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.     

Deposition of diamond-like carbon films on the inner surface of narrow stainless steel tubes

Diamond-like carbon (DLC) films were deposited on the inner surface of 304-type stainless steel tube with an inner diameter of 10 mm by DC glow discharge plasma. The influence of the deposition time, pressure and the ratios of CH₄ in CH₄/Ar gas mixture on the DLC film deposition were investigated. The images of Scanning Electron Microscopy (SEM) show that the DLC films are featureless and free of porosity. Fibre-like structure was recognized on the film surface by Atomic Force Microscopy (AFM). The film deposition rate decreases with increasing the deposition time. Relative higher deposition rate (40 nm/min) can be obtained at 20-30 Pa, higher and lower pressure will significantly decrease the deposition rate. Raman spectrum analysis shows that the films deposited in 30 min at 20-30 Pa have more sp³ content. The corrosion resistance of the films was measured by potentiodynamic polarization test. The DLC films deposited on the inner surface of the 304-type stainless steel tube significantly improve its corrosion resistance.     

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.     

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.     

Synthesis of functional diamond-like carbon nanocomposite films containing titanium dioxide nanoparticles

Synthesis of diamond-like carbon (DLC) films with UV-induced-hydrophilicity function was studied by inductively-coupled plasma (ICP) chemical vapor deposition. Titanium tetraisopropoxide (TTIP) and oxygen gases were employed as the precursors to deposit diamond-like nanocomposite films containing titanium dioxide (TiO₂) nanoparticles. X-ray diffraction and high-resolution transmission electron microscopy revealed that TiO₂ nanocrystallites were formed in the DLC films when oxygen concentration was higher than TTIP concentration during deposition. The DLC nanocomposite film was hydrophobic without ultraviolet (UV) irradiation, and became highly hydrophilic under UV irradiation, exhibiting the self-cleaning effect. A very broad peak centered at 1580 cm^− 1 was observed in the Raman spectra confirming the formation of DLC films. The hardness of the film was about 8 GPa with a stress of 3 GPa. ICP was essential in forming the photocatalytic TiO₂ nanoparticles in the DLC matrix.     

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.     

Dependence of optical and structural properties of ZnS and MgF2 multilayers as a function of the number of layers

In this paper, optical and structural properties of ZnS and MgF₂ multilayers grown by thermal evaporation are studied. Effects of annealing at different temperatures on samples with different number of layers are investigated. The maximum of reflection is shifted to different wavelengths, depending on the number of layers of the annealed samples. Using X-ray diffraction analysis, structural properties have been studied, and grain size and microstrain have been obtained by the Scherrer-Wilson formula, with grain sizes ranging from 10 nm to 22 nm for MgF₂ and from 0.9 nm to 210 nm for ZnS, and microstrain values from 2.5 × 10^− 3 to 3 × 10^− 3 for MgF₂, and from 1.2 × 10^− 3 to 2.6 × 10^− 3 for ZnS. Competition between crystallite size and microstrain is observed.     

Effect of annealing on optical properties of thin films with β-FeSi2 quantum dots

Reactive deposition epitaxy was used to prepare β-FeSi₂ nanodots on a Si(001) surface. The influence of annealing on optical properties has been studied. Annealing increases the particle size and decreases absorption. The indirect optical transition at 0.84-0.89 eV dominates the absorption spectra below 1.3-1.5 eV. The film with smaller nanoparticles exhibits higher absorption with direct optical transition energies in the 1.3-1.5 eV range. It suggests that direct transition is dominant only in small (around 3 nm diameter) β-FeSi₂ nanodots. Larger particles are dominated by the indirect optical transition.     

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.     

A comparative study on the NO2 gas sensing properties of ZnO thin films, nanowires and nanorods

ZnO thin films were fabricated using the spin coating method, ZnO nanowires by cathodically induced sol-gel deposition by the means of an anodic aluminum oxide (AAO) template, and ZnO nanorods with the hydrothermal technique. For thin film preparation, a clear, homogeneous and stable ZnO solution was prepared by the sol-gel method using zinc acetate (ZnAc) precursor which was then coated on a glass substrate with a spin coater. Vertically aligned ZnO nanowires which were approximately 65 nm in diameter and 10 μm in length were grown in an AAO template by applying a cathodic voltage in aqueous zinc nitrate solution at room temperature. For fabrication of the ZnO nanorods, the sol-gel ZnO solution was coated on glass substrate by spin coating as a seed layer. Then ZnO nanorods were grown in zinc nitrate and hexamthylenetetramine aqueous solution. The ZnO nanorods are approximately 30 nm in diameter and 500 nm in length. The ZnO thin film, ZnO nanowires and nanorods were characterized by X-ray diffraction (XRD) analysis and scanning electron microscope (SEM). The NO₂ gas sensing properties of ZnO thin films, nanowires and nanorods were investigated in a dark chamber at 200 °C in the concentration range of 100 ppb-10 ppm. It was found that the response times of both ZnO thin films and ZnO nanorods were approximately 30 s, and the sensor response was depended on shape and size of ZnO nanostructures and electrode configurations.     

The effects of plasma pre-treatment and post-treatment on diamond-like carbon films synthesized by RF plasma enhanced chemical vapor deposition

Diamond-like carbon (DLC) films were synthesized by RF plasma enhanced chemical vapor deposition and the effects of plasma pre-treatment and post-treatment on the DLC films were investigated. Experimental results show that the surface roughness of the substrate, ranging from 0.2 to 1.2 nm, created by the plasma pre-treatment, will affect the surface roughness of the DLC films deposited using methane as the carbon source. However, the film surface roughness (0.1-0.4 nm) is much smaller than that of the substrate. Raman analysis and hardness measurement by nanoindentation indicate that the structure and the hardness of the DLC films are relatively unchanged for the film surface roughness investigated. For the argon or hydrogen plasma post-treatment of the DLC films deposited using acetylene as the carbon source, it is found that surface roughness decreases with the post-treatment time. Although the hardness decreases after post-treatment, it remains relatively constant with increasing post-treatment time.     

Thin film growth of boron nitride on α-Al2O3 (0 0 1) substrates by reactive sputtering

Boron nitride thin films were grown on α-Al₂O₃ (0 0 1) substrates by reactive magnetron sputtering. Infrared attenuated total reflection (ATR) spectra of the films gave an intense signal associated with in-plane B-N stretching TO mode of short range ordered structure of BN hexagonal sheets. X-ray diffraction for the film prepared at a low working pressure (ca. 1 × 10⁻³ Torr) gave a diffraction peak at slightly lower angle than that corresponding to crystal plane h-BN (0 0 2). It is notable that crystal thickness calculated from X-ray peak linewidth (45 nm) was close to film thickness (53 nm), revealing well developed sheet stacking along the direction perpendicular to the substrate surface. When the substrates of MgO (0 0 1) and Si (0 0 1) were used, the short-range ordered structure of h-BN sheet was formed but the films gave no X-ray diffraction. The film showed optical band gap of 5.9 eV, being close to that for bulk crystalline h-BN.     

Growth of crystalline HgCr2S4 thin films at mild reaction conditions

Thin films of crystalline HgCr₂S₄ have been deposited on glass substrates at low temperature as low as 65 °C using a chemical bath deposition method. Typical thickness of the deposited HgCr₂S₄ thin films was 264 nm.The films were composed of closely packed irregular grains of 165-175 nm in diameter. The X-ray diffraction analysis and the selected area electron diffraction analysis revealed the deposited thin films were polycrystalline with highly (2 2 0) preferential orientation. The films exhibit a pure faint black. Their direct band gap energy was 2.39 eV with room temperature electrical resistivity of the order of 10⁻³ Ω cm.     

Ferroelectric properties of epitaxial Bi3.15Nd0.85Ti3O12 films on SiO2/Si using biaxially oriented MgO as templates

High quality epitaxial Bi_3.15Nd_0.85Ti₃O₁₂ (BNT) thin films with thicknesses from 30 to 80 nm have been integrated on SiO₂/Si substrates. MgO templates deposited by ion-beam-assisted deposition and SrRuO₃ (SRO) buffer layers processed by pulsed laser deposition have been used to initiate the epitaxial growth of BNT films on the amorphous SiO₂/Si substrates. The structural and ferroelectric properties were investigated. Microstructural studies by X-ray diffraction and transmission electron microscopy revealed high quality crystalline with an epitaxial relationship of (001)_BNT||(001)_SRO||(001)_MgO and [100]_BNT||[110]_SRO||[110]_MgO. A ferroelectric hysteresis loop with a remanent polarization of 3.1 μC/cm² has been observed for a 30 nm thick film. The polarization exhibits a fatigue-free characteristic up to 1.44 × 10¹⁰ switching cycles.     

Optical properties of thermochromic VO2 thin films on stainless steel: Experimental and theoretical studies

Thermochromic films of VO₂ were deposited by DC reactive magnetron sputtering on stainless steel substrate. Complex refractive indexes of VO₂ were determined by ellipsometric spectroscopy (0.35-16.5 μm) for different film thicknesses. Optical simulations were performed to model the spectral reflectance of the film/substrate system for a film thickness of 100 nm and 200 nm and to monitor the optical contrast of the thermochromic layers by comparing the spectral reflectance at 25 °C and 100 °C. The good agreement observed between experimental and theoretical spectra demonstrates the adequacy of the model for predicting the optical properties of the samples.     

The influence of fluorine doping on the optical properties of diamond-like carbon thin films

Optical properties of fluorine doped diamond-like carbon (F:DLC) films deposited by the direct current plasma enhanced chemical vapor deposition (PECVD) technique were studied in detail. Surface morphologies of the F:DLC films were studied by an atomic force microscope, which indicated surface roughness increased with increase in at.% of F in the films. The chemical binding was investigated by X-ray photoelectron spectroscopic studies. Fourier transformed infrared spectroscopic studies depicted the presence of CF_x (x = 1,2,3) and CH_n (n = 1,2) bonding within the F:DLC films. Optical transparency and the optical band gap decreased with the fluorine incorporation in the DLC film. Optical band gap calculated from the transmittance spectra decreased from 2.60 to 1.95 eV with a variation of 0-14.8 at.% of F concentration in the diamond-like carbon films. Urbach parameter determined from the band tail of the transmittance spectra showed that it increased with the doping concentration.     

Effect of composition on mechanical behaviour of diamond-like carbon coatings modified with titanium

In this study, diamond-like carbon (DLC) films modified with titanium were deposited by plasma decomposition of metallorganic precursor, titanium isopropoxide in CH₄/H₂/Ar gas atmosphere. The obtained films were composed of amorphous titanium oxide and nanocrystalline titanium carbide, embedded in an amorphous hydrogenated (a-C:H) matrix. The TiC/TiO₂ ratio in the DLC matrix was found to be dependent on the deposition parameters. The dependence of the films chemical composition on gas mixture and substrate temperature was investigated by X-ray photoelectron spectroscopy, whereas the crystallinity of TiC nanoparticles and their dimension were evaluated by X-ray diffraction. The size of TiC crystallites varied from 10 to 35 nm, depending on the process parameters. The intrinsic hardness of 10-13 GPa, elastic modulus of 170-200 GPa and hardness-to-modulus ratio of obtained coatings were measured by the nanoindentation technique. Obtained results demonstrated a correlation of mechanical properties with the chemical composition and the ratio of amorphous/crystalline phases in the films. In particular, the formation of nanocrystalline TiC with atomic concentration not exceeding 10% and with grain size between 10 nm and 15 nm resulted in significantly enhanced mechanical properties of composite material in comparison with ordinary DLC films.     

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.     

Magneto-optical Kerr-effect studies on copper oxide thin films produced by atomic layer deposition on SiO2

This work demonstrates the sensitivity of magneto-optical Kerr-effect (MOKE) spectroscopy to ultra-thin nonmagnetic films using the example of copper oxide. The films with an effective thickness between 0.6 nm and 6 nm are produced by atomic layer deposition (ALD) on silicon oxide substrates based on the Cu(I) β-diketonate precursor [(ⁿBu₃P)₂Cu(acac)] (acac = acetylacetonate) at a process temperature of 120 °C. The copper oxide films exhibit magneto-optical activity in the spectral ranges around 2.6 eV and above 4 eV. The evolution of the spectral features as a function of the number of ALD cycles is simulated numerically using the dielectric function and the Voigt constant of Cu₂O as input parameters. The comparison between experimental and simulated MOKE spectra strengthens the conclusion drawn from spectroscopic ellipsometry studies that the thin film optical constants differ markedly from the bulk ones.     

High-rate deposition of high-quality Sn-doped In2O3 films by reactive magnetron sputtering using alloy targets

Sn-doped In₂O₃ (ITO) films were deposited on heated (200 °C) fused silica glass substrates by reactive DC sputtering with mid-frequency pulsing (50 kHz) and a plasma control unit combined with a feedback system of the optical emission intensity for the atomic O* line at 777 nm. A planar In-Sn alloy target was connected to the switching unit, which was operated in the unipolar pulse mode. The power density on the target was maintained at 4.4 W cm^− 2 during deposition. The feedback system precisely controlled the oxidation of the target surface in “the transition region.” The ITO film with lowest resistivity (3.1 × 10^− 4 Ω cm) was obtained with a deposition rate of 310 nm min^− 1 and transmittance in the visible region of approximately 80%. The deposition rate was about 6 times higher than that of ITO films deposited by conventional sputtering using an oxide target.