Diverse Amorphous Carbonaceous Thin Films Obtained by Plasma Enhanced Chemical Vapor Deposition and Plasma Immersion Ion Implantation and Deposition

Diverse amorphous hydrogenated carbon and similar films containing additional elements were produced by Plasma Enhanced Chemical Vapor Deposition (PECVD) and by Plasma Immersion Ion Implantation and Deposition (PIIID). Thus a-C:H, a-C:H:F, a-C:H:N, a-C:H:Cl and a-C:H:O:Si were obtained, starting from the same feed gases, using both techniques. The same deposition system supplied with radiofrequency (RF) power was used to produce all the films. A cylindrical stainless steel chamber equipped with circular electrodes mounted horizontally was employed. RF power was fed to the upper electrode; substrates were placed on the lower electrode. For PIIID negative high tension pulses were also applied to the lower electrode. Raman spectroscopy confirmed that all the films are amorphous. Chemical characterization of each pair of films was undertaken using Infrared Reflection Absorption Spectroscopy and X-ray Photoelectron Spectroscopy. The former revealed the presence of specific structures, such as C-H, C-O, O-H. The latter allowed calculation of the ratio of hetero-atoms to carbon atoms in the films, e. g. F:C, N:C, and Si:C. Only relatively small differences in elemental composition were detected between films produced by the two methods. The deposition rate in PIIID is generally reduced in relation to that of PECVD; for a-C:H:Cl films the reduction factor is almost four.

Plasma-polymerized acetylene nanofilms modified by nitrogen ion implantation

Thin films were prepared by plasma enhanced chemical vapour deposition (PECVD) from a mixture of acetylene and argon, and post deposition-treated by plasma immersion ion implantation (PIII). The effect of PIII on the nanofilms properties was evaluated as a function of treatment time. The average thickness and roughness were diminished upon PIII. On the other hand, hardness (0.7-3.9 GPa) and elastic modulus (29-54 GPa) increased upon 60 min of ion bombardment. Such results are ascribed mainly to the densification of the film structure caused by the increment in the crosslinking degree with increasing the energy deposited in the films. Wettability of the samples, investigated by contact angle measurements, was reduced (from 64 to 21°) right after PIII. This result, attributed to the introduction of polar groups in the film structure, was not preserved as the sample was aged in atmosphere. After aging, contact angles were larger than 70° but still smaller than 90°. Although the wettability has decreased with aging, the hydrophilic character of the samples was preserved. For certain treatment times, nitrogen PIII turned the plasma-polymerized acetylene films smoother, denser, mechanically and tribologicaly more resistant than the as-deposited material. © 2013 Elsevier B.V.

Optical, mechanical and surface properties of amorphous carbonaceous thin films obtained by plasma enhanced chemical vapor deposition and plasma immersion ion implantation and deposition

Diverse amorphous hydrogenated carbon-based films (a-C:H, a-C:H:F, a-C:H:N, a-C:H:Cl and a-C:H:Si:O) were obtained by radiofrequency plasma enhanced chemical vapor deposition (PECVD) and plasma immersion ion implantation and deposition (PIIID). The same precursors were used in the production of each pair of each type of film, such as a-C:H, using both PECVD and PIIID. Optical properties, namely the refractive index, n, absorption coefficient, α, and optical gap, ETauc, of these films were obtained via transmission spectra in the ultraviolet-visible near-infrared range (wavelengths from 300 to 3300 nm). Film hardness, elastic modulus and stiffness were obtained as a function of depth using nano-indentation. Surface energy values were calculated from liquid drop contact angle data. Film roughness and morphology were assessed using atomic force microscopy (AFM). The PIIID films were usually thinner and possessed higher refractive indices than the PECVD films. Determined refractive indices are consistent with literature values for similar types of films. Values of ETauc were increased in the PIIID films compared to the PECVD films. An exception was the a-C:H:Si:O films, for which that obtained by PIIID was thicker and exhibited a decreased ETauc. The mechanical properties - hardness, elastic modulus and stiffness - of films produced by PECVD and PIIID generally present small differences. An interesting effect is the increase in the hardness of a-C:H:Cl films from 1.0 to 3.0 GPa when ion implantation is employed. Surface energy correlates well with surface roughness. The implanted films are usually smoother than those obtained by PECVD. ©2013 Elsevier B.V. All rights reserved.

Plasma enhanced chemical vapor deposition of titanium(IV) ethoxide-oxygen-helium mixtures

Thin films were deposited by plasma enhanced chemical vapor deposition from titanium (IV) ethoxide (TEOT)-oxygen-helium mixtures. Actinometric optical emission spectroscopy was used to obtain the relative plasma concentrations of the species H, CH, O and CO as a function of the percentage of oxygen in the feed, R(ox). The concentrations of these species rise with increasing R(ox) and tend to fall for R(ox) greater than about 45%. As revealed by a strong decline in the emission intensity of the actinometer Ar as R(ox) was increased, the electron mean energy or density (or both) decreased as greater proportions of oxygen were fed to the chamber. This must tend to reduce gas-phase fragmentation of the monomer by plasma electrons. As the TEOT flow rate was fixed, however, and since the species H and CH do not contain oxygen, the rise in their plasma concentrations with increasing R(ox) is explained only by intermediate reactions involving oxygen or oxygen-containing species. Transmission infrared (IRS) and X-ray photoelectron (XPS) spectroscopies were employed to investigate film structure and composition. The presence of CH(2), CH(3), C=C, C-O and C=O groups was revealed by IRS. In addition, the presence of C-O and C=O groups was confirmed by XPS, which also revealed titanium in the +4 valence state. The Ti content of the films, however, was found to be much less than that of the monomer material itself. (C) 2007 Elsevier B.V. All rights reserved.

Characterization of Si : O : C : H films fabricated using electron emission enhanced chemical vapour deposition

Silicon-based polymers and oxides may be formed when vapours of oxygen-containing organosilicone compounds are exposed to energetic electrons drawn from a hot filament by a bias potential applied to a second electrode in a controlled atmosphere in a vacuum chamber. As little deposition occurs in the absence of the bias potential, electron impact fragmentation is the key mechanism in film fabrication using electron-emission enhanced chemical vapour deposition (EEECVD). The feasibility of depositing amorphous hydrogenated carbon films also containing silicon from plasmas of tetramethylsilane or hexamethyldisiloxane has already been shown. In this work, we report the deposition of diverse films from plasmas of tetraethoxysilane (TEOS)-argon mixtures and the characterization of the materials obtained. The effects of changes in the substrate holder bias (Vs) and of the proportion of TEOS in the mixture (XT) on the chemical structure of the films are examined by infrared-reflection absorption spectroscopy (IRRAS) at near-normal and oblique incidence using unpolarised and p-polarised, light, respectively. The latter is particularly useful in detecting vibrational modes not observed when using conventional near-normal incidence. Elemental analyses of the film were carried out by X-ray photoelectron spectroscopy (XPS), which was also useful in complementary structural investigations. In addition, the dependencies of the deposition rate on Vs and XT are presented. (c) 2007 Elsevier B.V. All rights reserved.

Plasma-polymerized hexamethyldisilazane treated by nitrogen plasma immersion ion implantation technique

This paper describes the effect of nitrogen Plasma Immersion Ion Implantation (PIII) on chemical structure, refraction index and surface hardness of plasma-polymerized hexamethyldisilazane (PPHMDSN) thin films. Firstly, polymeric films were deposited at 13.56 MHz radiofrequency (RF) Plasma Enhanced Chemical Vapour Deposition (PECVD) and then, were treated by nitrogen PIII from 15 to 60 min. Fourier Transformed Infrared (FTIR) spectroscopy was employed to analyse the molecular structure of the samples, and it revealed that vibrations modes at 3350 cm(-1), 2960 cm(-1), 1650 cm(-1), 1250 cm(-1) and 1050 cm(-1) were altered by nitrogen PIII. Visible-ultraviolet (vis-UV) spectroscopy was used to evaluate film refractive index and the results showed a slight increase from 1.6 to 1.8 following the implantation time. Nanoindentation revealed a surface hardness rise from 0.5 to 2.3 GPa as PIII treatment time increased. These results indicate nitrogen PIII is very promising in improving optical and mechanical properties of PPHMDSN films.

Análise do comportamento biomecânico de fios ortodônticos após tratamento de superfície

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Influência do tratamento de superfície na força friccional de fios ortodônticos de NiTi-estudo in vitro

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Caracterização de filmes finos obtidos por deposição de vapor químico assistido a plasma (PECVD) e deposição e implantação iônica por imersão em plasma (PIIID)

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Efeito do recobrimento de filmes de carbono tipo diamante depositados a plasma na manutenção do torque de parafusos protéticos

Pós-graduação em Odontologia Restauradora - ICT

Caracterização de Filmes a-C:H:Cl e a-C:H:Si:Cl produzidos por deposição à vapor químico assistido por plasma (PECVD) e deposição e implantação iônica por imersão em plasma (PIIID)

Pós-graduação em Ciência e Tecnologia de Materiais - FC

Preparation and characterization of nanocrystalline h-BN films prepared by PECVD method

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

XPS investigation of plasma-deposited polysiloxane films irradiated with helium ions

This work describes an XPS investigation of plasma-deposited polysiloxane films irradiated with 170 keV He+ ions at fluences, Phi, ranging from 1 x 10(14) to 1 x 10(16) cm(-2). Modifications in the atomic concentrations of the surface atoms with (D were revealed by changes in the [O]/[Si], [O]/[C] and [C]/[Si] atomic ratios. Surface chemical structure modifications were evidenced by the increasing C1s peak width and asymmetry as Phi was increased, due to the formation of ether and carboxyl functionalities. Moreover, structural transformations were indicated by the positive binding energy shift of the Si2p peaks, due to the increasing Si oxidation. Correlations of the XPS data with other results from previous work on polysiloxanes illustrate the role of ion beam-induced bond breaking on the structural modifications.

Infrared spectroscopy investigation of various plasma-deposited polymer films irradiated with 170 keV He+ ions

This work illustrates the advantages of using p-polarized radiation at an incidence angle of 70 degrees in contrast to the conventional unpolarized beam at normal (or near-normal) incidence for the infrared spectroscopic study of polycarbosilane, polysilazane and polysiloxane thin films synthesized by plasma enhanced chemical vapor deposition (PECVD) and subsequently irradiated with 170 keV He+ ions at fluences from 1 x 10(14) to 1 x 10(16) cm(-2). Several bands not seen using the conventional mode could be observed in the polarized mode. (c) 2006 Elsevier B.V. All rights reserved.

Effects of nitrogen ion irradiation on plasma polymerized films produced from titanium tetraiso pro poxide-oxygen-helium mixtures

In this work films were produced by the plasma enhanced chemical vapor deposition (PECVD) of titanium tetraisopropoxide-oxygen-helium mixtures and irradiated with 150 keV singly-charged nitrogen ions (N(+)) at fluences, phi, between 10(14) and 10(16) cm(-2). Irradiation resulted in compaction, which reached about 40% (measured via the film thickness) at the highest fluence. Infrared reflection-absorption spectroscopy (IRRAS) revealed the presence of Ti-O bonds in all films. Both O-H and C-H groups were present in the as-deposited films, but the density of each of these decreased with increasing phi and was absent at high phi, indicating a loss of hydrogen. X-ray photoelectron spectroscopy (XPS) analyses revealed an increase in the C to Ti atomic ratio as phi increased, while the O to Ti ratio hardly altered, remaining at around 2.8. The optical gap of the films, derived from data obtained by ultraviolet-visible spectroscopy (UVS), remained at about 3.6 eV for all fluences except the highest, for which an abrupt fall to around 1.0 eV was observed. For the irradiated films, the electrical conductivity, measured using the two-point method, showed a systematic increase with increasing phi. (c) 2008 Elsevier B.V. All rights reserved.