Nanocontact printing

Abstract

A method of stamping of molecular patterns and/or devices based on the reversible self-assembly of molecules, particularly organic molecules is disclosed. This method is suitable for the stamping of almost any nanofabricated device and can be used to transferring a large amount of pattern information from one substrate to another at the same time.

1 .- 110 . (canceled) 
     
     
         111 . A composition, comprising:
 a) a master comprising a pattern of a first set of molecules bound to a first substrate; and   b) a complement image comprising a pattern of a second set of molecules bound to a second substrate via a reactive functional group on each molecule of the second set of molecules, wherein each molecule in the second set of molecules has a recognition component that binds to at least a portion of a molecule from the first set of molecule.   
     
     
         112 . The composition of  claim 111 , wherein each molecule of the second set of molecule further comprises one or more of the following components:
 a) an exposed functionality;   b) a covalent bond or a first spacer that links the reactive functional group to the recognition component; and   c) a covalent bond or a second spacer that links the exposed functionality to the recognition component.   
     
     
         113 . The composition of  claim 112 , wherein the second set of molecules comprises two or more different molecules. 
     
     
         114 . The composition of  claim 113 , wherein one or more molecules from the first set of molecules determines where each of the molecules from the second set of molecules binds. 
     
     
         115 . The composition of  claim 114 , wherein two or more molecules of the second set of molecules have different recognition components. 
     
     
         116 . The composition of  claim 114 , wherein two or more molecules of the second set of molecules have both different recognition components and different exposed functionalities. 
     
     
         117 . The composition of  claim 114 , wherein the two or more different molecules of the second set of molecules form a pattern on the second substrate that has a height profile that comprises two or more depths. 
     
     
         118 . The composition of  claim 117 , wherein at least one of the two or more different molecules comprises a first spacer, and another of the two or more different molecules either does not comprise a spacer or comprises a second spacer that has a different length from the first spacer. 
     
     
         119 . The composition of  claim 112 , wherein a lateral dimension of at least one feature of the complement image is less than 200 nm. 
     
     
         120 . The composition of  claim 112 , wherein the bonds foraied between the first set of molecules and the second set of molecules are hydrogen bonds, ionic bonds, covalent bonds, van der Waals bonds, or a combination thereof. 
     
     
         121 . The composition of  claim 120 , wherein the bonds between the first set of molecules and the second set of molecules are broken. 
     
     
         122 . The composition of  claim 120 , wherein the bonds formed between the first set of molecules and the second set of molecules are hydrogen bonds. 
     
     
         123 . The composition of  claim 112 , wherein the reactive functional group on the second set of molecules is a thiol group or a protected thiol group, and the surface of the second substrate is gold, silver, copper, cadmium, zinc, palladium, platinum, mercury, lead, iron, chromium, manganese, tungsten, or any alloys thereof. 
     
     
         124 . The composition of  claim 112 , wherein the reactive functional group on the second set of molecules is a silane or a chlorosilane, and the surface of the second substrate is doped or undoped silicon. 
     
     
         125 . The composition of  claim 112 , wherein the reactive functional group on the second set of molecules is a carboxylic acid, and the surface of the second substrate is an oxide. 
     
     
         126 . The composition of  claim 125 , wherein the oxide is silica, alumina, quartz, or glass. 
     
     
         127 . The composition of  claim 112 , wherein the reactive functional group on the second set of molecules is a nitrile or an isonitrile, and the surface of the second substrate is platinum, palladium or any alloy thereof. 
     
     
         128 . The composition of  claim 112 , wherein the reactive functional group on the second set of molecules is a hydroxamic acid, and the surface of the second substrate is copper. 
     
     
         129 . The composition of  claim 112 , wherein a component of each of the first set of molecules is a nucleic acid sequence and the recognition component of the second set of molecules is a nucleic acid sequence that has at least three consecutive bases that are complementary to at least three consecutive bases of at least one molecule from the first set of molecules. 
     
     
         130 . The composition of  claim 129 , wherein the bonds formed between the first set of molecules and the second set of molecules are hydrogen bonds. 
     
     
         131 . The composition of  claim 130 , wherein the second set of molecules comprises two or more different molecules, 
     
     
         132 . The composition of  claim 131 , wherein one or more molecules from the first set of molecules determines where each of the molecules from the second set of molecules binds. 
     
     
         133 . The composition of  claim 132 , wherem the first set of molecules comprises two or more molecules having different nucleic acid sequences. 
     
     
         134 . The composition of  claim 132 , wherein two or more molecules of the second set of molecules have different nucleic acid sequences. 
     
     
         135 . The composition of  claim 134 , wherein the nucleic acid sequence of the first and second sets of molecules are selected from the group consisting of DNA, RNA, modified nucleic acid sequences and combinations thereof. 
     
     
         136 . The composition of  claim 135 , wherein the hydrogen bonds between the first set of molecules and the second set of molecules are broken. 
     
     
         137 . The composition of  claim 112 , wherein a component of each of the first set of molecules is a peptide nucleic acid (PNA) sequence and the recognition component of the second set of molecules is a PNA sequence. 
     
     
         138 . The composition of  claim 121 , wherem the exposed functionality of each molecule of the second set of molecules is absent or is, independently, selected from the group consisting of —OH, —CONH—, —CONHCO—, —NH 2) —NH—, —COOH, —COOR, —CSNH—, —NO 2 ″, —SO 2 , —SH, —RCOR—, —RCSR—, —RSR, —ROR—, —PO 4 ″ 3 , —OSO 3 ″ 2 , —SO 3 ″ ? -COO″, —SOO′, —RSOR—, —CONR 2 , —(OCH 2 CH 2 ) n OH (where n=1-20, preferably 1-8), —CH 3 , —PO 3 H″, -2-imidazole, —N(CH 3 ) 2 , —NR 2 , —PO3H2, —CN, —(CF 2 )RCF 3  (where n=1-20, preferably 1-8), and an olefin,
 wherein, R is hydrogen, a hydrocarbon, a halogenated hydrocarbon, a protein, an enzyme, a carbohydrates, a lectin, a hormone, a receptor, an antigen, an antibody, or a hapten. 
 
     
     
         139 . The composition of  claim 138 , further comprising a metal or a metal ion bound to the exposed functional group of at least one molecule from the second set of molecules. 
     
     
         140 . The composition of  claim 139 , wherein the exposed functional group is TMSH, and the metal or metal ion is Au°, Ag°, or Ag + . 
     
     
         141 . The composition of  claim 139 , wherein the exposed functional group is —COOH, and the metal or metal ion is Ag° or Ag + . 
     
     
         142 . The composition of  claim 112 , wherein each molecule of the second set of molecules has a first spacer, a second spacer, or a first and the second spacer, and the spacers are, independently, selected from the group consisting of an alkylene, a heteroalkylene, a heterocycloalkylene, an alkenylene, an alkynylene, an arylene, a heteroarylene, arylalkylene, and a heteroarylalkylene, wherein the alkylene, heteroalkylene, heterocycloalkylene, alkenylene, alkynylene, arylene, heteroarylene, arylalkylene, or heteroarylalkylene may be substituted or unsubstituted. 
     
     
         143 . The composition of  claim 142 , wherein the substituents for the alkylene, a heteroalkylene, an alkenylene, an alkynylene, an arylene, a heteroarylene, a heterocycloalkylene, an arylalkylene, and a heteroarylalkylene are selected from the group consisting of halogens and hydroxy. 
     
     
         144 . The composition of  claim 121 , wherein at least one portion of the second substrate surface is free of the second set of molecules. 
     
     
         145 . A composition, comprising:
 a) a first pattern of a first set of molecules bound to a first substrate; and   b) a second pattern of a second set of molecules bound to a second substrate via a reactive functional group on each molecule of the second set of molecules, wherein each molecule of the second set of molecules comprises a recognition component that binds to at least one molecule in the first set of molecules, and wherein the second pattern is a complement image of the first pattern.   
     
     
         146 . The composition of  claim 145 , wherein each molecule of the second set of molecule further comprises one or more of the following components:
 a) an exposed functionality;   b) a covalent bond or a first spacer that links the reactive functional group to the recognition component; and   c) a covalent bond or a second spacer that links the exposed functionality to the recognition component.   
     
     
         147 . The composition of  claim 146 , wherein the second set of molecules comprises two or more different molecules. 
     
     
         148 . The composition of  claim 147 , wherein one or more molecules from the first set of molecules determines where each of the molecules from the second set of molecules binds. 
     
     
         149 . The composition of  claim 148 , wherein two or more molecules of the second set of molecules have different recognition components. 
     
     
         150 . The composition of  claim 148 , wherein two or more molecules of the second set of molecules have both different recognition components and different exposed functionalities. 
     
     
         151 . The composition of  claim 148 , wherein the two or more different molecules of the second set of molecules form a pattern on the second substrate that has a height profile that comprises two or more depths. 
     
     
         152 . The composition of  claim 151 , wherein at least one of the two or more different molecules comprises a first spacer, and another of the two or more different molecules either does not comprise a spacer or comprises a second spacer that has a different length from the first spacer. 
     
     
         153 . The composition of  claim 146 , wherein a lateral dimension of at least one feature of the complement image is less than 200 nm. 
     
     
         154 . The composition of  claim 146 , wherein the reactive functional group of the second set of molecules is a thiol group and the surface of the second substrate is gold, silver, copper, cadmium, zinc, palladium, platinum, mercury, lead, iron, chromium, manganese, tungsten, or any alloys thereof. 
     
     
         155 . The composition of  claim 146 , wherein the reactive functional group of the second set of molecules is a silane or a chlorosilane group and the surface of the second substrate is doped or undoped silicon. 
     
     
         156 . The composition of  claim 146 , wherein the reactive functional group of the second set of molecules is a carboxylic acid, and the surface of the second substrate is an oxide. 
     
     
         157 . The composition of  claim 156 , wherein the oxide is silica, alumina, quartz, or glass. 
     
     
         158 . The composition of  claim 146 , wherein the reactive functional group of the second monolayer of complementary molecules is a nitrile or an isonitrile group, and the surface of the second substrate is platinum, palladium or any alloy thereof. 
     
     
         159 . The composition of  claim 146 , wherein the reactive functional group of the second monolayer of complementary molecules is a hydroxamic acid, and the surface of the second substrate is copper. 
     
     
         160 . The composition of  claim 146 , wherein a component of each of the first set of molecules is a nucleic acid sequence and the recognition component of the second set of molecules is a nucleic acid sequence that has at least three consecutive bases that are complementary to at least three consecutive bases of at least one molecule from the first set of molecules. 
     
     
         161 . The composition of  claim 160 , wherein the second set of molecules comprises two or more different molecules. 
     
     
         162 . The composition of  claim 161 , wherein one or more molecules from the first set of molecules determines where each of the molecules from the second set of molecules binds. 
     
     
         163 . The composition of  claim 162 , wherein the first set of molecules comprises two or more molecules having different nucleic acid sequences. 
     
     
         164 . The composition of  claim 162 , wherein two or more molecules of the second set of molecules have different nucleic acid sequences. 
     
     
         165 . The composition of  claim 164 , wherein the nucleic acid sequence of the first and second sets of molecules are selected from the group consisting of DNA, RNA, modified nucleic acid sequences and combinations thereof. 
     
     
         166 . The composition of  claim 146 , wherein a component of each of the first set of molecules is a peptide nucleic acid (PNA) sequence and the recognition component of the second set of molecules is a PNA sequence. 
     
     
         167 . The composition of  claim 146 , wherein the exposed functionality of each molecule of the second set of molecules is absent or is, independently, selected from the group consisting of —OH, —CONH—, —CONHCO—, —NH 2 , —NH—, —COOH, —COOR, —CSNH—, —NO 2 ″, —SO 2 , —SH, —RCOR—, —RCSR—, —RSR, —ROR—, —PO 4 ″ 3 , —OSO 3 ″ 2 , —SO 3 ″, —COO″, —SOO″, —RSOR—, —CONR 2 , —(OCH 2 CH 2 ) n OH (where n=1-20, preferably 1-8), —CH 3 , —PO 3 H*, -2-imidazole, —N(CH 3 ) 2 , —NR 2 , —PO 3 H 2 , —CN, —(CF 2 ) n CF 3  (where n=1-20, preferably 1-8), and an olefin,
 wherein, R is hydrogen, a hydrocarbon, a halogenated hydrocarbon, a protein, an enzyme, a carbohydrates, a lectin, a hormone, a receptor, an antigen, an antibody, or a hapten. 
 
     
     
         168 . The composition of  claim 167 , further comprising a metal or a metal ion bound to the exposed functional group of at least one molecule from the second set of molecules. 
     
     
         169 . The composition of  claim 168 , wherein the exposed functional group is -˜SH, and the metal or metal ion is Au°, Ag°, or Ag + . 
     
     
         170 . The composition of  claim 168 , wherein the exposed functional group is —COOH, and the metal or metal ion is Ag° or Ag + . 
     
     
         171 . The composition of  claim 146 , wherein each molecule of the second set of molecules has a first spacer, a second spacer, or a first and the second spacer, and the spacers are, independently, selected from the group consisting of an alkylene, a heteroalkylene, a heterocycloalkylene, an alkenylene, an alkynylene, an arylene, a heteroarylene, arylalkylene, and a heteroarylalkylene, wherein the alkylene, heteroalkylene, heterocycloalkylene, alkenylene, alkynylene, arylene, heteroarylene, arylalkylene, or heteroarylalkylene may be substituted or unsubstituted. 
     
     
         172 . The composition of  claim 171 , wherein the substituents for the alkylene, a heteroalkylene, a heterocycloalkylene, an alkenylene, an alkynylene, an arylene, a heteroarylene, an arylalkylene, and a heteroarylalkylene are selected from the group consisting of halogens and hydroxy. 
     
     
         173 . The composition of  claim 146 , wherein at least one portion of the second substrate surface is free of the second set of molecule. 
     
     
         174 . The composition of  claim 146 , wherein the portion of the second substrate that is free of the second set of molecules has been degraded. 
     
     
         175 . The composition of  claim 173 , wherein a material has been deposited on the portion of the second substrate that is free of the second set of molecules. 
     
     
         176 . The composition of  claim 175 , wherein the deposited material is selected from the group consisting of semiconductors, dielectrics, metals, metal oxides, metal nitrides, metal carbides, and combinations thereof. 
     
     
         177 . A composition, comprising:
 a) a first pattern of a first set of molecules bound to a first substrate; and   b) a second substrate, wherein the second substrate comprises a degraded portion and an undegraded portion and is a complement image of the first pattern.   
     
     
         178 . The composition of  claim 177 , wherein the complement image is formed by a method comprising the steps of:
 a) forming a second pattern of a second set of molecules on the second substrate, wherein the second pattern is a complement image of the first pattern, and wherein at least one portion of the second substrate surface is free of the second set of molecules;   b) degrading the portion of the second substrate that is free of the second set of molecules; and   c) removing the second set of molecules from the second substrate, thereby exposing the surface of the second substrate.   
     
     
         179 . A composition, comprising:
 a) a first pattern of a first set of molecules bound to a first substrate; and   b) a second substrate having a patterned layer of a material deposited thereon, wherein the patterned layer of deposited material on the second substrate is a complement image of the first pattern.   
     
     
         180 . The composition of  claim 179 , wherein the complement image is formed on the second substrate by a method comprising the steps of;
 a) forming a second pattern of a second set of molecules on the second substrate, wherein the second pattern is a complement image of the first pattern, and wherein at least one portion of the second substrate surface is
 free of the second set of molecules; 
   b) depositing a material on the portion of the second substrate that is free of
 the second set of molecules; and 
   c) removing the second set of molecules from the second substrate, thereby exposing the surface of the second substrate.   
     
     
         181 . The composition of  claim 179 , wherein the deposited material is selected from the group consisting of semiconductors, dielectrics, metals, metal oxides, metal nitrides, metal carbides, and combinations thereof. 
     
     
         182 .- 245 . (canceled)