Properties of a-C:H films deposited from a methane electron cyclotron wave resonant plasma

An electron cyclotron wave resonant methane plasma discharge was used for the high rate deposition of hydrogenated amorphous carbon (a-C:H). Deposition rates of up to ∼400 Å/min were obtained over substrates up to 2.5 in. in diameter with a film thickness uniformity of ∼±10%. The deposited films were characterised in terms of their mass density, sp3 and hydrogen contents, C-H bonding, intrinsic stress, scratch resistance and friction properties. The deposited films possessed an average sp3 content, mass density and refractive index of ∼58%, 1.76 g/cm3 and 2.035 respectively.Mechanical characterisation indicated that the films possessed very low steady-state coefficients of friction (ca. 0.06) and a moderate shear strength of ∼141 MPa. Nano-indentation measurements also indicated a hardness and elastic modulus of ∼16.1 and 160 GPa respectively. The critical loads required to induce coating failure were also observed to increase with ion energy as a consequence of the increase in degree of ion mixing at the interface. Furthermore, coating failure under scratch test conditions was observed to take place via fracture within the silicon substrate itself, rather than either in the coating or at the film/substrate interface. © 2003 Elsevier B.V. All rights reserved.

Nitrogen incorporation into tetrahedral hydrogenated amorphous carbon

Structural changes induced by the incorporation of nitrogen into ta-C : H films have been studied by Electron Energy Loss Spectroscopy, X-Ray Photoelectron Spectroscopy, Fourier Transformed Infrared Spectroscopy and Ultraviolet-Visible Spectroscopy. ta-C:H films have been synthesised using a low pressure Electron Cyclotron Wave Resonance (ECWR) source which provides a plasma beam with a high degree of ionisation and dissociation. Nitrogen was incorporated by adding N2 to the C2H2 plasma used for the deposition of ta-C : H films. The N/C atomic ratio in the films rises rapidly until the N2/C2H2 gas ratio reaches three, and then increases more gradually, while the deposition rate decreases steeply. Chemical sputtering of the forming films and the formation of molecular nitrogen within the films limit the maximum nitrogen content to about N/C = 0.6. For low nitrogen content the films retain their diamond-like properties, however as N/C atomic ratio increases, a polymeric-like material is formed, with >C=N- structures and terminating C=N and NH groups that decrease the connectivity of the network.

Hydrogen content estimation of hydrogenated amorphous carbon by visible Raman spectroscopy

In the present study, we report the hydrogen content estimation of the hydrogenated amorphous carbon (a-C:H) films using visible Raman spectroscopy in a fast and nondestructive way. Hydrogenated diamondlike carbon films were deposited by the plasma enhanced chemical vapor deposition, plasma beam source, and integrated distributed electron cyclotron resonance techniques. Methane and acetylene were used as source gases resulting in different hydrogen content and sp2/sp3 fraction. Ultraviolet-visible (UV-Vis) spectroscopic ellipsometry (1.5-5 eV) as well as UV-Vis spectroscopy were provided with the optical band gap (Tauc gap). The sp2/sp3 fraction and the hydrogen content were independently estimated by electron energy loss spectroscopy and elastic recoil detection analysis-Rutherford back scattering, respectively. The Raman spectra that were acquired in the visible region using the 488 nm line shows the superposition of Raman features on a photoluminescence (PL) background. The direct relationship of the sp2 content and the optical band gap has been confirmed. The difference in the PL background for samples of the same optical band gap (sp2 content) and different hydrogen content was demonstrated and an empirical relationship between the visible Raman spectra PL background slope and the corresponding hydrogen content was extracted. © 2004 American Institute of Physics.

Oxidative chemisorption of SO_2 on γ - Al_2O_3 and deposition of H_2-permselective SiO_2 films

The interaction of SO_2 with γ - Al_2O_3 and the deposition of H_2 permselective SiO_2 films have been investigated. The adsorption and oxidative adsorption of SO_2 on γ - Al_2O_3 have been examined at temperatures 500-700°C by Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). At temperatures above 500°C most of SO_2 adsorbed on the strong sites on alumina. The adsorbed SO_2 species was characterized by an IR band at 1065 cm^(-1). The equilibrium coverage and initial rate of adsorption decreased with temperature suggesting a two-step adsorption. When γ - Al_2O_3 was contacted with a mixture of SO_2 and O_2, adsorption of SO_2 and oxidation of the adsorbed SO_2 to a surface sulfate characterized by broad IR bands at 1070 cm^(-1), 1390 cm^(-1) took place. The results of a series of TGA experiments under different atmospheres strongly suggest that surface SO_2 and surface sulfate involve the same active sites such that SO_2 adsorption is inhibited by already formed sulfate. The results also indicate a broad range of site strengths.

The desorption of adsorbed SO_2 and the reductive desorption of oxidatively adsorbed SO_2 have been investigated by microreactor experiments and thermogravimetric analysis (TGA). Temperature programmed reduction (TPR) of adsorbed SO_2 showed that SO_2 was desorbed without significant reaction with H_2 when H_2 concentration was low while considerable reaction occurred when 100% H_2 was used. SO_2 adsorbed on the strong sites on alumina was reduced to sulfur and H_2S. The isothermal reduction experiments of oxidatively adsorbed SO_2 reveal that the rate of reduction is very slow below 550°C even with 100% H_2. The reduction product is mainly composed of SO_2. TPR experiments of oxidatively adsorbed SO_2 showed that H_2S arose from a sulfate strongly chemisorbed on the surface.

Films of amorphous SiO_2 were deposited within the walls of porous Vycor tubes by SiH_4 oxidation in an opposing reactants geometry : SiH_4 was passed inside the tube while O_2 was passed outside the tube. The two reactants diffused opposite to each other and reacted within a narrow front inside the tube wall to form a thin SiO_2 film. Once the pores were plugged the reactants could not reach each other and the reaction stopped. At 450°C and 0.1 and 0.33 atm of SiH_4 and O_2, the reaction was complete within 15 minutes. The thickness of the SiO_2 film was estimated to be about 0.1 µm. Measurements of H_2 and N_2 permeation rates showed that the SiO_2 film was highly selective to H_2 permeation. The H_2:N_2 flux at 450°C varied between 2000-3000.

Thin SiO_2 films were heat treated in different gas mixtures to determine their stability in functioning as high-temperature hydrogen-permselective membranes. The films were heat-treated at 450-700°C in dry N_2, dry O_2, N_2-H_2O, and O_2-H_2O mixtures. The permeation rates of H_2 and N_2 changed depending on the original conditions of film formation as well as on the heat treatment. Heating in dry N_2 slowly reduced the permeation rates of both H_2 and N_2. Heating in a N_2-H_2O atmosphere led to a steeper decline of H_2 permeability. But the permeation rate of N_2 increased or decreased according to whether the film deposition had been carried out in the absence or presence of H_2O vapor, respectively. Thermal treatment in O_2 caused rapid decline of the permeation rates of H_2 and N_2 in films that were deposited under dry conditions. The decline was moderate in films deposited under wet conditions.

Conduction through thin titanium dioxide films

Conduction through TiO₂ films of thickness 100 to 450 Å have been investigated. The samples were prepared by either anodization of Ti evaporation of TiO₂, with Au or Al evaporated for contacts. The anodized samples exhibited considerable hysteresis due to electrical forming, however it was possible to avoid this problem with the evaporated samples from which complete sets of experimental results were obtained and used in the analysis. Electrical measurements included: the dependence of current and capacitance on dc voltage and temperature; the dependence of capacitance and conductance on frequency and temperature; and transient measurements of current and capacitance. A thick (3000 Å) evaporated TiO₂ film was used for measuring the dielectric constant (27.5) and the optical dispersion, the latter being similar to that for rutile. An electron transmission diffraction pattern of a evaporated film indicated an essentially amorphous structure with a short range order that could be related to rutile. Photoresponse measurements indicated the same band gap of about 3 ev for anodized and evaporated films and reduced rutile crystals and gave the barrier energies at the contacts.

The results are interpreted in a self consistent manner by considering the effect of a large impurity concentration in the films and a correspondingly large ionic space charge. The resulting potential profile in the oxide film leads to a thermally assisted tunneling process between the contacts and the interior of the oxide. A general relation is derived for the steady state current through structures of this kind. This in turn is expressed quantitatively for each of two possible limiting types of impurity distributions, where one type gives barriers of an exponential shape and leads to quantitative predictions in c lose agreement with the experimental results. For films somewhat greater than 100 Å, the theory is formulated essentially in terms of only the independently measured barrier energies and a characteristic parameter of the oxide that depends primarily on the maximum impurity concentration at the contacts. A single value of this parameter gives consistent agreement with the experimentally observed dependence of both current and capacitance on dc voltage and temperature, with the maximum impurity concentration found to be approximately the saturation concentration quoted for rutile. This explains the relative insensitivity of the electrical properties of the films on the exact conditions of formation.

Optical properties and structure of Sb-rich AgInSbTe phase change thin films

A new composition content quaternary-alloy-based phase change thin film, Sb-rich AgInSbTe, has been prepared by DC-magnetron sputtering on a K9 glass substrate. After the film has been subsequently annealed at 200degreesC for 30 min, it becomes a crystalline thin film. The diffraction peak of antimony (Sb) are observed by shallow (0.5 degree) x-ray diffraction in the quaternary alloy thin film. The analyses of the measurement from differential scanning calorimetry (DSC) show that the crystallization temperature of the phase change thin film is about 190degreesC and increases with the heating rate. By Kissinger plot, the activation energy for crystallization is determined to be 3.05eV. The reflectivity, refractive index and extinction coefficient of the crystalline and amorphous phase change thin films are presented. The optical absorption coefficient of the phase change thin films as a function of photon energy is obtained from the extinction coefficient. The optical band gaps of the amorphous and crystallization phase change thin films are 0.265eV and 1.127eV, respectively.

Thermal, structural and optical properties of NiOx thin films deposited by reactive dc-magnetron sputtering

The NiOx thin films were deposited by reactive dc-magnetron sputtering from a nickel metal target in Ar + O-2 with the relative O-2 content 5%. The as-deposited NiOx, thin films could represent a two-component system comprising crystalline NiO particles dispersed in an amorphous Ni2O3. Decomposition temperature of the as-deposited NiO, thin films was at about 263 degrees C. After annealed at 400 degrees C for 30 min in air, the surface morphology of the films became very rough due to the decomposition of the Ni2O3, leading to the changes of the optical properties of the NiO, thin films. The reflectivity of the films annealed at 400 degrees C was lower than that of the as-deposited one and the optical contrast was 52% at 405 nm. (c) 2006 Elsevier B.V. All rights reserved.

SbOx thin films used for write-once blue laser recording

SbOx thin films are deposited by reactive dc-magnetron sputtering from all antimony metal target in Ar+O-2 with the relative O-2 content 7%. It is found that the as-deposited films call represent a two-component system comprising amorphous Sb and amorphous Sb2O3. The crystallization of Sb is responsible for the changes of optical properties of the films. The results of the static, test show that the SbOx thin films have good writing sensitivity for blue laser beams and the recording marks are very clear and circular. High reflectivity contrast of about 41% is obtained at a writing power 6 mW and writing pulse width 300 ns. In addition, the films show a good stability after reading 10000 times.