Evolution of optical properties with deposition time of silicon nitride and diamond-like carbon films deposited by radio-frequency plasma-enhanced chemical vapor deposition method

The paper presents investigations of the optical properties of thin high-refractive-index silicon nitride (SiN_x) and diamond-like carbon (DLC) films deposited by the radio-frequency plasma-enhanced chemical vapor deposition method for applications in tuning the functional properties of optical devices working in the infrared spectral range, e.g., optical sensors, filters or resonators. The deposition technique offers the ability to control the film's optical properties and thickness on the nanometer scale. We obtained thin, high-refractive-index films of both types at deposition temperatures below 350 °C, which is acceptable under the thermal budget of most optical devices. In the case of SiN_x films, it was found that for short deposition processes (up to 5 min long) the refractive index of the film increases in parallel with its thickness (up to 50 nm), while for longer processes the refractive index becomes almost constant. For DLC films, the effect of refractive index increase was observed up to 220 nm in film thickness.     

Spectrographic ellipsometry study of a liquid crystal display substrate consisting of thin films of SiO2, polyimide and indium tin oxide on glass

Variable angle spectrometric ellipsometry at room temperature is used to determine thin film parameters of substrates used in liquid crystal displays. These substrates consist of sequential thin films of polyimide (PI), on indium tin oxide (ITO),on SiO₂ deposited on a glass backing approximately 1.1 mm thick. These films were studied by sequentially examining more complex systems of films (SiO₂, SiO₂-ITO, SiO₂-ITO-PI). The SiO₂ layer appears to be optically uniform and flat. The ITO film is difficult to characterize. When this surface film's lower surface is SiO₂ and upper surface is an air-ITO-interface it is found that including surface roughness and variation of the optical properties with ITO thickness in the model improved the fit; suggesting that both phenomena exist in the ITO films. However, the surface roughness and graded nature of optical properties could be not determinable by ellipsometry when the ITO is coated with a polyimide film. The PI films are ellipsometrically flat and over the wavelength range from 500 to 1400 nm the real refractive index of polyimide films varying in thickness between 25 and 80 nm is well modeled by a two-term Cauchy model with no absorption. The ellipsometric thickness of the ITO layer is the same as the profilometric thickness; however, the ellipsometric thickness of the polyimide layers is roughly 10 nm larger than that obtained from the profilometer. These final observations are consistent with the literature.     

Influence of calcination ambient and film thickness on the optical and structural properties of sol-gel TiO2 thin films

Influence of both calcination ambient and film thickness on the optical and structural properties of sol-gel derived TiO₂ thin films have been studied. X-ray diffraction results show that prepared films are in an anatase form of TiO₂. Films calcined in argon or in low vacuum (∼2 × 10⁻¹ mbar) are found to be smaller in crystallite size, more transparent at low wavelength region of ∼300-450 nm, denser, have higher refractive index and band gap energy compared to air-calcined films. Scanning electron microscopic study reveals that surfaces of TiO₂ films calcined in argon or in low vacuum are formed by densely packed nano-sized particulates. Presence of voids and signs of agglomeration can be seen clearly in the surface microstructure of air-calcined films. In the thickness range ∼200-300 nm, band gap energy and crystallite size of TiO₂ films remain practically unaffected with film thickness but refractive index of thinner film is found to be marginally higher than that of thicker film. In this work, it has been shown that apart from temperature and soaking time, partial pressure of oxygen of the ambient is also an important parameter by which crystallite size, microstructure and optical properties of the TiO₂ films may be tailored during calcination period.     

Effect of the oxygen flow on the properties of ITO thin films deposited by ion beam assisted deposition (IBAD)

ITO films were deposited onto glass substrates by ion beam assisted deposition method. The oxygen ions were produced using a Kaufman ion source. The oxygen flow was varied from 20 until 60 sccm and the effect of the oxygen flow on properties of ITO films has been studied. The structural properties of the film were characterized by X-ray diffraction and atomic force microscopy. The optical properties were characterized by optical transmission measurements and the optical constants (refractive index n and extinction coefficient k) and film thickness have been obtained by fitting the transmittance using a semi-quantum model. The electrical properties were characterized by Hall effect measurements. It has been found that the ITO film with low electrical resistivity and high transmittance can be obtained with 40 sccm oxygen flow (the working pressure is about 2.3 × 10^− 2 Pa at this oxygen flow).     

Optical and structural properties of nanocrystalline anatase (TiO2) thin films prepared by non-aqueous sol-gel dip-coating

Anatase (TiO₂) thin films were grown by non-aqueous sol-gel dip-coating using titanium (IV) n-butoxide as precursor and 1-butanol as solvent. High withdrawal speed of 4.7 mm/s in dip-coating resulted in defect free films of 100 nm average film thickness after subsequent heat treatments. According to scanning electron microscope and X-ray diffraction measurements, the films consisted of nanocrystalline anatase with 30 nm mean crystallite size. Refractive index n(λ) and extinction coefficient k(λ) were determined over the wavelength range from 200 to 1650 nm. The optical band gap of the film material was approximately 3.2 eV. The results showed very similar optical characteristics to those that are accomplished with chemically more reactive aqueous sol-gel processes. Furthermore, it was found that in addition to porosity, coordination number of Ti atoms to nearest oxygen neighbors is likely to have a significant role in explaining differences of optical properties between bulk anatase and thin film materials of the present work.     

Ellipsometric studies on cupric telluride thin films

The optical properties of cupric telluride (CuTe) thin films have been studied in the wavelength range 310-800 nm using spectroscopic ellipsometry (SE). Thin films of thickness between 30 and 150 nm were prepared by thermal evaporation at the rate of 15.6 Å/s on well cleaned glass substrates kept at 300 K under the vacuum better than 2×10⁻⁵ mbar. It has been found that the optical band gap increases with the thickness of the films. The refractive index of the films increases with the energy but the extinction coefficient first increases and then decreases gradually with energy. The analysis of the absorption coefficient determined from the extinction coefficient reveals that there is allowed direct transition with a band gap of about 1.5 eV. The increase in the band gap with the increase in the film thickness has been ascribed to defect levels in the band gap formed by defects in the films.     

Influence of film thickness on the texture, morphology and electro-optical properties of indium tin oxide films

In the present study, the structural, electrical, and optical properties of indium tin oxide (ITO) films are reported as a function of film thickness (162-840 nm). The properties are discussed in terms of the (100) preferred orientation evolution with the increase of film thickness. This preferred orientation allowed accommodation of more oxygen vacancies, resulting in the increase of carrier concentration from 2.43 × 10²⁰ cm⁻³ to 7.11 × 10²⁰ cm⁻³ and therefore enhancing the electrical conductivity. The absorption in the infrared region was also found to increase with the increasing free carrier concentration, which was attributed to the plasma excitation. The X-ray photoelectron spectroscopy depth profile showed that the Sn⁴⁺ concentration did not change with film thickness. However, the oxygen concentration was decreased slightly after the thickness of the ITO films was increased to 100 nm, as the consequence of the formation of the (100) texture allowing the accommodation of more oxygen vacancies. The results show that the fabrication process can be manipulated to control the electrical properties and the infrared absorption of the sputtered ITO films.     

Structural and opto-electrical properties of the tin-doped indium oxide thin films fabricated by the wet chemical method with different indium starting materials

Tin-doped indium oxide (ITO) thin films were fabricated by the sol-gel spin-coating method with different indium precursor solutions synthesized from In(NO₃)₃ or InCl₃ (denoted as N-ITO and Cl-ITO, respectively). For both N-ITO and Cl-ITO thin films, the increase of mobility/conductivity and the reduction of carrier concentration with increasing annealing temperatures from 400 to 700 °C are related to the increase of crystallization/densification and the annihilation of oxygen vacancies. The refractive index (1.84 at λ = 550 nm), packing density (0.83), conductivity [(234 (Ω-cm)^− 1], and optical band gap (3.95 eV) of N-ITO thin films are higher than that of Cl-ITO thin films, which can be attributed to the higher densification, lower crystallinity, and more free charge carriers of N-ITO thin films. These properties make the indium nitrate-derived ITO thin films have better potential applications for some commercial products.     

Characterization of ITO/CdO/glass thin films evaporated by electron beam technique

A thin buffer layer of cadmium oxide (CdO) was used to enhance the optical and electrical properties of indium tin oxide (ITO) films prepared by an electron-beam evaporation technique. The effects of the thickness and heat treatment of the CdO layer on the structural, optical and electrical properties of ITO films were carried out. It was found that the CdO layer with a thickness of 25 nm results in an optimum transmittance of 70% in the visible region and an optimum resistivity of 5.1×10⁻³ Ω cm at room temperature. The effect of heat treatment on the CdO buffer layer with a thickness of 25 nm was considered to improve the optoelectronic properties of the formed ITO films. With increasing annealing temperature, the crystallinity of ITO films seemed to improve, enhancing some physical properties, such as film transmittance and conductivity. ITO films deposited onto a CdO buffer layer heated at 450 °C showed a maximum transmittance of 91% in the visible and near-infrared regions of the spectrum associated with the highest optical energy gap of 3.61 eV and electrical resistivity of 4.45×10⁻⁴ Ω cm at room temperature. Other optical parameters, such as refractive index, extinction coefficient, dielectric constant, dispersion energy, single effective oscillator energy, packing density and free carrier concentration, were also studied.     

Preparation of transparent conductive indium tin oxide thin films from nanocrystalline indium tin hydroxide by dip-coating method

Indium tin oxide (ITO) thin films with well-controlled layer thickness were produced by dip-coating method. The ITO was synthesized by a sol-gel technique involving the use of aqueous InCl₃, SnCl₄ and NH₃ solutions. To obtain stable sols for thin film preparation, as-prepared Sn-doped indium hydroxide was dialyzed, aged, and dispersed in ethanol. Polyvinylpyrrolidone (PVP) was applied to enhance the stability of the resulting ethanolic sols. The transparent, conductive ITO films on glass substrates were characterized by X-ray diffraction, scanning electron microscopy and UV-Vis spectroscopy. The ITO layer thickness increased linearly during the dipping cycles, which permits excellent controllability of the film thickness in the range ~ 40-1160 nm. After calcination at 550 °C, the initial indium tin hydroxide films were transformed completely to nanocrystalline ITO with cubic and rhombohedral structure. The effects of PVP on the optical, morphological and electrical properties of ITO are discussed.     

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.     

Structural, optical and electrical peculiarities of r.f. plasma sputtered indium tin oxide films

In this work the influence of the deposition conditions on the structural, electrical and optical properties of the ITO films was studied. Films were deposited by r.f. plasma sputtering technique in Ar and varying Ar + O₂ gas mixtures, with and without substrate heating.Transmittance and reflectance of the films were measured in the range 350-2500 nm; the refractive index (n) and the extinction coefficient (k) were calculated by the spectral data simulation. The sheet resistance of the films was measured by four-point probe method. X-ray diffraction analysis was performed to study the texture of the films. Threshold behaviour was observed in the optical and electrical properties of ITO films deposited in Ar + O₂ atmosphere at a certain oxygen concentration determined by a fix combination of all other deposition conditions. A schematic diagram for the change of the film properties versus composition was suggested, which explains the obtained results.     

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.     

Influence of Au underlayer thickness on the electro-optical properties of ITO/Au layered films deposited by magnetron sputtering on unheated polycarbonate substrates

Transparent and conducting tin-doped indium oxide (ITO) and ITO/Au multilayered films were prepared on polycarbonate (PC) substrates by magnetron sputtering without intentional substrate heating. In order to consider the influence of the Au thickness on the optoelectrical properties and structure of ITO/Au films, the thickness of the Au underlayer was varied from 5 to 20 nm. The optoelectrical properties of the films were quite dependent on the Au film thickness. The lowest sheet resistance of 11 Ω/sq. and an optical transmittance of 61% with respect to air was obtained from ITO (95 nm)/Au (5 nm) films. Thin film crystallinity was also affected by the presence of the Au underlayer and varied with the thickness of the Au films. In X-ray diffraction (XRD) spectra, ITO films did not show any characteristic diffraction peak, while ITO/Au films with a 5-nm Au underlayer showed a characteristic diffraction peak. From the figure of merit, it can be concluded that the most effective Au thickness in ITO/Au films is 5 nm.     

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.     

The growth of indium-tin-oxide thin films on glass substrates using DC reactive magnetron sputtering

The growth of indium-tin-oxide thin films as a function of thickness using DC reactive magnetron sputtering was investigated. As the film thickness grew, the crystallinity increased showing both (2 2 2) and (4 0 0) planes. However, the peak intensity ratio of I₂₂₂/I₄₀₀ in the X-ray diffraction pattern decreased with the thickness, implying a preferred orientation along the (4 0 0) planes at the higher thickness. The grain sizes and domain boundaries grew clearly and the specific resistivities decreased with the film thickness. Two components of the specific resistivities, carrier mobility and carrier concentration, showed opposite behaviour: (i) increasing carrier concentration; (ii) decreasing carrier mobility with increase in the film thickness. Furthermore, the graded growth of the ITO thin film could also be shown from the optical properties and morphological properties by UV/Vis/NIR spectroscopy and scanning electron microscopy.     

Optical properties of the c-axis oriented LiNbO3 thin film

C-axis oriented Lithium Niobate (LiNbO₃) thin films have been deposited onto epitaxially matched (001) sapphire substrate using pulsed laser deposition technique. Structural and optical properties of the thin films have been studied using the X-ray diffraction (XRD) and UV-Visible spectroscopy respectively. Raman spectroscopy has been used to study the optical phonon modes and defects in the c-axis oriented LiNbO₃ thin films. XRD analysis indicates the presence of stress in the as-grown LiNbO₃ thin films and is attributed to the small lattice mismatch between LiNbO₃ and sapphire. Refractive index (n = 2.13 at 640 nm) of the (006) LiNbO₃ thin films was found to be slightly lower from the corresponding bulk value (n = 2.28). Various factors responsible for the deviation in the refractive index of (006) LiNbO₃ thin films from the corresponding bulk value are discussed and the deviation is mainly attributed to the lattice contraction due to the presence of stress in deposited film.     

Characterization of nanocrystalline indium tin oxide thin films prepared by ion beam sputter deposition method

Indium tin oxide (ITO) thin films were deposited on glass substrates by ion beam sputter deposition method in three different deposition conditions [(i) oxygen (O₂) flow rate varied from 0.05 to 0.20 sccm at a fixed argon (1.65 sccm) flow rate, (ii) Ar flow rate changed from 1.00 to 1.65 sccm at a fixed O₂ (0.05 sccm) flow rate, and (iii) the variable parameter was the deposition time at fixed Ar (1.65 sccm) and O₂ (0.05 sccm) flow rates]. (i) The X-ray diffraction (XRD) patterns show that the ITO films have a preferred orientation along (400) plane; the orientation of ITO film changes from (400) to (222) direction as the O₂ flow rate is increased from 0.05 to 0.20 sccm. The optical transmittance in the visible region increases with increasing O₂ flow rate. The sheet resistance (R_s) of ITO films also increases with increasing O₂ flow rate; it is attributed to the decrease of oxygen vacancies in the ITO film. (ii) The XRD patterns show that the ITO film has a strong preferred orientation along (222) direction. The optical transmittance in the visible spectral region increases with an increase in Ar flow rate. The R_s of ITO films increases with increasing Ar flow rate; it is attributed to the decrease of grain size in the films. (iii) A change in the preferred orientations of ITO films from (400) to (222) was observed with increasing film thickness from 314 to 661 nm. The optical transmittance in the visible spectral region increases after annealing at 200 °C. The R_s of ITO film decreases with the increase of film thickness.     

Characterization of ITO/CdO/glass thin films evaporated by electron beam technique

Abstract

A thin buffer layer of cadmium oxide (CdO) was used to enhance the optical and electrical properties of indium tin oxide (ITO) films prepared by an electron-beam evaporation technique. The effects of the thickness and heat treatment of the CdO layer on the structural, optical and electrical properties of ITO films were carried out. It was found that the CdO layer with a thickness of 25 nm results in an optimum transmittance of 70% in the visible region and an optimum resistivity of 5.1×10^?3 Ω cm at room temperature. The effect of heat treatment on the CdO buffer layer with a thickness of 25 nm was considered to improve the optoelectronic properties of the formed ITO films. With increasing annealing temperature, the crystallinity of ITO films seemed to improve, enhancing some physical properties, such as film transmittance and conductivity. ITO films deposited onto a CdO buffer layer heated at 450 °C showed a maximum transmittance of 91% in the visible and near-infrared regions of the spectrum associated with the highest optical energy gap of 3.61 eV and electrical resistivity of 4.45×10^?4 Ω cm at room temperature. Other optical parameters, such as refractive index, extinction coefficient, dielectric constant, dispersion energy, single effective oscillator energy, packing density and free carrier concentration, were also studied.     

Optical and electrical characterization of r.f. sputtered ITO films developed as art protection coatings

Transparent and conductive tin-doped indium oxide (ITO) films have been prepared by r.f. plasma sputtering technique in Ar and Ar + O₂ gas mixture. The influence of the deposition conditions, film thickness, and substrate heating, as well as the post-annealing treatment on the optical and electrical properties of the ITO films has been investigated.The present study has extended the optical behaviour characterization of the ITO films in a wide UV-VIS-IR spectral region in addition to the comprehensive optical studies of this material at shorter wavelengths.The optical constants: refractive index (n), extinction (k) and absorption (α) coefficient, and the optical band gap (E_go) have been calculated for the ITO films in the spectral range between 350 and 2500 nm. A combination of several well-known theoretical models has been applied to describe precisely the complex optical behaviour of ITO films in separate spectral parts. In this approach, a good overlapping between the experimental and the simulated spectra in the whole investigated spectral region has been achieved.The deposition conditions and the optical and electrical properties of the ITO films have been optimized with respect to the requirements for their applications in art protection coatings.