Determination and analysis of dispersive optical constants of CuIn3S5 thin films

CuIn₃S₅ thin films were prepared from powder by thermal evaporation under vacuum (10⁻⁶ mbar) onto glass substrates. The glass substrates were heated from 30 to 200 °C. The films were characterized for their optical properties using optical measurement techniques (transmittance and reflectance). We have determined the energy and nature of the optical transitions of films. The optical constants of the deposited films were determined in the spectral range 300-1800 nm from the analysis of transmission and reflection data. The Swanepoel envelope method was employed on the interference fringes of transmittance patterns for the determination of variation of refractive index with wavelength. Wemple-Di Domenico single oscillator model was applied to determine the optical constants such as oscillator energy E₀ and dispersion energy E_d of the films deposited at different substrate temperatures. The electric free carrier susceptibility and the ratio of the carrier concentration to the effective mass were estimated according to the model of Spitzer and Fan.     

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

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

Infrared optical properties of Ba(Zr0.20Ti0.80)O3 and Ba(Zr0.30Ti0.70)O3 thin films prepared by sol-gel method

Ba(Zr_xTi_1−x)O₃ (BZT) (x = 0.20 and 0.30) thin films are deposited on Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrate by sol-gel method. X-ray diffraction patterns show that the thin films have a good crystallinity. Optical properties of the films in the wavelength range of 2.5-12 μm are studied by infrared spectroscopic ellipsometry (IRSE). The optical constants of the BZT thin films are determined by fitting the IRSE data using a classical dispersion formula. As the wavelength increases, the refractive index decreases, while the extinction coefficients increase. The effective static ionic charges are derived, which are smaller than that in a purely ionic material for the BZT thin films.     

Experimental determination of optical constants in the vacuum ultra violet wavelength region between 80 and 140 nm: A reflectance versus thickness method and its application to ZnSe

The 80-120 nm spectral range is a key domain for solar physics. Below 105 nm solids do not transmit light and the reflectance of available mirrors is particularly low which makes optical measurements specifically difficult. Optical constants of the materials may consequently be unavailable or unreliable.We present here a two media reflectance method at normal incidence suited to this VUV range, in which the variable is not the incidence angle but the thickness of the top layer made of the material to be analyzed. The real (n) and imaginary (k) parts of the complex index are directly and graphically determined in the (n, k) plane as the common intersection point of isoreflectance curves corresponding to samples different only in the thickness of the top layer.The method is tested and illustrated with ZnSe films evaporated on Al covered float glass substrates. In the literature, the reflectance magnitudes measured on ZnSe crystals differ strongly from an author to the other, leading to discrepant data for ZnSe in the VUV domain.We obtain precise and reliable values of (n, k), which fit the experimental values determined on freshly cleaved ZnSe crystals by J.L. Freeouf and the theoretical values calculated from the electronic band structure of ZnSe by John P. Walter and Marvin L. Cohen, but strongly differ from the optical constants selected by E.D. Palik in his tables.     

Influence of ZrO2 in HfO2 on reflectance of HfO2/SiO2 multilayer at 248 nm prepared by electron-beam evaporation

Influence of ZrO₂ in HfO₂ on the reflectance of HfO₂/SiO₂ multilayer at 248 nm was investigated. Two kinds of HfO₂ with different ZrO₂ content were chosen as high refractive index material and the same kind of SiO₂ as low refractive index material to prepare the mirrors by electron-beam evaporation. The impurities in two kinds of HfO₂ starting coating materials and in their corresponding single layer thin films were determined through glow discharge mass spectrum (GDMS) technology and secondary ion mass spectrometry (SIMS) equipment, respectively. It showed that between the two kinds of HfO₂, either the bulk materials or their corresponding films, the difference of ZrO₂ was much larger than that of the other impurities such as Ti and Fe. It is the Zr element that affects the property of thin films. Both in theoretical and in experimental, the mirror prepared with the HfO₂ starting material containing more Zr content has a lower reflectance. Because the extinction coefficient of zirconia is relatively high in UV region, it can be treated as one kind of absorbing defects to influence the optical property of the mirrors.     

Determination and analysis of dispersive optical constant of TiO2 and Ti2O3 thin films

Electron beam evaporation technique was used to prepare TiO₂ and Ti₂O₃ thin films onto glass substrates of thicknesses 50, 500 and 1000 nm for each sample. The structural investigations revealed that the as-deposited films are amorphous in nature. Transmittance measurements in the wavelength range (350-2000 nm) were used to calculate the refractive index n and the absorption index k using Swanepoel's method. The optical constants such as optical band gap , optical conductivity σ_opt, complex dielectric constant, relaxation time τ and dissipation factor tan δ were determined. The analysis of the optical absorption data revealed that the optical band gap E_g was indirect transitions. The optical dispersion parameters E_o and E_d were determined according to Wemple and Didomenico method.     

Optical and electrical properties of thermally evaporated In49Se48Sn3 films

Nearly stoichiometric thin films of In₄₉Se₄₈Sn₃ were deposited at room temperature, by conventional thermal evaporation of the presynthesized materials, onto precleaned glass substrates. The microstructural studies on the as-deposited and annealed films, using transmission electron microscopy and diffraction (TEMD), revealed that the as-deposited films are amorphous in nature, while those annealed at 498 K are crystalline. The optical properties of the investigated films were determined from the transmittance and reflectance data, in the spectral range 650-2500 nm. An analysis of the optical absorption spectra revealed a non-direct energy gap characterizing the amorphous films, while both allowed and forbidden direct energy gaps characterized the crystalline films. The electrical resistance of the deposited films was carried out during heating and cooling cycles in the temperature range 300-600 K. The results show an irreproducible behavior, while after crystallization the results become reproducible. The analysis of the temperature dependence of the resistance (ln(R) vs. 1000/T) for crystalline films shows two straight lines corresponding to both extrinsic and intrinsic conduction. The room temperature I-V characteristics of the as-deposited films sandwiched between similar Ag metal electrodes shows an ohmic behavior, while non-ohmic behavior attributed to space charge limited conduction has been observed when the films are sandwiched between dissimilar Ag/Al metal electrodes.     

Correlation between microstructure and optical properties of nano-crystalline TiO2 thin films prepared by sol-gel dip coating

Titanium dioxide thin films have been prepared from tetrabutyl-orthotitanate solution and methanol as a solvent by sol-gel dip coating technique. TiO₂ thin films prepared using a sol-gel process have been analyzed for different annealing temperatures. Structural properties in terms of crystal structure were investigated by Raman spectroscopy. The surface morphology and composition of the films were investigated by atomic force microscopy (AFM). The optical transmittance and reflectance spectra of TiO₂ thin films deposited on silicon substrate were also determined. Spectroscopic ellipsometry study was used to determine the annealing temperature effect on the optical properties and the optical gap of the TiO₂ thin films. The results show that the TiO₂ thin films crystallize in anatase phase between 400 and 800 °C, and into the anatase-rutile phase at 1000 °C, and further into the rutile phase at 1200 °C. We have found that the films consist of titanium dioxide nano-crystals. The AFM surface morphology results indicate that the particle size increases from 5 to 41 nm by increasing the annealing temperature. The TiO₂ thin films have high transparency in the visible range. For annealing temperatures between 1000 and 1400 °C, the transmittance of the films was reduced significantly in the wavelength range of 300-800 nm due to the change of crystallite phase and composition in the films. We have demonstrated as well the decrease of the optical band gap with the increase of the annealing temperature.     

Structure, electrical and optical properties of TiNx films by atmospheric pressure chemical vapor deposition

Titanium nitride (TiN_x) films with various nitride compositions (x) were prepared on glass substrates by atmospheric pressure chemical vapor deposition using TiCl₄ and NH₃ as precursors. The structural, compositional, electrical and optical properties of the films were studied and the results were discussed with respect to nitride composition. The results showed a linear relationship between the lattice constant and the nitride composition. Resistivity of the films was minimized near x = 1. All the TiN_x films exhibited a transmission band with a peak value of about 15% in the visible region (400-700 nm). As the wavelength increased to transition point (λ_T-R), the reflectance of the obtained films presented a sharp increase and then reached a high value of about 50% near 2000 nm. Moreover, the red-shift of transmission band and the transition wavelength (λ_T-R) with increasing the nitride composition were also discussed.     

Visible photocurrent response of TiO2 anode

The photoelectrochemical response to the electromagnetic radiation over the visible range is particularly sought for from the point of view of the efficiency of hydrogen generation by water photolysis in a photoelectrochemical solar cell, PEC. The PEC used in this work comprises thin film TiO₂ - based photoanode, Pt foil covered with Pt black as a cathode and SCE as a reference electrode, immersed in an electrolyte solution. Titanium dioxide thin films are deposited by means of rf reactive sputtering and modified, when necessary, by Au or Ag ultra-thin overcoatings. Here we show that even unmodified TiO₂ photoanode, shows a photocurrent peak over the visible range of the light spectrum (λ = 500-650 nm). The effect of the surface modification by noble metals and properties of the aqueous electrolyte on the visible photocurrent are studied. The optical spectra indicate an increased absorption due to noble metal deposits at 410 nm for Ag and at 600 nm for Au. In contrast, the photocurrent peak over the visible range (500 nm < λ < 650 nm) changes its symmetry and decreases in intensity with the increasing thickness of noble metals layers. The visible photoresponse is explained in terms of OH formation at the interface between TiO₂ electrode and aqueous electrolyte.     

The ferroelectric and ferromagnetic characterization of CoFe2O4/Pb(Mg1/3Nb2/3)O3-PbTiO3 multilayered thin films

The multiferroic (PMN-PT/CFO)_n (n = 1,2) multilayered thin films have been prepared on SiO₂/Si(1 0 0) substrate with LNO as buffer layer via a rf magnetron sputtering method. The structure and surface morphology of multilayered thin films were determined by X-ray diffraction (XRD) and atom force microscopy (AFM), respectively. The smooth, dense and crack-free surface shows the excellent crystal quality with root-mean-square (RMS) roughness only 2.9 nm, and average grain size of CFO thin films on the surface is about 44 nm. The influence of the thin films thickness size, periodicity n and crystallite orientation on their properties including ferroelectric, ferromagnetic properties in the (PMN-PT/CFO)_n multilayered thin films were investigated. For multilayered thin films with n = 1 and n = 2, the remanent polarization Pr are 17.9 μC/cm² and 9.9 μC/cm²; the coercivity H_c are 1044 Oe and 660 Oe, respectively. In addition, the relative mechanism are also discussed.     

Microstructural, optical and photocatalytic properties of CdS doped TiO2 thin films

CdS doped TiO₂ thin films (with CdS content=0, 3, 6, 9 and 12 at%) were grown on glass substrates. The X-ray diffraction analysis revealed that the films are polycrystalline of monoclinic TiO₂ structure. The microstructure parameters of the films such as crystallite size (D_ν) and microstrain (e) are calculated. Both the crystallites size and the microstrain are decreased with increasing CdS content. The optical constants have been determined in terms of Murmann's exact equations. The refractive index and extinction coefficient are increased with increasing CdS content. The optical band gap is calculated in the strong absorption region. The possible optical transition in these films is found to be an allowed direct transition. The values of E_g^opt are found to decrease as the CdS content increased. The films with 3 at% CdS content have better decomposition efficiency than undoped TiO₂. The films with 6 at% and 9 at% CdS content have decomposition efficiency comparable to that of undoped TiO₂, although they have lower band gap. The CdS doped TiO₂ could have a better impact on the decomposing of organic wastes.     

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

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

Effect of annealing temperature on the optical and electrical properties of amorphous As45.2Te46.6In8.2 thin films

The optical absorption of the As-prepared and annealed As_45.2Te_46.6In_8.2 thin films are studied. Films annealed at temperatures higher than 453 K show a decrease in the optical energy gap (E_o). The value of E_o increases from 1.9 to 2.43 eV with increasing thickness of the As-prepared films from 60 to 140 nm. The effect of thickness on high frequency dielectric constant (?_∞) and carrier concentration (N) is also studied. The crystalline structures of the As_45.2Te_46.6In_8.2 thin films resulting from heat treatment of the As-prepared film at different elevated temperatures is studied by X-ray diffraction. An amorphous-crystalline transformation is observed after annealing at temperatures higher than 453 K. The electrical conductivity at low temperatures is found due to the electrons transport by hopping among the localized states near the Fermi level. With annealing the films at temperatures higher than 473 K (the crystallization onset temperature) for 1 h, the electrical conductivity increases and the activation energy decreases, which can be attributed to the amorphous-crystalline transformations.     

Switching phenomenon and optical properties of Se85Te10Bi5 films

Se₈₅Te₁₀Bi₅ films of different thicknesses ranging from 126 to 512 nm have been prepared. Energy-dispersive X-ray (EDX) spectroscopy technique showed that films are nearly stoichiometric. X-ray diffraction (XRD) measurements have showed that the Se₈₅Te₁₀Bi₅ films were amorphous. Electrical conduction activation energy (ΔE_σ) for the obtained films is found to be 0.662 eV independent of thickness in the investigated range. Investigation of the current voltage (I-V) characteristics in amorphous Se₈₅Te₁₀Bi₅ films reveals that it is typical for a memory switch. The switching voltage V_th increases with the increase of the thickness and decreases exponentially with temperature in the range from 298 to 383 K. The switching voltage activation energy (ε) calculated from the temperature dependence of V_th is found to be 0.325 eV. The switching phenomenon in amorphous Se₈₅Te₁₀Bi₅ films is explained according to an electrothermal model for the switching process. The optical constants, the refractive index (n) and the absorption index (k) have been determined from transmittance (T) and reflectance (R) of Se₈₅Te₁₀Bi₅ films. Allowed non-direct transitions with an optical energy gap (E_g^opt) of 1.33 eV have been obtained. ΔE_σ is almost half the obtained value of E_g^opt, which suggested band to band conduction as indicated by Davis and Mott.     

The effect of Ag addition on the optical properties of Se90Te10 films

Se₉₀Te_10−xAg_x (0 ≤ x ≤ 6) compositions were prepared by quenching technique. Thin films with different thicknesses of the obtained compositions were deposited on dry clean glass substrates by thermal evaporation technique. Energy dispersive X-ray spectroscopy (EDX) indicates that samples are nearly stoichiometric. X-ray diffraction patterns indicate that they are in the amorphous state. The optical constants, the refractive index n and the absorption index k, have been calculated from transmittance T and reflectance R through the spectral range of 400-2500 nm for the studied films with different thicknesses (165-711 nm). From the analysis of refractive index n data, high frequency dielectric constant ?_∞ was determined. Both ?_∞ and n are found to decrease with the increase of Ag content. The optical band gap is calculated for all compositions from the absorption coefficient analysis. The effect of the Ag addition on the obtained optical parameters has been discussed. The analysis of absorption index k data, revealed the existence of allowed indirect transitions for all compositions. It is indicated also that increase with increasing Ag content.     

Effect of Ga addition on optical properties of crystalline Ga20Se80 system

Ga_xSe_100−x (20 ≤ x ≤ 50) in polycrystalline form was prepared by direct fusion of stoichiometric proportions of pure elements. The spectral behavior of transmittance (T) and the reflectance (R) in the wavelength range 400–2500 nm for all films of different thicknesses were measured to obtain different optical parameters (refractive index, n, and absorption index, k). The study of inter-band transitions indicates that the existence of direct forbidden transitions and indirect forbidden transitions with energy gaps decrease with increasing Ga percentage.     

Derivation of the optical constants of spin coated CeO2-TiO2-ZrO2 thin films prepared by sol-gel route

Ternary thin films of cerium titanium zirconium mixed oxide were prepared by the sol-gel process and deposited by a spin coating technique at different spin speeds (1000-4000 rpm). Ceric ammonium nitrate, Ce(NO₃)₆(NH₄)₂, titanium butoxide, Ti[O(CH₂)₃CH₃]₄, and zirconium propoxide, Zr(OCH₂CH₂CH₃)₄, were used as starting materials. Differential calorimetric analysis (DSC) and thermogravimetric analysis (TGA) were carried out on the CeO₂-TiO₂-ZrO₂ gel to study the decomposition and phase transition of the gel. For molecular, structural, elemental, and morphological characterization of the films, Fourier Transform Infrared (FTIR) spectral analysis, X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS), cross-sectional scanning electron microscopy (SEM), and atomic force microscopy (AFM) were carried out. All the ternary oxide thin films were amorphous. The optical constants (refractive index, extinction coefficient, band gap) and thickness of the films were determined in the 350-1000 nm wavelength range by using an nkd spectrophotometer. The refractive index, extinction coefficient, and thickness of the films were changed by varying the spin speed. The oscillator and dispersion energies were obtained using the Wemple-DiDomenico dispersion relationship. The optical band gap is independent of the spin speed and has a value of about E_g≈2.82±0.04 eV for indirect transition.     

FTIR sensitivity enhancement on Pt/SiO2/Au layered structures: A novel method for CO adsorption studies on Pt surfaces

Specular reflectance FTIR study of carbon monoxide adsorbed on platinum is performed on Pt/SiO₂/Au layered structures prepared by deposition of thin films on silicon (1 0 0) wafers. The layered structures consist of 5 nm thick platinum films over SiO₂ films of varying thicknesses with 50 nm thick reflecting gold films underneath. Due to optical interference effects, the reflectance of each of these structures varies with the incident infrared wavelength and goes through a minimum at a wavelength that depends on the thickness of the SiO₂ layer. The decrease in the reflectance R causes an effective increase in the ΔR/R value resulting in a large increase in the infrared absorption band intensity of linearly-adsorbed CO. The peak height changes with changing the SiO₂ thickness in the structures and is greatest for the sample which has lowest reflectance near the absorption wavelength of CO (∼2100 cm⁻¹). This improvement in the ratio of FTIR signal to background reflectance can be very useful for probing low surface area model catalytic surfaces at atmospheric pressures and under reaction conditions. A spectrum of CO adsorbed on nanofabricated Pt nanowire catalysts on TiO₂ support is also shown as an example of the sensitivity enhancement on layered structures.