Novel attachment chemistry for organic molecules to silicon

Abstract

A simple chemical approach for the covalent assembly of organic molecules on silicon surfaces via robust linkages is provided. This is achieved by the efficient reaction between a nucleophilic functional group and a halogenated Si surface. The nucleophile anchor is the bridge between two surface Si atoms. The resulting organic layer is thermally stable. The method demonstrated herein is generally applicable for the assembly of a variety of functional organic molecules under vacuum environment or in solution phase.

What is claimed is:  
     
         1 . A method for attaching organic molecules to a silicon surface comprising reacting a nucleophilic organic molecule with a halogenated silicon surface.  
     
     
         2 . A method according to  claim 1 , wherein said silicon surface comprises a silicon selected from the group consisting of crystalline silicon, amorphous silicon, flat silicon, and porous silicon.  
     
     
         3 . A method according to  claim 1 , wherein the reaction of said nucleophilic organic compound with said halogenated silicon surface is preformed in solution phase or in a substantially vacuum environment.  
     
     
         4 . A method according to  claim 1 , wherein said halogenated silicon surface is prepared by reacting a clean silicon surface with a halogen source to form a halogenated silicon surface.  
     
     
         5 . A method according to  claim 4 , wherein said clean silicon surface is prepared by heating a silicon surface to a temperature sufficient to substantially clean the silicon surface of impurities.  
     
     
         6 . A method according to  claim 1 , wherein said halogenated silicon surface is prepared by reacting a hydrogen terminated silicon surface with a halogen source in gas phase or in solution to form a halogenated silicon surface.  
     
     
         7 . A method according to  claim 4 , wherein said halogen source is a chlorine source and said halogenated silicon surface is a chlorinated silicon surface.  
     
     
         8 . A method according to  claim 6 , wherein said halogen source is a chlorine source and said halogenated silicon surface is a chlorinated silicon surface.  
     
     
         9 . A method according to  claim 7 , wherein said chlorine source is selected from the group consisting of Cl 2 , SOCl 2 , phosgene and oxalyl chloride.  
     
     
         10 . A method according to  claim 8 , wherein said chlorine source is selected from the group consisting of Cl 2 , SO 2 Cl 2 , Cl 3 CSO 2 Cl, n-chlorosuccinimide, C 6 H 5 Cl 2 , t-C 4 H 9 OCl, PCl 5  phosgene and oxalyl chloride.  
     
     
         11 . A method according to  claim 6 , wherein said silicon is reacted with said halogen source in the presence of a radical initiator catalyst, and said reaction is carried out in solution.  
     
     
         12 . A method according to  claim 11 , wherein said catalyst is selected from the group consisting of azocompounds, peroxides, photons, and Bu 3 SnH  
     
     
         13 . A method according to  claim 12 , wherein said catalyst is benzoyl peroxide.  
     
     
         14 . A method according to  claim 1 , wherein said nucleophilic organic compound contains a nucleophilic functionality selected from the group consisting of amines, ═NH, —OH, —SH, SeH, TeH, and PH 2 .  
     
     
         15 . A surface material comprising a nucleophilic organic molecule covalently bonded to silicon, wherein said surface material is produced by a process comprising reacting a nucleophilic organic molecule with a halogenated silicon surface.  
     
     
         16 . A surface material according to  claim 15 , wherein said silicon surface comprises a porous silicon or a crystalline silicon.  
     
     
         17 . A surface material according to  claim 15 , wherein the reaction of said nucleophilic organic molecule with said halogenated silicon surface is preformed in solution phase or in a substantially vacuum environment.  
     
     
         18 . A surface material according to  claim 15 , wherein said halogenated silicon surface is prepared by reacting a clean silicon surface in gas phase with a halogen source to form a halogenated silicon surface.  
     
     
         19 . A surface material according to  claim 18 , wherein said clean silicon surface is prepared by heating a native oxide covered silicon surface in vacuo to sufficiently high temperatures.  
     
     
         20 . A surface material according to  claim 15 , wherein said halogenated silicon surface is prepared by reacting a hydrogen terminated silicon surface with a halogen source in gas phase or in solution to form a halogenated silicon surface.  
     
     
         21 . A surface material according to  claim 18 , wherein said halogen source is a chlorine source and said halogenated silicon surface is a chlorinated silicon surface.  
     
     
         22 . A surface material according to  claim 20 , wherein said halogen source is a chlorine source and said halogenated silicon surface is a chlorinated silicon surface.  
     
     
         23 . A surface material according to  claim 21 , wherein said chlorine source is selected from the group consisting of Cl 2 , SOCl 2 , phosgene and oxalyl chloride.  
     
     
         24 . A surface material according to  claim 22  wherein said chlorine source is selected from the group consisting of Cl 2 , SO 2 Cl 2 , Cl 3 CSO 2 Cl, n-chlorosuccinimide, C 6 H 5 Cl 2 , t-C 4 H 9 OCl, PCl 5  phosgene and oxalyl chloride.  
     
     
         25 . A surface material according to  claim 24 , wherein said silicon is reacted with said halogen source in solution in the presence of a radical initiator catalyst.  
     
     
         26 . A surface material according to  claim 25 , wherein said catalyst is selected from the group consisting of azocompounds, peroxides, photons, and Bu 3 SnH.  
     
     
         27 . A surface material according to  claim 26 , wherein said catalyst is benzoyl peroxide.  
     
     
         28 . A surface material according to  claim 15 , wherein said nucleophilic organic compound contains a nucleophilic functionality selected from the group consisting of amines ═NH, —OH, —SH, SeH, TeH, and PH 2 .  
     
     
         29 . A method of producing an improved device for detecting multiple binding reactions, comprising reacting an organic molecule containing a nucleophilic functionality with a halogenated silicon surface of said device.  
     
     
         30 . The method according to  claim 29 , wherein said nucleophilic molecule is a bifunctional molecule.  
     
     
         31 . The method according to  claim 30 , wherein said bifunctional molecule contains at least two functional groups selected from the group consisting of amines, ═NH, —OH, —SH, SeH, TeH, and PH 2 .  
     
     
         32 . The method according to  claim 31 , wherein said two functional groups are —OH and —SH.  
     
     
         33 . The method according to  claim 30 , further comprising linking said bifunctional molecule to a binding reagent selected from the group consisting of DNA, proteins, legends, and oligonucleotide probes.  
     
     
         34 . The method according to  claim 33 , wherein said bifunctional molecule is linked directly to said binding reagent.  
     
     
         35 . The method according to  claim 33 , wherein said bifunctional molecule is linked to said binding reagent via a second bifunctional spacer molecule.  
     
     
         36 . The method according to  claim 33 , wherein the binding reagents are oligonucleotide probes.  
     
     
         37 . The method according to  claim 33 , wherein the binding reagents are attached within channels densely packed in a solid substrate.  
     
     
         38 . A device for detecting multiple binding reactions, wherein said device is produced by reacting an organic molecule containing a nucleophilic functionality with a halogenated silicon surface of said device.  
     
     
         39 . The device according to  claim 38 , wherein said organic molecule is a bifunctional molecule.  
     
     
         40 . The device according to  claim 39 , wherein said bifunctional molecule contains at least two functional groups selected from the group consisting of amines, ═NH, —OH, —SH, SeH, TeH, and PH 2 .  
     
     
         41 . The device according to  claim 40 , wherein said two functional groups are —OH and —SH.  
     
     
         42 . The device according to  claim 39 , further comprising linking said bifunctional molecule to a binding reagent selected from the group consisting of DNA, proteins, legends, and oligonucleotide probes.  
     
     
         43 . The device according to  claim 42 , wherein said bifunctional molecule is linked directly to said binding reagent.  
     
     
         44 . The device according to  claim 43 , wherein said bifunctional molecule is linked to said binding reagent via a second bifunctional spacer molecule.  
     
     
         45 . The device according to  claim 42 , wherein the binding reagents are oligonucleotide probes.  
     
     
         46 . The device method according to  claim 42 , wherein the binding reagents are attached within channels densely packed in a solid substrate.