Hydrolysis and silanization of the hydrosilicon surface of freshly prepared porous silicon by an amine catalytic reaction

A novel catalytic reaction using a trace of organic amine as the catalyst enables hydrolysis of the silicon–hydrogen groups on the fresh prepared porous silicon (PS), generating the hydroxyl-terminated surfaces without extensive oxidation of the Si–Si backbonds. The reactivity of the hydroxyl-terminated surfaces with various silanization reagents was investigated, which proceeds by abstraction of the surface –OH to form an organic monolayer of Si–O–Si–C bonds and importantly retains the intrinsic structural properties of the PS layers. Furthermore, an in situ silanization modification of the silicon–hydrogen surfaces has been established. Stability testing shows that the resulting organic monolayers are densely packed and are shown to be highly stable under a variety of conditions including hot water, hot organic solvent, acid, and base, but can be removed by a HF rinse.

[1]  J. Buriak,et al.  Exciton-mediated hydrosilylation on photoluminescent nanocrystalline silicon. , 2001, Journal of the American Chemical Society.

[2]  B. Martin,et al.  Surface Sol-Gel Synthesis of Ultrathin Semiconductor Films , 2000 .

[3]  A. V. Rao,et al.  In Situ Fourier‐Transform Electromodulated Infrared Study of Porous Silicon Formation: Evidence for Solvent Effects on the Vibrational Linewidths , 1991 .

[4]  H. Ahmed,et al.  Nanoscale colloidal particles: Monolayer organization and patterning , 1997 .

[5]  Kamitsos.  Reply to "Comment on 'Infrared-reflectance spectra of heat-treated, sol-gel-derived silica' " , 1996, Physical review. B, Condensed matter.

[6]  Jae Hee Song,et al.  Functionalization of Nanocrystalline Porous Silicon Surfaces with Aryllithium Reagents: Formation of Silicon−Carbon Bonds by Cleavage of Silicon−Silicon Bonds , 1998 .

[7]  Molecular Identification by Time‐Resolved Interferometry in a Porous Silicon Film , 2001 .

[8]  P. E. Laibinis,et al.  Derivatization of Porous Silicon by Grignard Reagents at Room Temperature , 1998 .

[9]  H. Shao,et al.  Determination of locations of sulfur, amide-nitrogen and azo-nitrogen in self-assembled monolayers of alkanethiols and azobenzenethiols on Au (111) and GaAs (100) by angle-resolved X-ray photoelectron spectroscopy , 1999 .

[10]  P. E. Laibinis,et al.  IMPROVED POLYPYRROLE/SILICON JUNCTIONS BY SURFACIAL MODIFICATION OF HYDROGEN-TERMINATED SILICON USING ORGANOLITHIUM REAGENTS , 1999 .

[11]  F. Ross,et al.  Pore morphology and the mechanism of pore formation in n-type silicon , 1992 .

[12]  M. Engelhard,et al.  Porous silicon as a versatile platform for laser desorption/ionization mass spectrometry. , 2001, Analytical chemistry.

[13]  Paul E. Laibinis,et al.  THERMAL DERIVATIZATION OF POROUS SILICON WITH ALCOHOLS , 1997 .

[14]  Jeffery L. Coffer,et al.  Steric Considerations in the Amine-Induced Quenching of Luminescent Porous Silicon , 1995 .

[15]  M. Sailor,et al.  Reaction of Photoluminescent Porous Silicon Surfaces with Lithium Reagents To Form Silicon−Carbon Bound Surface Species , 1999 .

[16]  Michael J. Sailor,et al.  A Porous Silicon Optical Biosensor: Detection of Reversible Binding of IgG to a Protein A-Modified Surface , 1999 .

[17]  L. Canham,et al.  Derivatized Mesoporous Silicon with Dramatically Improved Stability in Simulated Human Blood Plasma , 1999 .

[18]  J. Buriak,et al.  Chemical and Biological Applications of Porous Silicon Technology , 2000 .

[19]  D. Kwong,et al.  Study of thermal oxidation and nitrogen annealing of luminescent porous silicon , 1994 .

[20]  D. J. Lockwood,et al.  Ideal passivation of luminescent porous silicon by thermal, noncatalytic reaction with alkenes and aldehydes , 2001 .

[21]  Kirk Ct,et al.  Quantitative analysis of the effect of disorder-induced mode coupling on infrared absorption in silica. , 1988 .

[22]  D. W. Johnson,et al.  The optical constants of quartz, vitreous silica and neutron-irradiated vitreous silica (I) , 1976 .

[23]  J. Jorné,et al.  Electronic States and Luminescence in Porous Silicon Quantum Dots: The Role of Oxygen , 1999 .

[24]  Jonathan K. M. Chun,et al.  Proton Gated Emission from Porous Silicon , 1993 .

[25]  F. Ozanam,et al.  Preparation and characterization of surface-modified luminescent porous silicon , 1995 .

[26]  R. Maoz,et al.  On the formation and structure of self-assembling monolayers. I. A comparative atr-wettability study of Langmuir—Blodgett and adsorbed films on flat substrates and glass microbeads , 1984 .

[27]  M. Sailor,et al.  Chemical Modification of the Photoluminescence Quenching of Porous Silicon , 1993, Science.

[28]  A. G. Cullis,et al.  The structural and luminescence properties of porous silicon , 1997 .

[29]  M. Sailor,et al.  Light-Induced Reactions of Porous and Single-Crystal Si Surfaces with Carboxylic Acids , 1996 .

[30]  M. Ghadiri,et al.  A porous silicon-based optical interferometric biosensor. , 1997, Science.

[31]  Dongsheng Xu,et al.  In Situ Silanization Reaction on the Surface of Freshly Prepared Porous Silicon , 2002 .

[32]  J. E. Bateman,et al.  Alkylation of Porous Silicon by Direct Reaction with Alkenes and Alkynes. , 1998, Angewandte Chemie.

[33]  K. D. Hirschman,et al.  Silicon-based visible light-emitting devices integrated into microelectronic circuits , 1996, Nature.

[34]  J. Buriak,et al.  LEWIS ACID MEDIATED FUNCTIONALIZATION OF POROUS SILICON WITH SUBSTITUTED ALKENES AND ALKYNES , 1998 .

[35]  I. Haller.  Covalently attached organic monolayers on semiconductor surfaces , 1978 .

[36]  Leigh T. Canham,et al.  Lewis Acid Mediated Hydrosilylation on Porous Silicon Surfaces , 1999 .

[37]  Guanzhong Wang,et al.  Origin of the blue and red photoluminescence from aged porous silicon , 1998 .

[38]  Honglae Sohn,et al.  Detection of Fluorophosphonate Chemical Warfare Agents by Catalytic Hydrolysis with a Porous Silicon Interferometer , 2000 .

[39]  George,et al.  Hydrogen desorption kinetics from monohydride and dihydride species on silicon surfaces. , 1988, Physical review. B, Condensed matter.

[40]  A. Dillon,et al.  FTIR Studies of H2O and D2O Decomposition on Porous Silicon Surfaces , 1991 .

[41]  R. Muller,et al.  Chemical Surface Modification of Porous Silicon , 1993 .

[42]  F. Ozanam,et al.  Electrochemical Methoxylation of Porous Silicon Surface , 1995 .