Nanolithography methods and products therefor and produced thereby

Abstract

In one aspect, a method of nanolithography is provided using a driving force to control the movement of a deposition compound from a scanning probe microscope tip to a substrate. Another aspect of the invention provides a tip for use in nanolithography having an internal cavity and an aperture restricting movement of a deposition compound from the tip to the substrate. The rate and extent of movement of the deposition compound through the aperture is controlled by a driving force.

What is claimed is:  
     
         1 . A method of nanolithography, comprising: 
 providing a substrate;    providing a tip comprising an internal cavity having an external opening to the surface of said tip, wherein said opening comprises an internal diameter of less than about 200 nanometers    loading said cavity with a deposition compound, wherein said deposition compound does not pass through said external opening in the absence of a driving force; and    subjecting said tip to a driving force to deliver said deposition compound through said external opening to be deposited on said substrate.    
     
     
         2 . The method of  claim 1 , wherein said internal cavity comprises a medium semi-permeable to said deposition compound.  
     
     
         3 . The method of  claim 2 , wherein said deposition compound passes through said medium through the external opening onto said substrate.  
     
     
         4 . The method of  claim 3 , wherein said medium is at least one of a polymeric gel and a liquid suspension.  
     
     
         5 . The method of  claim 4 , wherein said deposition compound is a biomolecule.  
     
     
         6 . The method of  claim 1 , wherein the substrate is gold and the deposition compound is a protein or peptide or has the formula R 1 SH, R 1 SSR 2 , R 1 SR 2 , R 1 SO 2 H, (R 1 ) 3 P, R 1 NC, R 1 CN,(R 1 ) 3 N, R 1 COOH, or ArSH, wherein: 
 R 1 and R 2  each has the formula X(CH 2 ) n and, if a compound is substituted with both R   1 and R 2 , then R 1 and R 2  can be the same or different;    n is 0-30;    Ar is an aryl;    X is —CH 3 , —CHCH 3 , —COOH, —CO 2 (CH 2 ) m CH 3 , —OH, —CH 2 OH, ethylene glycol, hexa(ethylene glycol), —O(CH 2 ) m CH 3 , —NH 2 , —NH(CH 2 )mNH 2 , halogen, glucose, maltose, fullerene C 60 , a nucleic acid, a protein, or a ligand; and    m is 0-30.    
     
     
         7 . The method of  claim 6 , wherein the deposition compound has the formula R 1 SH or ARSH.  
     
     
         8 . The method of  claim 1 , wherein the substrate is aluminum, gallium arsenide or titanium dioxide and the deposition compound has the formula R 1 SH, wherein: 
 R 1 has the formula X(CH 2 ) n ;    n is 0-30;    Xis —CH 3 , —CHCH 3 , —COOH, —CO 2 (CH 2 ) m CH 3 , —OH, —CH 2 OH, ethylene glycol, hexa(ethylene glycol), —O(CH 2 ) m CH 3 , —NH 2 —NH(CH 2 ) m NH 2 , halogen, glucose, maltose, fullerene C 60 , a nucleic acid, a protein, or a ligand; and    m is 0-30.    
     
     
         9 . The method of  claim 8 , wherein the deposition compound is selected from the group consisting of 2-mercaptoacetic acid and n-octadecanethiol.  
     
     
         10 . The method of  claim 1 , wherein the substrate is silicon dioxide and the deposition compound is selected from the group consisting of a protein, a peptide and a compound having the formula R 1 SH or R 1 SiCl 3 , wherein: 
 R 1  has the formula X(CH 2 ) n ;    n is 0-30;    X is —CH 3 , —CHCH 3 , —COOH, —CO 2 (CH 2 ) m CH 3 , —OH, —CH 2 OH, ethylene glycol, hexa(ethylene glycol), —O(CH 2 ) m CH 3 , —NH 2 , —NH(CH 2 ) m NH 2 , halogen, glucose, maltose, fullerene C 60 , a nucleic acid, a protein, or a ligand; and    mis 0-30.    
     
     
         11 . The method of  claim 10 , wherein the deposition compound is 16-mercapto-1-hexadecanoic acid, octadecyltrichlorosilane or 3-(2-aminoethylamino)propyltrimethoxysilane.  
     
     
         12 . The method of  claim 1 , wherein the substrate is oxidized gallium arsenide or silicon dioxide and the deposition compound is a silazane.  
     
     
         13 . The method of  claim 1 , wherein said external opening comprises an internal diameter of about 1 nanometers to about 15 nanometers.  
     
     
         14 . The method of  claim 1 , wherein movement of said deposition compound is achieved by said driving force.  
     
     
         15 . The method of  claim 14 , wherein said driving force is selected from the group consisting of an electrical, a magnetic and a chemical driving force.  
     
     
         16 . The method of  claim 15 , wherein said driving force is an electrical driving force created by a negatively charged deposition compound and a positively charged substrate.  
     
     
         17 . The method of  claim 15 , wherein said driving force is an electrical driving force created by a positively charged deposition compound and a negatively charged substrate.  
     
     
         18 . The method of  claim 15 , wherein said driving force is a magnetic driving force created between a magnetically charged deposition compound and a magnetically active substrate.  
     
     
         19 . The method of  claim 15 , wherein said driving force is a chemical driving force created by a substrate having a chemical attraction to said deposition compound.  
     
     
         20 . The method of  claim 1 , wherein said external opening is a size-specific aperture adaptable to sub-nanometer scale features.  
     
     
         21 . The method of  claim 20 , wherein said size-specific aperture is produced by a process selected from the group consisting of focused ion beam, mechanical/ion polishing of narrow tip-cones and electron beam drilling.  
     
     
         22 . The method of  claim 21 , wherein said size-specific aperture comprises an ultra-thin membrane.  
     
     
         23 . The method of  claim 22 , wherein said ultra-thin membrane is about 2 nanometers to about 100 nanometers thick.  
     
     
         24 . The method of  claim 22 , wherein said ultra-thin membrane comprises a substance selected from the group consisting of SiO 2 , Si 3 N 4 , diamond and amorphous carbon.  
     
     
         25 . The method of  claim 22 , wherein said ultra-thin membrane comprises a circular aperture.  
     
     
         26 . The method of  claim 22 , wherein said ultra-thin membrane comprises a square aperture.  
     
     
         27 . The method of  claim 20 , wherein said size-specific aperture comprises an ultra-thin crystalline membrane.  
     
     
         28 . The method of  claim 27 , wherein said ultra-thin crystalline membrane is selected from the group consisting of magnesium oxide, sapphire, diamond and semiconductors.  
     
     
         29 . The method of  claim 1 , wherein said tip is an atomic force microscope tip.  
     
     
         30 . The method of  claim 1 , wherein said tip is a near field scanning optical microscope tip.  
     
     
         31 . The method of  claim 1 , wherein said tip is coated with a hydrophobic compound.  
     
     
         32 . The method of  claim 31 , wherein the hydrophobic compound has the formula RNH 2  wherein: 
 R is an alkyl of the formula CH 3 (CH 2 ) n or an aryl; and    nis 0-30.    
     
     
         33 . The method of  claim 32 , wherein the hydrophobic compound is 1-dodecylamine.  
     
     
         34 . A method of nanolithography, comprising: 
 providing a substrate;    providing a scanning probe microscope tip comprising an internal cavity having an external opening to the surface of said tip, wherein said tip is coated with a hydrophobic compound and wherein said opening comprises an internal diameter of about 1 nanometers to about 15 nanometers;    loading said cavity with a deposition compound, wherein said deposition compound does not pass through said external opening in the absence of a driving force; and    subjecting said tip to a driving force to deliver said deposition compound through said external opening to be deposited on said substrate, wherein said driving force is selected from the group consisting of an electrical, a magnetic and a chemical driving force.    
     
     
         35 . A nanolithography device comprising a scanning probe microscope tip comprising an internal cavity having an external opening to the surface of said tip.  
     
     
         36 . The device of  claim 35 , wherein said external opening comprises a size-specific aperture.  
     
     
         37 . The device of  claim 36 , wherein said size-specific aperture is created by electron beam drilling.  
     
     
         38 . The device of  claim 36 , wherein said size-specific aperture is adapted to sub-nanometer scale features.  
     
     
         39 . The device of  claim 36 , wherein said size-specific aperture is produced by at least one of focused ion beam, mechanical/ion polishing of narrow tip-cones and electron beam drilling.  
     
     
         40 . The device of  claim 36 , wherein said size-specific aperture comprises an ultra-thin membrane.  
     
     
         41 . The device of  claim 40 , wherein said ultra-thin membrane is about 2 nanometers to about 10 nanometers thick.  
     
     
         42 . The device of  claim 40 , wherein said ultra-thin membrane comprises a substance selected from the group consisting of SiO 2 , Si 3 N 4  and amorphous carbon.  
     
     
         43 . The device of  claim 40 , wherein said ultra-thin membrane comprises an aperture in a shape selected from the group consisting of elliptical and polygonal apertures.  
     
     
         44 . The device of  claim 40 , wherein said ultra-thin membrane comprises a square aperture.  
     
     
         45 . The device of  claim 36 , wherein said aperture comprises an ultra-thin crystalline membrane.  
     
     
         46 . The device of  claim 45 , wherein said ultra-thin crystalline membrane is selected from the group consisting of magnesium oxide, sapphire, diamond and semiconductors.  
     
     
         47 . The device of  claim 36 , wherein said aperture comprises a nanotube.  
     
     
         48 . The device of  claim 47 , wherein said nanotube comprises a carbon nanotube mounted to an atomic force microscope tip.  
     
     
         49 . The method of  claim 1 , wherein said tip is coated with a hydrophilic compound.  
     
     
         50 . A method of nanolithography, comprising: 
 providing a substrate;    providing a scanning probe microscope tip;    coating the tip with a deposition compound; and    subjecting said coated tip to a driving force to deliver said deposition compound to said substrate so as to produce a desired pattern.    
     
     
         51 . The method of  claim 50 , wherein the substrate is gold and the deposition compound is a protein or peptide or has the formula R 1 SH, R 1 SSR 2 , R 1 SR 2 , R 1 SO 2 H, (R 1 ) 3 P, R 1 NC, R 1 CN,(R 1 ) 3 N, R 1 COOH, or ArSH, wherein: 
 R 1 and R 2  each has the formula X(CH 2 ) n and, if a compound is substituted with both R 1 and R 2 , then R 1 and R 2  can be the same or different;    n is 0-30;    Ar is an aryl;    X is —CH 3 , —CHCH 3 , —COOH, —CO 2 (CH 2 ) m CH 3 , —OH, —CH 2 OH, ethylene glycol, hexa(ethylene glycol), —O(CH 2 ) m CH 3 , —NH 2 , —NH(CH 2 ) m NH 2 , halogen, glucose, maltose, fullerene C 60 , a nucleic acid, a protein, or a ligand; and    mis 0-30.    
     
     
         52 . The method of  claim 51 , wherein the deposition compound has the formula R 1 SH or ArSH.  
     
     
         53 . The method of  claim 50 , wherein the substrate is aluminum, gallium arsenide or titanium dioxide and the deposition compound has the formula R 1 SH, wherein: 
 R 1 has the formula X(CH 2 ) n ;    n is 0-30;    Xis —CH 3 , —CHCH 3 , —COOH, —CO 2 (CH 2 ) m CH 3 , —OH, —CH 2 OH, ethylene glycol, hexa(ethylene glycol), —O(CH 2 ) m CH 3 , —NH 2 , —NH(CH 2 )mNH 2 , halogen, glucose, maltose, fullerene C 60 , a nucleic acid, a protein, or a ligand; and    m is 0-30.    
     
     
         54 . The method of  claim 53 , whereinthe deposition compound is selected from the group consisting of 2-mercaptoacetic acid and n-octadecanethiol.  
     
     
         55 . The method of  claim 50 , wherein the substrate is silicon dioxide and the deposition compound is selected from the group consisting of a protein, a peptide and a compound having the formula R 1 SH or R 1 SiCl 3 , wherein: 
 R 1 has the formula X(CH 2 ) n ;    n is 0-30;    X is —CH 3 , —CHCH 3 , —COOH, —CO 2 (CH 2 ) m CH 3 , —OH, —CH 2 OH, ethylene glycol, hexa(ethylene glycol), —O(CH 2 ) m CH 3 , —NH 2 , —NH(CH 2 ) m NH 2 , halogen, glucose, maltose, fullerene C 60 , a nucleic acid, a protein, or a ligand; and    m is 0-30.    
     
     
         56 . The method of  claim 55 , wherein the deposition compound is 16-mercapto-1-hexadecanoic acid, octadecyltrichlorosilane or 3-(2-aminoethylamino)propyltrimethoxysilane.  
     
     
         57 . The method of  claim 50 , wherein the substrate is oxidized gallium arsenide or silicon dioxide and the deposition compound is a silazane.  
     
     
         58 . The method of  claim 50  wherein the tip is coated with the deposition compound by contacting the tip with a solution of the deposition compound one or more times.  
     
     
         59 . The method of  claim 58  further comprising drying the tip each time it is removed from the solution of the deposition compound, and the dried tip is contacted with the substrate to produce the desired pattern.  
     
     
         60 . The method of  claim 58  further comprising drying the tip each time it is removed from the solution of the deposition compound, except for the final time so that the tip is still wet when it is contacted with the substrate to produce the desired pattern.  
     
     
         61 . The method of  claim 58  further comprising: 
 rinsing the tip after it is has been used to apply the pattern to the substrate;  
 coating the tip with a different deposition compound; and  
 contacting the coated tip with the substrate so that the deposition compound is applied to the substrate so as to produce a desired pattern.  
 
     
     
         62 . The method of  claim 61  wherein the rinsing, coating and contacting steps are repeated using as many different deposition compounds as are needed to make the desired pattern(s).  
     
     
         63 . The method of  claim 50 , wherein said deposition compound is a biomolecule.  
     
     
         64 . The method of  claim 50 , wherein movement of said deposition compound is achieved by said driving force.  
     
     
         65 . The method of  claim 64 , wherein said driving force is selected from the group consisting of an electrical, a magnetic and a chemical driving force.  
     
     
         66 . The method of  claim 65 , wherein said driving force is an electrical driving force created by a negatively charged deposition compound and a positively charged substrate.  
     
     
         67 . The method of  claim 65 , wherein said driving force is an electrical driving force created by a positively charged deposition compound and a negatively charged substrate.  
     
     
         68 . The method of  claim 65 , wherein said driving force is a magnetic driving force created between a magnetically charged deposition compound and a magnetically active substrate.  
     
     
         69 . The method of  claim 65 , wherein said driving force is a chemical driving force created by a substrate having a chemical attraction to said deposition compound.  
     
     
         70 . The method of  claim 50 , wherein said tip is an atomic force microscope tip.  
     
     
         71 . The method of  claim 50 , wherein said tip is a near field scanning optical microscope tip.  
     
     
         72 . The method of  claim 50 , wherein said tip is coated with a hydrophobic compound.  
     
     
         73 . The method of claim  72 , wherein the hydrophobic compound has the formula RNH 2  wherein: 
 Ris an alkyl of the formula CH 3 (CH 2 )n or an aryl; and    n is 0-30.    
     
     
         74 . The method of claim  73 , wherein the hydrophobic compound is 1-dodecylamine.