy and field emission scanning electron microscopy measurements, all deposited layer shows homogeneous, compact and low roughness. The band values of the deposited thin film were approximately found as to be 3.1–3.4 eV. According to the results, Zr elements created more optical defect and shifted to the band gap value towards to blue region.     

The effect of sputtering gas pressure on structure and photocatalytic properties of nanostructured titanium oxide self-cleaning thin film

Titanium oxide thin films were deposited by DC reactive magnetron sputtering on ZnO (80 nm thickness)/soda-lime glass and SiO₂ substrates at different gas pressures. The post annealing on the deposited films was performed at 400 °C in air atmosphere. The results of X-ray diffraction (XRD) showed that the films had anatase phase after annealing at 400 °C. The structure and morphology of deposited layers were evaluated by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The surface grain size and roughness of TiO₂ thin films after annealing were around 10-15 nm and 2-8 nm, respectively. The optical transmittance of the films was measured using ultraviolet-visible light (UV-vis) spectrophotometer and photocatalytic activities of the samples were evaluated by the degradation of Methylene Blue (MB) dye. Using ZnO thin film as buffer layer, the photocatalytic properties of TiO₂ films were improved.     

Optical and structural properties of CuSbS2 thin films grown by thermal evaporation method

Structural, optical and electrical properties of CuSbS₂ thin films grown by thermal evaporation have been studied relating the effects of substrate heating conditions of these properties. The CuSbS₂ thin films were carried out at substrate temperatures in the temperature range 100-200 °C. The structure and composition were characterized by XRD, SEM and EDX. X-ray diffraction revealed that the films are (111) oriented upon substrate temperature 170 °C and amorphous for the substrate temperatures below 170 °C. No secondary phases are observed for all the films. The optical absorption coefficients and band gaps of the films were estimated by optical transmission and reflection measurements at room temperature. Strong absorption coefficients in the range 10⁵-10⁶ cm^− 1 at 500 nm were found. The direct gaps Eg lie between 0.91-1.89 eV range. It is observed that there is a decrease in optical band gap Eg with increasing the substrate temperature. Resistivity of 0.03-0.96 Ω cm, in dependence on substrate temperature was characterized. The all unheated films exhibit p-type conductivity. The characteristics reported here also offer perspective for CuSbS₂ as an absorber material in solar cells applications.     

Nanoporous TiO2 thin film based conductometric H2 sensor

Nanoporous titanium dioxide (TiO₂) based conductometric sensors have been fabricated and their sensitivity to hydrogen (H₂) gas has been investigated. A filtered cathodic vacuum arc (FCVA) system was used to deposit ultra-smooth Ti thin films on a transducer having patterned inter-digital gold electrodes (IDTs). Nanoporous TiO₂ films were obtained by anodization of the titanium (Ti) thin films using a neutral 0.5% (wt) NH₄F in ethylene glycol solution at 5 V for 1 h. After anodization, the films were annealed at 600 °C for 8 h to convert the remaining Ti into TiO₂. The scanning electron microscopy (SEM) images revealed that the average diameters of the nanopores are in the range of 20 to 25 nm. The sensor was exposed to different concentrations of H₂ in synthetic air at operating temperatures between 100 °C and 300 °C. The sensor responded with a highest sensitivity of 1.24 to 1% of H₂ gas at 225 °C.     

Effect of assist ion beam voltage on intrinsic stress and optical properties of Ta2O5 thin films deposited by dual ion beam sputtering

The optical properties and intrinsic stress of Ta₂O₅ thin films deposited by dual ion beam sputtering (DIBS) were studied as a function of the assist ion beam voltage (250-650 V). When the assist ion beam voltage was in the range of 350-450 V, the transmittance at the quarter-wave point reached its highest value (lowest absorption). The refractive index increased to 2.185 as the assist ion beam voltage increased from 250 to 350 V, but decreased as the assist ion beam voltage was further increased from 350 to 650 V.     

Production of CuInSe2 thin films by a sequential processes of evaporations and selenization

Thin films of copper indium diselenide (CuInSe₂) were prepared by selenization of CuInSe₂-Cu-In multilayered structure on glass substrate. The selenization procedure was carried out in a vapour of elemental selenium in a vacuum chamber. The obtained films were characterised by XRD and SEM measurements. The effects of substrate temperature on the structural, electrical and optical properties were studied. It was found that single phase CuInSe₂ thin films with significant adhesion to substrate can be produced by selenization of CuInSe₂-Cu-In multilayered structure at 450°C, when the first non single phase CuInSe₂ layer was deposited at substrate temperature of 400°C. The thin films were found to be direct band gap semiconductors with a band gap of 0.97 eV.     

rf-Magnetron sputter deposited ZrO2 dielectrics for metal-insulator-semiconductor capacitors

ZrO₂ gate dielectric thin films were deposited by radio frequency (rf)-magnetron sputtering, and its structure, surface morphology and electrical properties were studied. As the oxygen flow rate increases, the surface becomes smoother. The experimental results indicate that a high temperature annealing is desirable since it improves the electrical properties of the ZrO₂ gate dielectric thin films by decreasing the number of interfacial traps at the ZrO₂/Si interface. The carrier transport mechanism is dominated by the thermionic emission.     

Effect of chopping on the properties of bismuth oxide thin films

Nanocrystalline bismuth oxide thin films have been deposited by thermal oxidation, in air, of vacuum evaporated chopped bismuth thin films. The optical properties and adhesion have been studied. The oxidation temperature and duration were varied. As revealed by structural investigations, polycrystalline and multiphase bismuth oxide thin films were obtained. At all oxidation temperatures, monoclinic Bi₂O₃ is predominant. The films showed high transmittance in the visible range of spectrum. The direct band gap of the films obtained was between 2.78 eV and 3.04 eV. The refractive index observed is in the range 1.934 to 2.096. The adhesion of films was in the range 215 × 10² to 470 × 10² kgF/cm². The values are strongly influenced by the heat treatment characteristics. It was observed that chopping helps in improving the adhesion and increasing refractive index, packing density and band gap of bismuth oxide thin films. These bismuth oxide films can have potential use in optical waveguides.     

Properties of nanocrystalline zinc oxide thin films prepared by thermal decomposition of electrodeposited zinc peroxide

Zinc peroxide thin films were electrodeposited from aqueous solution at room temperature using H₂O₂ as the oxidation agent. Nanocrystalline zinc oxide thin films were then obtained from thermal decomposition of zinc peroxide thin films. The grain sizes of ZnO through thermal decomposition of ZnO₂ at 200 °C, 300 °C and 400 °C were estimated from the peak width of ZnO(110) obtained from X-ray diffraction and were 6.3 nm, 9.1 nm and 12.9 nm, respectively. The optical properties of zinc oxide thin films have been studied. The photoluminescence results indicate that ZnO thin films have low Stokes blue shift (about 110 meV) and low oxygen vacancies.     

Nanocrystalline SnO2 and Au:SnO2 thin films prepared by direct current magnetron reactive sputtering

Nanocrystalline pure and gold doped SnO₂(Au:SnO₂) films were prepared on unheated glass substrates by dc magnetron reactive sputtering and, subsequently, the as deposited films were annealed in air. The films structure, surface morphology, photoluminescence, electrical and optical properties were investigated. After annealing the as deposited SnO₂ films, crystallinity increased and the surface roughness decreased. The intensity of PL peaks increases sharply with the annealing temperature. The optical transmittance of the films was around 89% after annealing the as deposited SnO₂ films at 450 °C. The as deposited Au:SnO₂ films show better crystallinity than the as deposited SnO₂ films, the average grain size was around 4.4 nm. The emission peaks of Au:SnO₂ films are slightly blue shifted as compare to undoped SnO₂ films. The Au:SnO₂ films show the lowest electrical resistivity of 0.001 Ωcm with optical transmittance of 76%, after annealing at 450 °C.     

Preparation of Zr1−x AlxO2 by annealing of ZrOx/Al thin films in the air atmosphere

Preparation of Zr_1−xAl_xO₂ by annealing of ZrO_x/Al thin layers in the reactive medium is presented in this work. At first ZrO_x thin films were deposited by reactive cathodic arc evaporation. Cathodic arc evaporation is the most versatile PVD coating technology. The process uses arc evaporation to create highly ionized plasma. It allows the “droplets” to escape into the coating under special condition in the chamber. After complete analysis of the process of arc deposition, ZrO_x thin films with thickness of ∼600 nm were deposited on Al₂O₃ and quartz substrates. Using vaporization on ZrO_x thin films 10% mol of Al was deposited and these ZrO_x/Al thin films were annealed at 500–900 °C in the air medium. The Zr_0.9Al_0.1O₂ thin films with nanocrystallite and two phases, monoclinic and cubic, were produced using the above-mentioned technique. The structure and optical properties of films were investigated by XRD, ellipsometry, photospectometry, respectively.     

Role of oxygen in enhancing N-type conductivity of CuInS2 thin films

Post-growth treatments in air atmosphere were performed on CuInS₂ films prepared by the single-source thermal evaporation method. Their effect on the structural, optical and electrical properties of the films was studied by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), optical reflection and transmission and resistance measurements. The films were annealed from 100 to 350 °C in air. The stability of the observed N-type conductivity after annealing depends strongly on the annealing temperature. Indeed it is shown that for annealing temperatures above 200 °C the N-type conductivity is stable. The resistance of the N-CuInS₂ thin films correlates well with the corresponding annealing temperature. The samples after annealing have direct bandgap energies of 1.45-1.50 eV.