Characterisation of SiOxCyHz thin films deposited by low-temperature PECVD

SiO_xC_yH_z thin films were deposited from hexamethyldisiloxane (HMDSO)/O₂ mixtures in a parallel plate, capacitively coupled, RF plasma reactor. Polyethylene terephthalate (PET), Si(1 0 0) wafers and KBr tablets were chosen as substrates. Effect of HMDSO/O₂ ratio, total treatment pressure and power input on the properties of the deposited films were investigated. The structure and bondings were studied by means of Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. Wettability characteristics of the deposited thin films were investigated by means of water droplet contact angle measurements. Surface morphology was investigated with atomic force microscopy. Barrier properties of the SiO_xC_yH_z thin films were investigated by measuring the water vapour transmission rate of the coated PET substrates. Correlations between the characteristics of the deposited film and their barrier properties were discussed.     

Optical characterization of vacuum evaporated a-Se80Te20−xCux thin films

Thin films of a-Se₈₀Te_20−xCu_x (where x=2, 6, 8 and 10) were deposited on glass substrates by vacuum evaporation technique. The absorbance, reflectance and transmittance of as-deposited thin films were measured in the wavelength region 400-1000 nm. The optical band gap and optical constants of amorphous thin films have been studied as a function of photon energy. The optical band gap increases on incorporation of copper in Se₈₀Te_20−xCu_x system. The value of refractive index (n) decreases while the value of the extinction coefficient (k) increases with increasing photon energy. The results are interpreted in terms of concentration of localized states.     

Optical and chemical characterization of thin TiNx films deposited by DC-magnetron sputtering

Thin titanium nitride (TiN_x) films were deposited on silicon substrates by means of a reactive DC-magnetron plasma. Layers were synthesized under various conditions of discharge power and nitrogen flows in two operation modes of the magnetron (the so-called “balanced” and “unbalanced” modes). The optical constants of the TiN_x films were investigated by spectroscopic ellipsometry (SE). X-ray photoelectron spectroscopy (XPS) was used to determine the relative atomic concentration and chemical states of the TiN_x films. The density and thickness of the films have been investigated by means of grazing incidence X-ray reflectometry (GIXR). The results of the layer analyses were combined with plasma investigations carried out by means of energy resolved mass spectrometry (ERMS) under the same conditions. It is shown that the magnetron mode has a clear influence on the titanium deposition rate and the incorporation of nitrogen into the layers.     

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

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

XPS analysis of WxCy thin films prepared by sputter deposition

W_xC_y thin films with different compositions were studied in order to correlate their properties with the thin-film composition and chemical bonding of C and W atoms. Three W_xC_y thin films with C concentrations in the range 40-80 at% were deposited on WC-Co substrates by the plasma beam sputtering technique. The composition of the thin films and chemical states of elements were analysed by X-ray photoelectron spectroscopy (XPS) depth profiling. The C and W concentrations in the films were quantified using XPS intensities from a WC-Co substrate with a known composition. The C1s peaks in the high energy resolution XPS spectra of thin films allowed identification of the WC phase and the amorphous carbon phase as a function of the film composition. The results show that the amorphous carbon a-C phase is present in those films with composition x<y. The measured hardness of the films decreases with a decrease of the WC concentration.     

Effects of TeOx films on temperature coefficients of delay of Love-type wave devices based on TeOx/36°YX-LiTaO3 structures

Tellurium oxide (TeO_x) thin films are prepared on 36°YX-LiTaO₃ substrates by RF magnetron sputtering technique under different deposition conditions. The structures and compositions of the TeO_x films are analyzed by X-ray diffraction, Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy, which show that the TeO_x films are amorphous and with different ratios of Te to O prepared in different conditions. Then the Love-type wave devices based on TeO_x/36°YX-LiTaO₃ structures are fabricated, and the temperature coefficient of delay (TCD) of the Love-type wave devices are investigated. The results show that, when TeO_x films deposited at suitable deposition conditions, the TCD of the Love-type wave devices are less than that of the shear-horizontal (SH) wave devices fabricated on the bare 36°YX-LiTaO₃ substrates, which demonstrates that the TCD of the TeO_x films is negative. Moreover, the TCD of the devices are strongly dependent upon the preparation conditions and the thicknesses of the TeO_x films. Therefore, the TCD of the Love-type wave devices can be optimized by suitably selecting the preparation conditions and the thickness of TeO_x films.     

Sputter-assisted plasma CVD of polymer-like amorphous CNx:H films using supermagnetron plasma

By using a sputter-assisted chemical vapor deposition (CVD) of supermagnetron plasma, amorphous CN_x:H films were deposited on the lower part of two parallel electrodes. By applying rf power to the upper electrode (UPRF) at 5 W to 800 W, polymer-like a-CN_x:H films were deposited on substrates placed on the lower electrode with an rf power (LORF) of 10 W. The deposition rate increased as UPRF increased. The hardness was as low as about 6.5 GPa, which is less than that of glass (13.1 GPa). The refractive index changed only slightly as UPRF changed from 1.6 to 1.75. The FT-IR spectrum showed strong absorption bands of NH and CH bonds at high and low UPRFs, respectively. The optical band gap was as large as 2.1 to 2.5, and it decreased as UPRF increased. These a-CN_x:H films showed white photoluminescence (PL) with broadband. With the increase of UPRF from 5 W to 800 W, the PL peak energy shifted down from 2.3 eV to 1.9 eV.     

SiOx-doped DLC films: Charge transport, dielectric properties and structure

In the present study, SiO_x-doped diamond-like carbon (DLC) films were synthesized by ion beam deposition on different substrates. Electrical properties, morphology and structure of the DLC films were investigated. Poole-Frenkel emission was the main carrier transport mechanism in all investigated metal-SiO_x-doped DLC-metal samples. Dielectric properties of the samples were dependent on both the bottom and top electrode metal. The trans-polyacetylene chain vibrations detected from the Raman spectra have been observed for all the SiO_x-doped DLC films. Different dielectric properties of the film deposited onto the different metal interlayers were explained both by different roughness of the metal films and by different structure of the ion beam-synthesized SiO_x-doped DLC films.     

Mechanical and environmental properties of Ge1−xCx thin film

Ge_1−xC_x thin film was prepared by plasma-enhanced chemical vapor deposition (PECVD) using GeH₄ and CH₄ as precursors and its mechanical and environmental properties were investigated. The samples were measured by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectrum, FT-IR spectrometer, WS-92 testing apparatus of adhesion and FY-03E testing apparatus of salt and fog. The results show that the infrared refractive index of Ge_1−xC_x thin film varies from 2 to 4 with different x values. The adhesion increases with increasing gas flow ratio of GeH₄/CH₄ and decreases with increasing film thickness. The nanoindentation hardness number decreases with increasing germanium content. Three series films exhibit the best anti-corrosion property when the RF power is about 80 W, or substrate temperature is about 150 °C, or DC bias is about −100 V. Furthermore, increasing the gas flow ratio of GeH₄/CH₄ improves the anti-corrosion property of these films.     

Effect of the oxygen fraction on the structure and optical properties of HfOxNy thin films

The main purpose of this work was to prepare hafnium oxynitride (HfO_xN_y) thin films. HfO_xN_y thin films were deposited by radio frequency reactive magnetron sputtering from a pure Hf target onto Quartz and ZnS substrates at room temperature. The depositions were carried out under an oxygen-nitrogen-argon atmosphere by varying the flow rate of the reactive gases (oxygen/nitrogen ratio). The variation of the flow rate of the reactive gases changed the structure and properties of the films. Glancing incidence X-ray diffraction (GIXRD) was used to study the structural changes of as-deposited films; a new crystalline hafnium oxynitride phase was formed in a region of oxygen/nitrogen ratio. Cross-section of the films observed by SEM revealed that the films grew with a columnar-type structure, and surface observation with AFM showed values of surface roughness changed with the flow rate of the reactive gases, higher oxygen fraction had lower surface roughness than lower oxygen fraction. Visible spectra, infrared spectra, refractive index, absorption coefficient also changed with the variation of the oxygen fraction.     

Supermagnetron plasma CVD of highly effective a-CNx:H electron-transport and hole-blocking films suited to Au/a-CNx:H/p-Si photovoltaic cells

Hydrogenated carbon nitride (a-CN_x:H) films (0-500 nm) were deposited on p-Si wafers to make Au/a-CN_x:H/p-Si photovoltaic cells using i-C₄H₁₀/N₂ supermagnetron plasma chemical vapor deposition. At a lower electrode RF power (LORF) of 50 W and an upper electrode RF power (UPRF) of 50-800 W, hard a-CN_x:H films with optical band gaps of 0.7-1.0 eV were formed. At a film thickness of 25 nm (UPRF of 500 W), the open circuit voltage and short circuit current density were 247 mV and 2.62 mA/cm², respectively. The highest energy conversion efficiency was 0.29%. The appearance of the photovoltaic phenomenon was found to be due to the electron-transport and hole-blocking effect of thin a-CN_x:H film.     

Bottom electrodes dependence of microstructures and dielectric properties of compositionally graded (Ba1−xSrx)TiO3 thin films

Compositionally graded (Ba_1−xSr_x)TiO₃ (BST) thin films, with x decreasing from 0.3 to 0, were deposited on Pt/Ti/SiO₂/Si and Ru/SiO₂/Si substrates by radio frequency magnetron sputtering technology. The microstructure and dielectric properties of the graded BST thin films were investigated. It was found that the films on Ru electrode have better crystallization, and that RuO₂ is present between the Ru bottom electrode and the graded BST thin films by X-ray diffraction and SEM analysis. Dielectric measurement reveals that the graded BST thin films deposited on Ru bottom electrode have higher dielectric constant and tunability. The enhanced dielectric behavior is attributed to better crystallization as well as smaller space charge capacitance width and the formation of RuO₂ that is more compatible with the BST films. The graded BST films on Ru electrode show higher leakage current due to lower barrier height and rougher surface of bottom electrode.     

Compositional variation of refractive index and absorption edge parameters in Hf1−xTixO2 thin films

Experimental ellipsometric studies of Hf_1−xTi_xO₂ thin films were carried out to determine refractive indices as well as spectrometric studies of these films were carried out to determine interferential transmission spectra. The dispersion curves of the refractive indices are well described by the optical-refractometric relation. Compositional dependences of optical pseudogap and refractive indices of Hf_1−xTi_xO₂ thin films are investigated. Effect of compositional disordering on the optical absorption edge in Hf_1−xTi_xO₂ thin films is studied.     

Magnetron sputtering of TiOxNy films

This article reports on the characterization and preparation of N-doped titanium dioxide (TiO₂) films by reactive magnetron sputtering from Ti(99.5) targets in a mixture of Ar/O₂/N₂ atmosphere on unheated glass substrates. A dual magnetron system supplied by a dc bipolar pulsed power source was used to sputter the TiO_xN_y films. The amount of N in the TiO_xN_y film ranges from 5 to 40 at%. Its structure was measured using X-ray diffraction (XRD), the optical band gap was calculated from Tauc plots and the decrease of the water contact angle α_ir after the film activation by UV irradiation was investigated as a function of at% of N in the TiO_xN_y film. The yellow-coloured TiO_xN_y films with high (≈8 at%) amount of N exhibited a strong decrease of the band gap E_g down to 2.7 eV. A significant decrease of the water contact angle α_ir after UV irradiation has been observed for 2 μm thick transparent nanocrystalline (anatase+rutile) N-doped TiO₂ films containing less than 6 at% of N.     

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

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

The influence of post deposition plasma treatment on SnOx structural properties

Thin tin-oxide (SnO_x) films were deposited by atmospheric pressure chemical vapor deposition (APCVD) and exposed to hydrogen plasma. The influence of such treatment on the films properties was investigated by X-ray diffraction (XRD), UV-visible spectroscopy, scanning electron microscopy (SEM), X-ray photoemission spectroscopy (XPS) and grazing incidence small angle X-ray scattering (GISAXS). XRD showed that the deposited films are nano-crystalline, with a typical average of the individual crystal sizes between 15 and 40 nm and with a preferred orientation, depending on the parameters of the deposition. By exposure to the hydrogen plasma the micro-strain increased, the crystals became smaller and less preferentially oriented. The influence of the hydrogen plasma treatment, studied by SEM and XPS, indicated that part of the surface layer was etched away, presumably through the process of SnO_x reduction. The GISAXS results suggested that the nano-crystals in as-deposited samples had the shape of non-truncated pyramids. After plasma treatment, their shape is greatly rounded and the GISAXS signal becomes isotropic.     

Optimization of n nc-Si:H and a-SiNx:H layers for their application in nc-Si:H TFT

The n-type doped silicon thin films were deposited by plasma enhanced chemical vapor deposition (PECVD) technique at high and low H₂ dilutions. High H₂ dilution resulted in n⁺ nanocrystalline silicon films (n⁺ nc-Si:H) with the lower resistivity (ρ ∼0.7 Ω cm) compared to that of doped amorphous silicon films (∼900 Ω cm) grown at low H₂ dilution. The change of the lateral ρ of n⁺ nc-Si:H films was measured by reducing the film thickness via gradual reactive ion etching. The ρ values rise below a critical film thickness, indicating the presence of the disordered and less conductive incubation layer. The 45 nm thick n⁺ nc-Si:H films were deposited in the nc-Si:H thin film transistor (TFT) at different RF powers, and the optimum RF power for the lowest resistivity (∼92 Ω cm) and incubation layer was determined. On the other hand, several deposition parameters of PECVD grown amorphous silicon nitride (a-SiN_x:H) thin films were changed to optimize low leakage current through the TFT gate dielectric. Increase in NH₃/SiH₄ gas flow ratio was found to improve the insulating property and to change the optical/structural characteristics of a-SiN_x:H film. Having lowest leakage currents, two a-SiN_x:H films with NH₃/SiH₄ ratios of ∼19 and ∼28 were used as a gate dielectric in nc-Si:H TFTs. The TFT deposited with the NH₃/SiH₄∼19 ratio showed higher device performance than the TFT containing a-SiN_x:H with the NH₃/SiH₄∼28 ratio. This was correlated with the N−H/Si−H bond concentration ratio optimized for the TFT application.     

Optical absorption behaviour of evaporated CuxS thin films

The optical absorption behaviour of thin films of copper sulphide (Cu_xS) formed by a vacuum deposition process at substrate temperatures of 27, 125 and 200°C was studied with a view to establishing a correlation with their structure. From the reflection and transmission data, the optical constants and the absorption coefficient were computed. Both the direct edge at 1.8 eV and the indirect edge at 0.855 eV, 1.075 eV and 1.105 eV respectively for these films were observed. These transitions explain the observed dependence of the absorption coefficient on the photon energy. The unusually high values of the absorption coefficient for the film deposited at room temperature were due to scattering-absorption and are explained on the basis of Maxwell Garnett theory. For Cu_xS compositions with 1.96 < x < 2.0, no changes in the direct edge were observed. The indirect edge shifts upwards by 0.22 eV when disordering of the copper sublattice occurs in the Cu₂S phase. The indirect transitions are associated with the changes in lattice structure and stoichiometry.     

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.     

Influence of the argon flow rate on the arsenic fraction of a-GaxAs1−x sputtered at high substrate temperature

The experimental study of the chemical composition of amorphous gallium arsenide (a-Ga_xAs_1−x) versus argon flow rate, Q, by rf sputtering, shows that the As fraction of sputtered films is controlled by the argon flow rate. At the substrate temperature, T_s=500 °C, the films are stoichiometric when deposited under the argon flow rate between 8 and 22 sccm. These observations indicate that at low argon flow rate the As fraction of films is governed only by the preferential re-sputtering of As during the film growth. In addition, a correlation between the deposition rate R, and chemical composition x was deduced from these results.