Abstract
A novel technique based in the combination of vapor silanization and chemical vapor deposition, hereafter referred to as activated vapor silanization (AVS), is shown to be an effective biofunctionalization technique. The AVS process results in thin organic films with a high surface amine concentration when deposited on substrates with different chemical characteristics, such as silicon, porous silicon, or gold. Chemical characterization shows that the films are composed of carbon (hydrocarbon, C–Si, C–C), silicon (different oxidation states), nitrogen (primary and secondary amines), oxygen, and hydrogen. Relevantly, the amines are also distributed along the film thickness, ensuring functionality even after some degradation of the films. AVS films behave practically as monocrystalline silicon substrates under loading–unloading tests. In addition, the AVS films behave as permeable membranes for molecules smaller than 5 Å, and the amine surface concentration is estimated to be 8 NH2/nm2 for molecules of about 12 Å, which is three times higher than that obtained with standard silanization procedures.
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K.L. Prime G.M. Whitesides: Self-assembled organic monolayers—Model systems for studying adsorption of proteins at surfaces. Science 252, 1164 1991
R.P. Andres, J.D. Bielefeld, J.I. Henderson, D.B. Janes, V.R. Kolagunta, C.P. Kubiak, W.J. Mahoney R.G. Osifchin: Self-assembly of a two-dimensional superlattice of molecularly linked metal clusters. Science 273, 1690 1996
J.M. Buriak: Organometallic chemistry on silicon surfaces: Formation of functional monolayers bound through Si–C bonds. Chem. Commun. 12, 1051 1999
M.P. Stewart, E.G. Robins, T.W. Geders, M.J. Allen, H.C. Choi J.M. Buriak: Three methods for stabilization and functionalization of porous silicon surfaces via hydrosilylation and electrografting reactions. Phys. Status Solidi A 182, 109 2000
T. Kuhnen, R. Ruffolo, M. Stradioto, D. Ulbrich, M.J. McGlinchey, M.A. Brook: Using hydrosilylation to assemble organometallic polymers containing combinations of silicon-based functional groups. Organometallics 16, 5042 1997
J.B. Brzoska, I. Benazouz F. Rondelez: Silanization of solid substrates—A step toward reproducibility. Langmuir 10, 4367 1994
A.Y. Fadeev T.J. McCarthy: Trialkylsilane monolayers covalently attached to silicon surfaces: Wettability studies indicating that molecular topography contributes to contact angle hysteresis. Langmuir 15, 3759 1999
D.G. Kurth T. Bein: Surface reactions on thin-layers of silane coupling agents. Langmuir 9, 2965 1999
L.D. White C.P. Trip: Reaction of (3-aminopropyl)dimethylethoxysilane with amine catalysts on silica surfaces. J. Colloid Interface Sci. 232, 400 2000
M. Manso-Silvan, R.J. Martin-Palma, J. Perez-Rigueiro J.M. Martinez-Duart: Surface functionalisation by the condensation of hybrid titanate-amino sols. Thin Solid Films 415, 253 2002
D. Wang F.R. Jones: Surface analytical study of the interaction between γ-amino propyl triethoxysilane and e-glass surface. 2. X-ray photoelectron-spectroscopy. J. Mater. Sci. 28, 2481 1993
P.X. Zhu, Y. Masuda K. Koumoto: Site-selective adhesion of hydroxyapatite microparticles on charged surfaces in a supersaturated solution. J. Colloid Interface Sci. 243, 31 2001
V.A. Basyuk A.A. Chuiko: Infrared spectra of amide products formed during chemisorption of α-amino acid vapors on the surface of γ-aminopropyl-aerosil. Zh. Prikl. Spektrosk. 52, 935 1990
R.J. Martín-Palma, M. Manso, J. Pérez-Rigueiro, J.P. García-Ruiz J.M. Martínez-Duart: Surface biofunctionalization of materials by amine groups. J. Mater. Res. 19, 2415 2004
M. Arroyo-Hernández, J. Pérez-Rigueiro J.M. Martínez-Duart: Formation of amine functionalized films by chemical vapor deposition. Mater. Sci. Eng., C 26, 938 2006
M. Arroyo-Hernandez, R.J. Martin-Palma, J. Perez-Rigueiro, J.P. Garcia-Ruiz, J.L. Garcia-Fierro J.M. Martinez-Duart: Biofunctionalization of surfaces of nanostructured porous silicon. Mater. Sci. Eng., C 23, 697 2003
M. Mayer: SIMNRA User’s Guide Max Planck Institute Garching, Germany IPP Report 9/113 1997
V. Quillet, F. Abel M. Schott: Absolute cross section measurements for H and D elastic recoil using 1 to 2.5 MeV 4He ions, and for the 12C(d,p)13C and 16O(d,p1)17O nuclear reactions. Nucl. Instrum. Methods Phys. Res., Sect. B 83, 47 1993
J.H. Moon, J.W. Shin, S.Y. Kim J.W. Park: Formation of uniform aminosilane thin layers: An imine formation to measure relative surface density of the amine group. Langmuir 12, 4621 1996
W.C. Oliver G.M. Pharr: An improved technique for determining hardness and elastic modulus using load and displacement sensing indentation experiments. J. Mater. Res. 7, 1564 1992
D.G. Kurth T. Bein: Thin films of (3-aminopropyl)triethoxysilane on aluminum oxide and gold substrates. Langmuir 11, 3061 1995
T. Ogasawara, A. Nara, H. Okabayashi, E. Nishio C.J. O’Connor: Time-resolved near-infrared and two-dimensional near-infrared correlation spectroscopic studies of the polymerization process of silane coupling agents. Dynamic behavior of water molecules in the 3-aminopropyltriethoxysilane–ethanol–water system. Colloid Polym. Sci. 278, 1070 2000
T.R. Gengenbach, R.C. Chatelier H.J. Griesser: Correlation of the nitrogen 1s and oxygen 1s XPS binding energies with compositional changes during oxidation of ethylene diamine plasma polymers. Surf. Interface Anal. 24, 611 1996
J.L. Magalhaes, L.M. Moreira, U.P. Rodrigues-Filho, J. Giz, M.A. Pereira-da Silva, R. Landers, R.C.G. Vinhas P.A.P. Nascente: Surface chemistry of the iron tetraazamacrocycle on the aminopropyl-modified surface of oxidized n-Si(100) by AFM and XPS. Surf. Interface Anal. 33, 293 2002
J.H. Moon, J.H. Kim, K.J. Kim, T.H. Kang, B. Kim, C.H. Kim, J.H. Hahn J.W. Park: Absolute surface density of the amine group of the aminosilylated thin layers: Ultraviolet–visible spectroscopy, second harmonic generation and synchrotron-radiation photoelectron spectroscopy study. Langmuir 10, 4367 1994
Acknowledgments
The authors thank G. Hueso for his technical contributions. M. Arroyo-Hernández has been supported by a grant from the Education Ministry of Spain. Partial funding of this project has been provided by the CICyT (Contract No. TEC2004-05260-C02-01).
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Arroyo-Hernández, M., Pérez-Rigueiro, J., Conde, A. et al. Characterization of biofunctional thin films deposited by activated vapor silanization. Journal of Materials Research 23, 1931–1939 (2008). https://doi.org/10.1557/JMR.2008.0241
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DOI: https://doi.org/10.1557/JMR.2008.0241