Plasma Polymerized Hexamethyldisilazane Research Articles

Calcium phosphate composites to synergistically promote osteoconduction and corrosion resistance on bone materials via plasma polymerized hexamethyldisilazane coatings

A facile and effective plasma polymerized hexamethyldisilazane (ppHMDSZ) combining with calcium phosphate (Ca-P) coating to promote osteoconduction meanwhile provide resistance to corrosion is developed in this study. The composites of Ca-P and ppHMDSZ thin films were deposited on bone substitutes to investigate the osteoblast compatibility. The amount of the Ca-P coatings was modulated with a linear deposition rate of 7.37 μg/(cm2∙cycle) by alternative immersion cycles (1, 2, 5, and 10) in solutions containing calcium and phosphate, measured by quartz crystal microbalance (QCM). Importantly, cell behaviors including cell adhesion, proliferation, and functional activity responded positively toward the surface wettability and roughness of the Ca-P layers. Moreover, the human osteoblast cells (hFOB1.19) revealed excellent compatibility on the stainless steel coated with Ca-P/ppHMDSZ composite films. The combination of bioceramics and corrosion resisting plasma polymerized HMDSZ films showed a synergistic effect on the biocompatibility and osteoconductive for bone tissue engineering applications.

Dense and anti-corrosion thin films prepared by plasma polymerization of hexamethyldisilazane for applications in metallic implants

Abstract Plasma polymerized hexamethyldisilazane (ppHMDSZ) thin films with specific thickness and density coated on substrates (ppHMDSZ/substrate) to promote the corrosion resistance for the potential applications in metallic implants is reported in this study. Comparing with the conventional anti-corrosion thin film coatings, plasma polymerization method provided an effective, dry, and simpler process, which allowed to prepare dense thin films with the thickness of a few hundred nanometers. This study proposed that the anti-corrosion behavior could be correlated closely to the density of thin film coated on stainless steel (SS) that can be precisely controlled by the plasma deposition time. The physico-chemical properties of the as-prepared ppHMDSZ thin films were evaluated by field-emission scanning electron microscope (FE-SEM), water contact angle (WCA), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), and electron spectroscopy for chemical analysis (ESCA). The corrosion resistance of the ppHMDSZ coated stainless steel (ppHMDSZ/SS) was improved by depositing ~140 nm in thickness and 1.15 g/cm3 in density which reduced 90% of the original corrosion performance against the corrosion in Hank's solution, measured by potentiodynamic polarization tests. The resultant ppHMDSZ thin film coatings allowed to protect substrates toward corrosion and can be further applied in implants for tissue engineering and biomaterials.

Control of Polydimethylsiloxane Surface Hydrophobicity by Plasma Polymerized Hexamethyldisilazane Deposition

The properties of a polydimethylsiloxane (PDMS) surface were modified by a one-step deposition of plasma polymerized hexamethyldisilazane (pp-HMDS) by the arc discharge method. Scanning electron microscopy, atomic force microscopy, and Fourier-transform infrared spectroscopy analytical techniques were employed for morphological, structural, and chemical characterization of the pp-HMDS modified PDMS surface. The changes in PDMS substrate wetting properties were evaluated by means of contact angle measurements. The unmodified PDMS surface is hydrophobic with a contact angle of 122°, while, after pp-HMDS film deposition, a dual-scale roughness PDMS surface with contact angle values as high as 170° was obtained. It was found that the value of the contact angle depends on the plasma processing time. Chemically, the pp-HMDS presents methyl moieties, rendering it hydrophobic and making it an attractive material for creating a superhydrophobic surface, and eliminating the need for complex chemical routes. The presented approach may open up new avenues in design and fabrication of superhydrophobic and flexible organosilicon materials with a self-cleaning function.

Photothermal study of RF-plasma polymerized hexamethyldisilazane thin films

Plasma polymerization by RF excited low pressure plasmas is a powerful technique for synthesizing thin films for a wide range of applications such in microelectronics, biomaterials and aeronautical industries. Among these applications plasma polymerized hexamethyldisilazane (HMDSN here in) is a promising material due its biocompatibility, optical and electrical properties. In the present paper, we reported the thermal diffusivity measurements of plasma polymerized HMDSN thin films using the probe beam deflection technique (PBD). The samples are thermally thin and optically transparent, with thicknesses ranging from 170 to 600nm, difficulting their thermal characterization by other photo-thermal techniques (photoacoustic and pyroelectric). PBD measurements were carried out with a diode (20mW, λ=640nm) and a HeNe (0.9mW, λ=632nm) laser, used as pump source and probe beam, respectively. The probe beam was focused close to the sample surface and its direction was perpendicular to the pump beam. The transverse PBD in skimming configuration is employed and the deflection signal is analyzed using the phase method for the determination of thermal diffusivity. The results show the decreasing of thermal diffusivity with the decreasing of film thickness. HMDSN film׳s thermal diffusivity values are reported in this paper for the first time being in the range of typical polymeric samples.

Production and Characterization of Composite Material Useful as a Protective Barrier in Electronic Applications

This work describes the production and characterization of a selective membrane useful for electronic devices. The membrane was a composite made by a thin film of plasma-polymerized HFE (methyl nonafluoro(iso)butyl ether) immersed in plasma-polymerized HMDS (hexamethyldisilazane) film, a third phase being 5 µm starch particles included in this matrix. The film was deposited on silicon substrates and its physical, chemical and adsorption characteristics were determined. Infrared and x-ray photoelectron spectroscopy analyses showed fluorine and carboxyl groups on the bulk and the surface, respectively. SEM results indicate the film is conformal even if starch is present. Optical microscopy analysis showed good resistance toward acid and base solutions. Quartz crystal microbalance indicated adsorption of polar organic compounds on ppm range. This thin film is environment-friendly and can be used as a protective layer or in electronic devices due to adsorption of volatile organic compounds.

Simple method of hybrid PVD/PECVD to prepare well-dispersed cobalt–plasma polymerized hexamethyldisilazane nanocomposites

A simple and easy method to prepare well-dispersed cobalt–plasma polymerized hexamethyldisilazane (Co–pp HMDSN) nanocomposites is presented. A hybrid physical vapor deposition (PVD) and plasma enhanced chemical vapor deposition (PECVD) technique was used to prepare finely dispersed Co–pp HMDSN nanocomposites. The metal filling factor could be varied from 4% to 34%. Structural investigations were performed using transmission electron microscopy (TEM) and X-ray diffractometry (XRD). They revealed the presence of amorphous cobalt nanoparticles of size ~2–3nm at lower filling factor, whereas crystalline CoO nanoparticles of size ~6nm were observed at higher filling factor. Energy dispersive X-ray spectroscopy (EDX) and profilometry were employed to determine the filling factor. Compositional analysis using Fourier transform infrared (FTIR) spectroscopy indicated the presence of SiO and SiC bonds in the polymer matrix. The influence of oxygen was observed in all nanocomposites. With the increase in filling factor the polymer matrix was significantly modified. A set of well-dispersed Co–pp HMDSN nanocomposites with varying metal filling factors was prepared which is suitable as precursor for calcination. As the functional properties of the calcinated nanocomposites are dependent on the properties of the precursors, the importance of a detailed study of the precursors for calcination is emphasized. A simple and generalized procedure to introduce well-dispersed metal nanoparticles into a polymer matrix is demonstrated.

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.

Polymerized hexamethyldisilazane coated on equiatomic TiNi shape memory alloy using DC-pulsed plasma assisted chemical vapor deposition

SiC:H organic-like thin films are deposited on Ti 50Ni 50 shape memory alloy by asymmetric bipolar DC-pulsed plasma assisted chemical vapor deposition (PACVD) in the gas mixture of hexamethyldisilazane (HMDSN) and Ar at room temperature. The deposition rate of the plasma-polymerized HMDSN (PPHMDSN) thin film is faster than that of RF process and the PPHMDSN thin films not only enhance the corrosion resistance but make the corrosion current density decay four orders. The surface morphology of the films is very smooth and uniform and the root mean square of surface roughness is in the range between 3 and 5 nm. The organic-like thin films containing peroxides or free radicals can be grafted with polymer acrylamide (AAm) which can improve the biocompatibility of TiNi shape memory alloy.

Hydrophobic plasma polymerized hexamethyldisilazane thin films: characterization and uses

Hexametildisilazane (HMDS) plasma polymerized thin films obtained using low frequency power supplies can be used to make adsorbent films and turn surfaces hydrophobic. The aim of this work was to verify the hydrophobicity and adsorption properties of HMDS thin films (with and without the addition of oxygen, resulting in double or single layer films) obtained using an inductive reactor powered with a 13.56 MHz power supply. Single and double layer thin films were deposited on silicon for film characterization, polypropylene (PP) for ultraviolet (UVA/UVC) resistance tests, piezoelectric quartz crystal for adsorption tests. The double layer (intermixing) of HMDS plasma polymerized films and HMDS plasma oxidized surfaces showed a non-continuous layer. The films showed good adhesion to all substrates. Infrared analysis showed the presence of CHn, SiCH3, SiNSi and SiCH2Si within the films. Contact angle measurements with water showed hydrophobic surfaces. UVA/UVC exposure of the films resulted in the presence of cross-linking on carbonic radicals and SiCH2Si formation, which resulted in a possible protection of PP against UVA/UVC for a duration of up to two weeks. Adsorption tests showed that all organic reactants were adsorbed but not water. Plasma etching (PE) using O2 showed that even after 15 minutes of exposure the films do not change their hydrophobic characteristic but were oxidized. The results point out that HMDS films can be used: for ultraviolet protection of flexible organic substrates, such as PP, for sensor and/or preconcentrator development, due to their adsorption properties, and in spatial applications due to resistance for O2 attack in hostile conditions, such as plasma etching.

The Improvement of Biocompatibility of an Equiatomic TiNi Shape Memory Alloy by DC Plasma-Polymerized Hexamethyldisilazane Coatings

The Improvement of Biocompatibility of an Equiatomic TiNi Shape Memory Alloy by DC Plasma-Polymerized Hexamethyldisilazane Coatings

Plasmapolymerized silicon organic thin films from HMDSN for capacitive humidity sensors

Capacitive humidity sensors were fabricated employing a plasmapolymerized hexamethyldisilazane (HMDSN) thin film layer as the moisture sensitive material. The sensor design comprises interdigital electrodes, the plasmapolymer, and a porous top electrode. A humidity sensor with a simple structure and small dimensions (6 mm 2) has been developed and characterized exhibiting a response time below 1 min, good reversibility, and a high sensitivity. The variation of the plasmapolymerization parameter resulted in different humidity sensing properties which could be correlated to the results of the film analysis by FTIR, contact angle measurements, and SEM photography.

DC plasma-polymerized hexamethyldisilazane coatings of an equiatomic TiNi shape memory alloy

The TiNi corrosion resistance of Ti 50Ni 50 shape memory alloy can be substantially improved by DC plasma-polymerized hexamethyldisilazane (PHMDSN) coatings. The initial PHMDSN deposition rate increases with increasing DC voltage. The deposition rate decreases gradually with time until the glow discharge is extinguished. The higher DC voltage used in plasma polymerization will develop a film with a more inorganic nature from the IR spectrum analysis and water contact angle measurements. The PHMDSN coatings for DC voltage ≥1000 V are protection against the corrosion in Ringer’s solution and can be deformed up to a 2% strain. The corrosion current density of the TiNi alloy can be lowered by as many as four orders of magnitude. The pitting potential and re-passivation potential can also be enhanced to nobler potential after PHMDSN coatings. The widely scattered pitting potential of the as-homogenized TiNi can also be improved by the PHMDSN coatings.

プラズマ重合ヘキサメチルジシラザン薄膜の生成と絶縁破壊

プラズマ重合ヘキサメチルジシラザン薄膜の生成と絶縁破壊

The influence of polarization on hole transport in plasma-polymerized organosilicon films

The influence of polarization procedure on charge carrier transport in plasma polymerized organosilicon films was investigated. Mobility of holes was determined using the time-of-flight method. It was found that frozen-in polarization of the plasma polymerized hexamethyldisilazane films increases the value of drift mobility. This process is fully reversible and after depolarization the value of drift mobility returns to the one before polarization. >

Some properties of plasma-polymerized hexamethyldisilazane

Plasma polymerization of hexamethyldisilazane has been performed in a tubular type reactor. Thermal stability, plasma etching and dielectric properties of the films have been investigated after their various post deposition treatments. This included drying in a vacuum or air, or the exposure to N 2 plasma. Infrared spectroscopy has been employed to study the structure of these films.

Low temperature conductivity in plasma-polymerized silazane films

Low temperature conductivitu in plasma-polymerized hexamethyldisilazane films was investigated. A variable range hopping is responsible for this conductivity. It was found that a polarization process influenced the density of hopping states and hence, the average hopping distance. This process was studied by the TSD method.

Chemical characterization of plasma-polymerized hexamethyldisilazane by nuclear elastic recoil detection

Chemical composition profiles of plasma-polymerized hexamethyldisilazane thin films, deposited in microwave discharges, were measured by elastic recoil detection (ERD). The main fabrication variable during film deposition was the substrate temperature, which was varied from 25 to 650°C. Hydrogen, carbon and silicon concentrations and profiles to a depth of roughly 1 μm were measured by ERD. These concentrations were compared with results obtained by conventional chemical microanalysis, and agreement was found to be excellent. As in earlier work using other techniques, ERD confirmed the presence of a thin (approximately 50 nm) “oligomeric” layer at the free surface of the films. Erosive radiation damage caused by the probing ion beam on the carbon and hydrogen profiles was observed and investigated.

Wettability studies of plasma‐polymerized hexamethyldisilazane

Journal of Applied Polymer ScienceVolume 25, Issue 10 p. 2435-2438 NoteFree Access Wettability studies of plasma-polymerized hexamethyldisilazane N. K. Eib, N. K. Eib IBM Corporation, Hopewell Junction, NY 12533Search for more papers by this authorK. L. Mittal, Corresponding Author K. L. Mittal IBM Corporation, Hopewell Junction, NY 12533IBM Corporation, Hopewell Junction, NY 12533===Search for more papers by this authorA. Friedrichs, A. Friedrichs IBM Corporation, Hopewell Junction, NY 12533Search for more papers by this author N. K. Eib, N. K. Eib IBM Corporation, Hopewell Junction, NY 12533Search for more papers by this authorK. L. Mittal, Corresponding Author K. L. Mittal IBM Corporation, Hopewell Junction, NY 12533IBM Corporation, Hopewell Junction, NY 12533===Search for more papers by this authorA. Friedrichs, A. Friedrichs IBM Corporation, Hopewell Junction, NY 12533Search for more papers by this author First published: October 1980 https://doi.org/10.1002/app.1980.070251030Citations: 15AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL References 1 M. R. Havens, J. Vac. Sci. Tech., 13, 575 (1976). 2 J. C. Lee. Appl. Opt., 17, 2645 (1978). 3 J. S. Sandved and K. Kristiansen, Vacuum, 27 (4), 235 (1977). 4 G. Smolinsky, J. Vac. Sci. Tech., 11, 33 (1974). 5 A. M. Wrobel and M. Kryszewski in Plasma Polymerization M. Shen and A. T. Bell, eds., Am. Chem. Soc. Symp. Ser. No. 108, Am. Chem. Soc., Washington, DC, 1979, pp. 237– 249. 6 P. K. Tien, G. Smolinsky and R. J. Martin, Appl. Opt., 11, 637 (1972). 7 A. M. Wrobel, M. R. Wertheimer, J. Dib, and H. P. Schreiber, J. Macromol. Sci. Chem., to appear. 8 T. Hirotsu, J. Appl. Polym. Sci., 24, 195 (1979). 9(a) W. A. Zisman in Contact Angle, Wettability and Adhesion, Adv. Chem. Ser. No. 43, Am. Chem. Soc., Washington, DC, 1964. (b) Contact Angle, Wettability and Adhesion, Adv. Chem. Ser. No. 43, Am. Chem. Soc., Washington, DC p. 21. 10 N. K. Eib, K. L. Mittal, and H. R. Anderson, Jr., presented at the Adhesion Society Meeting, Savannah, GA, Feb. 10–13, 1980 11 N. K. Eib, K. L. Mittal and H. R. Anderson, Jr., presented at the Colloid and Surface Science Symposium, Leihgh University, Bethlehem, PA, June 15–18, 1980. Citing Literature Volume25, Issue10October 1980Pages 2435-2438 ReferencesRelatedInformation