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1. Cui, L., Ranade, A. N., Matos, M. A., Pingree, L.S., Frot, L. S., Dubois, G., Dauskardt, R. H, “Atmospheric Plasma Deposited Dense Silica Coatings on Plastics,” ACS Applied Materials & Interfaces (Nov. 2012). Abstract: We explore the application of a high-temperature precursor delivery system for depositing high boiling point organosilicate precursors on plastics using atmospheric plasma. Dense silica coatings were deposited on stretched poly(methyl methacrylate), polycarbonate and silicon substrates from the high boiling temperature precursor, 1, 2-bis(triethoxysilyl)-ethane, and from two widely used low boiling point temperatures, tetraethoxysilane and tetramethylcyclotetrasiloxane. The coating deposition rate, molecular network structure, density, Young’s modulus and adhesion to plastics exhibited a strong dependence on the precursor delivery temperature and rate, and the functionality and number of silicon atoms in the precursor molecules. The Young’s modulus of the coatings tanged from 6 to 34 GPa, depending strongly on the coating density. The adhesion of the coatings to plastics was affected by both the chemical structure of the precursor and the extent of the exposure of the plastic substrate to the plasma during the initial stage of deposition. The optimum combinations of Young’s modulus and good adhesion compared to commercial polysiloxane hard coatings on plastics. Atmospheric Plasma Deposited Dense Silica Coatings on Plastics
2. Ladwig, A. M., Koch, R. D., Wenski, E. G., and Hicks, R. F., “Atmospheric plasma deposition of diamond-like carbon coatings,” Diamond 18, 1129 (2009). Abstract: The atmospheric pressure plasma-enhanced chemical vapor deposition of diamond-like carbon (DLC) has been investigated. The DLC coatings were grown with a mixture of acetylene, hydrogen and helium that was fed through a linear plasma source. The plasma was driven with radio frequency power at 27.12 MHz. Deposition rates exceeded 0.10 µm/min at substrate temperatures between 155 and 200 °C.
3. Barankin, M. D., Gonzalez, E., Habib, S., Gao, L, Guschl, P. C. and Hicks, R. F., “Hydrophobic films by atmospheric plasma curing of spun-on liquid precursors,” Langmuir 25, 2495 (2009). Abstract: Hydrophobic coatings have been produced on glass and acrylic samples by using a low-temperature atmospheric pressure plasma to polymerize liquid ﬂuoroalkylsilane precursors. The ﬂuoroalkylsilane precursor was dissolved in isooctane and spun onto the substrate at 550 rpm. The sample was then exposed to the reactive species generated from a nitrogen plasma. The plasma was operated with 2.3 vol % N2 in helium at 7.4 W/cm2 at a radio frequency of 27.12 MHz. The total and polar component of the coating’s surface energy was found to equal 11.0 and 1.2 dyn/cm, respectively. Average water contact angles of 110° and 106° were measured on the coated glass and acrylic surfaces, respectively. X-ray photoelectron spectroscopy revealed that, after treatment, the ﬂuoroalkyl ligands remained intact on the Si atoms, with a F/C atomic ratio of 2.23.
4. Huang, C., Liu, C. H., and Wu, S. Y., “Surface characterization of the SiOx films prepared by a remote atmospheric pressure plasma jet,“ Surf. Interface Anal. 41, 44 (2009). Abstract: The deposition rate and surface properties of SiOx films were prepared and investigated using remote atmospheric pressure plasma (APP) jet. The APP, generated with low frequency power at 16 kHz, was fed with tetraethoxysilane (TEOS)/air gas mixture. After deposition, the SiOx films were analyzed for chemical characteristics, elemental composition, surface morphology, and hardness. It was found that the deposition substrate temperature is the key factor to affect the deposition rate of remote APP chemical vapor deposition process. Fourier transform infrared (FTIR) spectra indicated that APP deposited SiOx films are an inorganic feature. XPS examination revealed that the SiOx films contained approximately 30% silicon, 58% oxygen and 12% carbon. Atomic forced microscopy (AFM) analysis results indicated a smooth surface of SiOx films in deposition under higher substrate temperature. Also, pencil hardness tests indicated that the hardness of APP deposited SiOx films was greatly improved with increasing substrate temperatures.
5. Sailer, R. A., Wagner, A., Schmit, C., Klaverkamp, N., and Schulz, D. L., “Deposition of transparent conductive indium oxide by atmospheric-pressure plasma jet,” Surf. Coat. Technol. 203, 835 (2008). Abstract: Indium (III) beta-diketonate complexes were employed as the solid precursor sources in the atmospheric-pressure plasma chemical vapor deposition of indium oxide films using He carrier gas, O2 reactant gas and growth temperatures from 25 to 250C. Ellipsometry and X-ray reflectivity showed that the films varied in thicknesses from 40 to 70nm over the 30cm2 deposition growth area for a 12min duty cycle. The as-deposited films exhibit transmittance in excess of 90% over the visible spectrum while maintaining resistivity on the order of 10- 2Ω cm. Improved electrical properties (i.e., ρ < 10- 3Ω cm) were observed after thermal treatment (T ~ 200C) in a controlled gas ambient tube furnace. 2008 Elsevier B.V.
6. Schafer, J., Foest, R., Quade, A., Ohl, A., and Weltmann, K. D., “Local deposition of SiOx plasma polymer films by a miniaturized atmospheric pressure plasma jet (APPJ),” J. Phys. D: Appl. Phys.41, 194010 (2008). Abstract: An atmospheric plasma jet (APPJ, 27.17 MHz, Ar with 1% HMDSO) has been studied for the deposition of thin silicon-organic films. Jet geometries are attractive for local surface treatment or for conformal covering of 3D forms, e.g. inner walls of wells, trenches or cavities, because they are not confined by electrodes and their dimensions can be varied from several centimetres down to the sub-millimetre region.
7. Barankin, M. D., Gonzalez II, E., Ladwig, A. M., and Hicks, R. F., “Plasma-enhanced chemical vapor deposition of zinc oxide at atmospheric pressure and low temperature,” Solar Energy Mater. Solar Cells 91, 924 (2007). Abstract: The plasma-enhanced chemical vapor deposition of aluminum-doped zinc oxide has been demonstrated for the ﬁrst time at 800 Torr and under 250 1C. It was found that, while the growth rate did not change with substrate temperature, both the resistivity and optical absorption coefﬁcient declined with increasing temperature.
8. Ladwig, A., Babayan, S., Smith, M., Hester, M., Highland, W., Koch, R., and Hicks, R. F., “Atmospheric plasma deposition of glass coatings on aluminum,” Surf. Coat. Technol. 201, 6460 (2007). Abstract: The deposition and properties of glass coatings on aluminum was investigated using atmospheric pressure plasma-enhanced chemical vapor deposition. The plasma, generated with radio frequency power at 27.12 MHz, was fed helium, oxygen and two types of silicon precursors, hexamethyldisilazane and tetraethylorthosilicate. After deposition, the coatings were analyzed for composition, adhesion and dielectric strength. X-ray photoelectron spectroscopy revealed that the glass coatings contained approximately 25% silicon, 50% oxygen and 25% carbon. Scratch tests indicated that the coatings were strongly adherent to the substrates. The glass coatings achieved DC dielectric strengths in between 50 and 250 V for a thickness range of 0.5 to 1.3 μm. The maximum breakdown voltage measured was 400 V. Scanning electron microscopy revealed that breakdown occurred at cracks and other defects in the coatings. These defects appeared to form around areas of surface roughness and contamination.
9. Moravej, M., and Hicks, R. F., “Atmospheric plasma deposition of coatings using a capacitive discharge source,” Chem. Vap. Deposition. 11, 469 (2005).
10. Alexandrov, S. E., and Hitchman, M. L., “Chemical vapor deposition enhanced by atmospheric pressure non-thermal non-equilibrium plasmas,” Chem. Vap. Deposition. 11, 457 (2005). Abstract: This review gives an overview of the characteristics of various non-thermal, non-equilibrium plasmas and discusses applications of AP-PECVD with dielectric barrier discharges, corona discharges, RF discharges, and microwave discharges.
11. Nowling, G. R., Yajima, M., Babayan, S. E., Moravej, M., Yang, X., Hoffman, W., and Hicks, R. F., “Chamberless plasma deposition of glass coatings on plastic,” Plasma Sources Sci. Technol. 14, 477 (2005). Abstract: A chamberless, remote plasma deposition process has been used to coat silicon and plastic substrates with glass at ambient conditions. The ﬁlms were deposited by introducing an organosilane precursor into the afterglow of an atmospheric plasma fed with helium and 2 vol% oxygen. The precursors examined were hexamethyldisilazane, hexamethyldisiloxane, tetramethyldisiloxane, tetramethylcyclotetrasiloxane and tetraethoxysilane. With hexamethyldisilazane, glass ﬁlms were deposited at rates of up to 0.25µm min−1 and contained as little as 13.0 mol% hydroxyl groups. These ﬁlms exhibited low porosity and superior hardness and abrasion resistance. With tetramethyldisiloxane, glass ﬁlms were deposited at rates up to 0.91µm min−1. However, these coatings contained signiﬁcant amounts of carbon and hydroxyl impurities (∼20 mol% OH), yielding a higher density of voids and poor abrasion resistance. In summary, the properties of glass ﬁlms produced by remote atmospheric plasma deposition strongly depend on the organosilane precursor selected.
12. Kim, S. H., Kim, J. H., Kang, B. K., and Uhm, H. S., “Superhydrophobic CFx coating via in-line atmospheric RF plasma of He-CF4-H2,” Langmuir 21, 12213 (2005). Abstract: Stable superhydrophobic coatings on various substrates are attained with an in-line atmospheric rf plasma process using CF4, H2, and He. The coating layer is composed of CFxnanoparticulates and has an average roughness of 10 nm. This roughness is much smaller than other surfaces reported for superhydrophobicity in the literature. The superhydrophobic coatings are produced on both metallic and insulating substrates without any need of separate microroughening or vacuum lines.
13. Moravej, M, Babayan, S. E., Nowling, G. R., Yang, X., and Hicks, R. F., “Plasma enhanced chemical vapour deposition of hydrogenated amorphous silicon at atmospheric pressure,”Plasma Sources Sci. Technol.13, 8 (2004). Abstract: Amorphous hydrogenated silicon ﬁlms were grown using an atmospheric pressure helium and hydrogen plasma with silane added downstream of the source. A maximum deposition rate of 120 ± 12 Å min−1 was recorded at a substrate temperature of 450˚C, 6.3 Torr H2, 0.3 Torr SiH4, 778 Torr He, 32.8 W cm−3, and an electrode-to-substrate spacing of 6.0 mm. The deposition rate increased rapidly with the silane and hydrogen partial pressures, up to 0.1 and 7.0 Torr, respectively, then remained constant thereafter. By contrast, the deposition rate decreased exponentially as the electrode-to-substrate distance was increased from 5.0 to 10.5 mm. The total hydrogen content of the ﬁlms ranged from 2.5 to 8.0 ± 1.0 at%. These results together with a model of the plasma chemistry indicate that H atoms and SiH3 radicals play an important role in the deposition process.
14. Cada, M., Churpita ,O., Hubicka, Z., Sichova, H., and Jastrabik, L., “Investigation of the low temperature atmospheric plasma deposition of TCO thin films on polymer substrates,” Surf. Coat. Technol. 177, 699 (2004). Abstract: Atmospheric barrier–torch discharge was used for low temperature deposition of thin conductive oxide thin films on polymer substrates. An atmospheric high-density plasma jet was excited at the outlet of the quartz nozzle with an external metallic ring electrode. The RF power was capacitively connected to the plasma via a dielectric wall of the quartz tube. There was not a direct contact of the atmospheric plasma with the metallic electrode in this configuration. In xO y and SnO x transparent and conductive thin films were deposited on polymer, quartz and silicon substrates by this technique. Vapours of solid phase of In-acetylacetonate and Sn-acetylacetonate carried by nitrogen flow were used for deposition of In xO y and SnO x thin films, respectively and vapours prepared of liquid solutions of In 3-tetramethylheptanedionate in n-Oktan. Some atmospheric plasma jet parameters were determined by emission spectroscopy and by planar Langmuir probe. Deposited films were analysed by means of electron microprobe system, XRD diffraction and electrical conductivity measurement.
15. Nowling, G. R., Babayan, S. E., Jankovic, V., and Hicks, R. F., “Remote plasma-enhanced chemical vapour deposition of silicon nitride at atmospheric pressure,” Plasma Sources Sci. Technol.11, 97 (2002). Abstract: Silicon nitride ﬁlms were deposited using an atmospheric pressure plasma source. The discharge was produced by ﬂowing nitrogen and helium through two perforated metal electrodes that were driven by 13.56 MHz radio frequency power. Deposition occurred by mixing the plasma efﬂuent with silane and directing the ﬂow onto a rotating silicon wafer heated to between 100˚C and 500˚C. Film growth rates ranged from 90 ± 10 to 1300 ± 130 Å min−1 . Varying the N2/SiH4 feed ratio from 55.0 to 5.5 caused the ﬁlm stochiometry to shift from SiN1.45 to SiN1.2. Minimum impurity concentrations of 0.04% carbon, 3.6% oxygen and 13.6% hydrogen were achieved at 500˚C, and an N2/SiH4 feed ratio of 22.0. The growth rate increased with increasing silane and nitrogen partial pressures, but was invariant with respect to substrate temperature and rotational speed. The deposition rate also decreased sharply with distance from the plasma. These results combined with emission spectra taken of the afterglow suggest that gas-phase reactions between nitrogen atoms and silane play an important role in this process.
16. Babayan, S. E., Jeong, J. Y., Schütze, A., Tu, V. J., Moravej, M., Selwyn, G. S., and Hicks, R. F., “Deposition of silicon dioxide films with a non-equilibrium atmospheric-pressure plasma jet,” Plasma Sources Sci. Technol. 10, 573 (2001). Abstract: Silicon dioxide ﬁlms were grown using an atmospheric-pressure plasma jet that was produced by ﬂowing oxygen and helium between two coaxial metal electrodes that were driven by 13.56 MHz radio frequency power. Silicon dioxide ﬁlms were deposited at rates ranging from 20 ± 2 to 300 ± 25 nm min−1. The deposition rate increased with decreasing temperature and increasing TEOS pressure, oxygen pressure and RF power. The results suggest that the mechanism in the atmospheric pressure plasma is the same as that in low-pressure plasmas.
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