Nonlithographic method to produce masks by selective reaction, articles produced, and composition for same

Abstract

A method for forming a self aligned pattern on an existing pattern on a substrate comprising applying a coating of the masking material to the substrate; and allowing at least a portion of the masking material to preferentially attach to portions of the existing pattern. The pattern is comprised of a first set of regions of the substrate having a first atomic composition and a second set of regions of the substrate having a second atomic composition different from the first composition. The first set of regions may include one or more metal elements and the second set of regions may include a dielectric. The masking material may comprise a polymer containing a reactive grafting site that selectively binds to the portions of the pattern. The masking material may include a polymer that binds to the portions of the pattern to provide a layer of functional groups suitable for polymerization initiation, a reactive molecule having functional groups suitable for polymerization propagation, or a reactive molecule, wherein reaction of the reactive molecule with the portion of the pattern generates a layer having reactive groups, which participate in step growth polymerization. Structures in accordance with the method. Compositions for practicing the method.

What is claimed is:  
     
         1 . A method for forming a self aligned pattern on an existing pattern on a substrate having a top surface comprising: 
 applying a coating of said masking material to said top surface of said substrate; and    allowing at least a portion of said masking material to preferentially attach to portions of said existing pattern to said top surface.    
     
     
         2 . The method of  claim 1 , wherein said pattern applied to said top surface is comprised of a first set of regions of the substrate having a first atomic composition and a second set of regions of the substrate having a second atomic composition different from the first composition.  
     
     
         3 . The method of  claim 2 , wherein said masking material comprises a self-assembled monolayer that selectively binds to said second set of regions of said pattern.  
     
     
         4 . The method of  claim 2 , wherein said first set of regions includes one or more metal elements and wherein said second set of regions includes a dielectric.  
     
     
         5 . The method of  claim 2 , wherein said masking material comprises a polymer containing a reactive grafting site that selectively binds to said second set of regions of said pattern applied to said top surface.  
     
     
         6 . The method of  claim 5 , wherein said polymer is selected from the group consisting of: poly(oxides), poly(carbonates), poly(esters), poly(anhydrides), poly(urethanes), poly(sulfonates), poly(siloxanes), poly(sulfides), poly(thioethers), poly(thioesters), poly(sulfones), poly(sufonamides), poly(amides), poly(imines), poly(ureas), poly(phosphazenes), poly(silanes), poly(siloxanes), poly(silazanes), poly(nitriles), poly(imides), poly(oxazoles), poly(benzoxazoles), poly(thiazoles), poly(pyrazoles), poly(triazoles), poly(thiophenes), poly(oxadiazoles), poly(thiazines), poly(thiazoles), poly(quionoxalines), poly(benzimidazoles), poly(oxindoles), poly(indolines), poly(pyridines) poly(triazines), poly(piperazines), poly(pyridines), poly(piperdines), poly(pyrrolidines), poly(carboranes), poly(fluoresceins), poly(acetals), and poly(anhydrides).  
     
     
         7 . The method of  claim 5 , wherein said polymer has a reactive functional group serving as said grafting site, said functional group being selected from the group consisting of: acyl chlorides, anhydrides, hydroxys, esters, ethers, aldehydes, ketones, carbonates, acids, epoxies, aziridines, phenols, amines, amides, imides, isocyanates, thiols, sulfones, halides, phosphines, phosphine oxides, nitros, azos, benzophenones, acetals, ketals, diketones, and organosilanes (Si x L y R z, ) where L is selected from the group consisting of hydroxy, methoxy, ethoxy, acetoxy, alkoxy, carboxy, amines, halogens, R is selected from the group consisting of hydrido, methyl, ethyl, vinyl, and phenyl (any alkyl or aryl).  
     
     
         8 . The method of  claim 1 , wherein said masking material includes a polymer that is generated from a reactive molecule that binds to said portions of said pattern to provide a layer of functional groups.  
     
     
         9 . The method of  claim 8 , wherein said layer is a molecular monolayer.  
     
     
         10 . The method of  claim 8 , wherein the said reactive molecule is bifunctional and includes a first moiety that binds to said portions of said pattern and a second moiety that serves as a polymerization initiator.  
     
     
         11 . The method of  claim 10 , wherein the said first moiety that binds to said portions of said pattern is selected from the group consisting of acyl chlorides, anhydrides, hydroxys, esters, ethers, aldehydes, ketones, carbonates, acids, epoxies, aziridines, phenols, amines, amides, imides, isocyanates, thiols, sulfones, halides, phosphines, phosphine oxides, nitros, azos, benzophenones, acetals, ketals, diketones, and organosilanes(Si x L y R z, ) where L is selected from the group consisting of hydroxy, methoxy, ethoxy, acetoxy, alkoxy, carboxy, amines, halogens, R is selected from the group consisting of hydrido, methyl, ethyl, vinyl, and phenyl (any alkyl or aryl).  
     
     
         12 . The method of  claim 10 , wherein the said second moiety that serves as a polymerization initiator is selected from the group consisting of peroxides, nitroxides, halides, azos, peresters, thioesters, hydroxy; metal organics having the stoichiometry of RX where R may consist of: benzyl, cumyl, butyl, alkyl, napthalene, and X may consist of sodium, lithium, and potassium; protonic acids, lewis acids, carbenium salts, tosylates, triflates, benzophenones, aryldiazonium, diaryliodonium, triarylsulfonium, acetals, ketals, and diketones.  
     
     
         13 . The method of  claim 10 , further comprising applying a reactive monomer to said layer of functional groups, so that said reactive monomer polymerizes on said layer.  
     
     
         14 . The method of  claim 13 , wherein said reactive monomer is a substituted ethylenic organic molecule.  
     
     
         15 . The method of  claim 13 , wherein said reactive monomer comprises a monomeric ring.  
     
     
         16 . The method of  claim 13 , wherein said reactive monomer polymerizes when exposed to one of a free radical, an anion, a cation, or a transition metal catalyst.  
     
     
         17 . The method of  claim 13 , wherein said reactive monomer polymerizes when exposed to thermal annealing or irradiation.  
     
     
         18 . The method of  claim 13 , wherein said reactive monomer is selected from the group consisting of: dienes, alkenes, acrylics, methacrylics, acrylamides, methacrylamides, vinylethers, vinyl alcohols, ketones, acetals, vinylesters, vinylhalides, vinylnitriles, styrenes, vinyl pyridines, vinyl pyrrolidones, vinyl imidazoles, vinylheterocyclics, cyclic lactams, cyclic ethers, cyclic lactones, cycloalkenes, cyclic thioesters, cyclic thioethers, aziridines, phosphozines, siloxanes, oxazolines, oxazines, thiiranes, capolactones, propylene glycol, and a substituted ethylenic organic molecule.  
     
     
         19 . The method of  claim 8 , further comprising applying a reactive monomer which undergoes polymerization on said layer.  
     
     
         20 . The method of  claim 19 , wherein said polymerization comprises a chain growth mechanism wherein polymerization proceeds through addition of a monomer to a reactive polymer.  
     
     
         21 . The method of  claim 1 , wherein said masking material includes a reactive molecule having functional groups suitable for polymerization propagation.  
     
     
         22 . The method of  claim 21 , wherein said reactive molecule is comprised of a first moiety that binds the reactive molecule to said portions of said existing pattern, and a second moiety that serves as a monomeric unit.  
     
     
         23 . The method of  claim 22 , wherein said first moiety that binds the reactive molecule to said portions of said existing pattern is selected from the group consisting of: carboxylic acids. acyl chlorides, anhydrides, hydroxys, esters, ethers, aldehydes, ketones, carbonates, acids, epoxies, aziridines, phenols, amines, amides, imides, isocyanates, thiols, sulfones, halides, phosphines, phosphine oxides, nitros, azos, benzophenones, acetals, ketals, diketones, organosilanes, and organosilanes (Si x L y R z, ) where L is selected from the group consisting of hydroxy, methoxy, ethoxy, acetoxy, alkoxy, carboxy, amines, halogens, R is selected from the group consisting of hydrido, methyl, ethyl, vinyl, phenyl (any alkyl or aryl).  
     
     
         24 . The method of  claim 22 , wherein said second moiety that serves as a monomeric unit comprises a substituted ethylenic organic molecule.  
     
     
         25 . The method of  claim 22 , wherein said second moiety that serves as a monomeric unit comprises a monomeric ring.  
     
     
         26 . The method of  claim 22 , wherein said reactive monomer polymerizes when exposed to one of a free radical, an anion, cation, or a transition metal catalyst.  
     
     
         27 . The method of  claim 22 , wherein said reactive monomer polymerizes when exposed to thermal annealing or irradiation.  
     
     
         28 . The method of  claim 22 , wherein said second moiety that serves as a monomeric unit is selected from the group consisting of: dienes, alkenes, acrylics, methacrylics, acrylamides, methacrylamides, vinylethers, vinyl alcohols, ketones, acetals, vinylesters, vinylhalides, vinylnitriles, styrenes, vinyl pyridines, vinyl pyrrolidones, vinyl imidazoles, vinylheterocyclics, styrene, cyclic lactams, cyclic ethers, cyclic lactones, cycloalkenes, cyclic thioesters, cyclic thioethers, aziridines, phosphozines, siloxanes, oxazolines, oxazines, and thiiranes.  
     
     
         29 . The method of  claim 21 , wherein said polymerization comprises a chain growth mechanism wherein polymerization proceeds through addition of a monomer to a reactive polymer.  
     
     
         30 . The method of  claim 21 , wherein said reactive molecule is deposited as a thin layer or a molecular monolayer.  
     
     
         31 . The method of  claim 1 , wherein said masking material includes a composition wherein polymerization proceeds by reactions that combine monomers and polymers having two or more functionalities that react with each other to produce polymers of a larger molecular weight.  
     
     
         32 . The method of  claim 1 , wherein said masking material comprises a reactive molecule, wherein reaction of the reactive molecule with the portion of the pattern generates a layer having reactive groups, which participate in step growth polymerization.  
     
     
         33 . The method of  claim 32 , further comprising applying a reactive monomer, having one or more functionalities to the layer a form a self aligned mask layer.  
     
     
         34 . The method of  claim 33 , wherein the one or more functionalities react with each other to form a covalent bond.  
     
     
         35 . The method of  claim 32 , wherein the reactive molecule comprises a first moiety that binds the reactive molecule to the portions of the pattern, and a second moiety that serves as a reaction site.  
     
     
         36 . The method of  claim 35 , wherein the first moiety that binds to portions of the pattern is selected from the group consisting of: organosilanes, hydroxy, acyl chlorides, and carboxylic acids.  
     
     
         37 . The method of  claim 35 , wherein the second moiety that serves as a reaction site is selected from the group consisting of: amines, nitrites, alcohols, carboxylic acids, sulfonic acids, isocyanates, acyl chlorides, esters, amides, anhydrides, epoxies, halides, acetoxy, vinyl, and silanols  
     
     
         38 . The method of  claim 33 , wherein the functionalities are provided by one or more functional groups selected from the group consisting of: amines, nitriles, alcohols, acids, carboxylic acids, sulfonic acids, isocyanates, acyl chlorides, esters, amides, anhydrides, epoxies, halides, acetoxy, vinyl, and silanols.  
     
     
         39  The method of  claim 33 , wherein said reactive monomer polymerizes when exposed to thermal annealing or irradiation.  
     
     
         40 . The method of  claim 1 , further comprising preparing a polymer to act as said masking material.  
     
     
         41 . The method of  claim 40 , further comprising forming a condensed phase containing said polymer, and contacting said portions of said pattern with said condensed phase.  
     
     
         42 . The method of  claim 41 , wherein said condensed phase is a liquid.  
     
     
         43 . The method of  claim 42 , wherein said liquid is a solvent for said polymer.  
     
     
         44 . The method of  claim 1 , further comprising: preparing a reactive molecule.  
     
     
         45 . The method of  claim 44 , further comprising forming a condensed phase containing said reactive molecule, and contacting said portions of said pattern with said condensed phase.  
     
     
         46 . The method of  claim 45 , wherein said condensed phase is a liquid.  
     
     
         47 . The method of  claim 46 , wherein said liquid is a solvent for said reactive molecule.  
     
     
         48 . The method of  claim 44 , wherein the reactive molecule is prepared in a vapor phase.  
     
     
         49 . The method of  claim 1 , further comprising: preparing a reactive monomer.  
     
     
         50 . The method of  claim 49 , further comprising forming a condensed phase containing said reactive monomer, and contacting said portions of said pattern having said layer with said condensed phase.  
     
     
         51 . The method of  claim 50 , wherein said condensed phase is a liquid.  
     
     
         52 . The method of  claim 51 , wherein said liquid is a solvent for said reactive monomer  
     
     
         53 . The method of  claim 49 , wherein the reactive monomer is prepared in a vapor phase.  
     
     
         54 . The method of  claim 1 , further comprising removing the masking material from portions of said pattern to which it does not attach.  
     
     
         55 . The method of  claim 54 , wherein said removing is accomplished by at least one of rinsing, ultrasonication, dissolution, thermolysis, irradiation, and annealing.  
     
     
         56 . The method of  Claim 1 , wherein the masking material is applied to the substrate by a method selected from: spin-coating, scan coating, dip coating, spray coating, and using a doctor blade.  
     
     
         57 . The method of  Claim 1 , wherein said pattern is comprised of a first set of regions of the substrate having a first atomic composition and a second set of regions of the substrate having a second atomic composition different from the first composition and wherein the areas of second atomic composition comprises copper and are patterned electrical interconnects.  
     
     
         58 . The method of  Claim 1 , wherein the substrate is selected from the following: a silicon wafer containing microelectronic devices , a ceramic chip carrier, an organic chip carrier, a glass substrate, a gallium arsenide substrate, a silicon carbide substrate, a semiconductor wafer, a circuit board, or a plastic substrate.  
     
     
         59 . The method of  claim 1 , further comprising chemically treating regions of the substrate prior to applying said coating.  
     
     
         60 . The method of  claim 59 , wherein said chemically treating comprises at least one of plasma treatment, application of an oxidizing or reducing solution, annealing in a reducing or oxidizing atmosphere, and application of a material that renders surface portions of the substrate, to which it is applied, to be hydrophobic or hydrophillic.  
     
     
         61 . The method of  claim 59 , wherein said chemically treating changes the wetting characteristics of the regions of the substrate.  
     
     
         62 . The method of  claim 59 , wherein said chemically treating in order to modify said second regions comprises applying an organosilane comprised of Si x L y R z,  where L is selected from the group consisting of hydroxy, methoxy, ethoxy, acetoxy, alkoxy, carboxy, amines, halogens, R is selected from the group consisting of hydrido, methyl, ethyl, vinyl, and phenyl (any alkyl or aryl).  
     
     
         63 . The method of  claim 59 , wherein said chemically treating in order to modify said second regions comprises applying a material selected from the group consisting of: hexamethyl disilazane, hexaphenyl disilazane, vinyltriacetoxysilane, aminopropyltrimethoxysilane, trimethychlorosilane, trimethylacetoxysilane and halogenated alkyl silanes.  
     
     
         64 . The method of  claim 59 , wherein said chemically treating in order to modify said first regions comprises applying one of hydroxys, esters, ethers, aldehydes, ketones, carbonates, acids, phenols, amines, amides, imides, thioesters, thioethers, ureas, urethanes, nitriles, isocyanates, thiols, sulfones, halides, phosphines, phosphine oxides, phosphonimides, nitros, azos, thioesters, thioethers, benzotriazole, pyridines, imidazoles, imides, oxazoles, benzoxazoles, thiazoles, pyrazoles, triazoles, thiophenes, oxadiazoles, thiazines, thiazoles, quionoxalines, benzimidazoles, oxindoles, indolines, nitrogenous compounds, ans phosphoric acids.  
     
     
         65 . The method of  claim 59 , wherein said chemically treating comprises at least one of thermal annealing and irradiating.  
     
     
         66 . The method of  claim 65 , wherein said irradiating comprises exposure to one of ultraviolet light, visible light, x-rays, and electrons.  
     
     
         67 . The method of  claim 1 , wherein the coating comprises a polymer that covalently bonds to said portions of said pattern.  
     
     
         68 . A structure comprising: 
 a self aligned pattern on an existing pattern on a substrate, said self aligned pattern including a masking material having an affinity for portions of said existing pattern, so that said masking material preferentially reactively grafts to said portions of said existing pattern.    
     
     
         69 . The structure of  claim 68 , wherein said pattern is comprised of a first set of regions of the substrate having a first atomic composition and a second set of regions of the substrate having a second atomic composition different from the first composition.  
     
     
         70 . The structure of  claim 69 , wherein said first set of regions includes one or more metal elements and wherein said second set of regions includes a dielectric.  
     
     
         71 . The structure of  claim 70 , wherein said self-aligned pattern is disposed upon said second set of regions.  
     
     
         72 . The structure of  claim 70 , wherein said self-aligned pattern is disposed only upon said second set of regions.  
     
     
         73 . The structure of  claim 70 , wherein said self-aligned pattern is not disposed upon said first set of regions.  
     
     
         74 . The structure according to  Claim 68 , comprising at least one conductive feature, formed on said substrate, with the substrate further comprising at least one insulating layer surrounding said conductive feature.  
     
     
         75 . The structure according to  Claim 74 , wherein said insulating layer surrounds said at least one conductive feature at its bottom and lateral surfaces.  
     
     
         76 . The structure according to  Claim 74 , further comprising at least one conductive barrier layer disposed at, at least one interface between said insulating layer and said at least one conductive feature.  
     
     
         77 . A structure according to  Claim 74 , where the combination of the at least one conductive feature and the insulating layers, is repeated to form a multilevel interconnect stack.  
     
     
         78 . The structure according to  Claim 77 , further comprising at least one conductive barrier layer disposed at, at least one interface between said insulating layer and said at least one conductive feature.  
     
     
         79 . The structure according to  Claim 68 , wherein said substrate is one of a microelectronic device chip, a ceramic chip carrier, and an organic chip carrier.  
     
     
         80 . A composition for selectively coating a pattern on a substrate, said composition comprising: 
 a carrier material for application to said substrate; and    a polymer in said carrier that reactively grafts to regions of said substrate having first chemical characteristics.    
     
     
         81 . The composition of  claim 62 , wherein said polymer is an amorphous polymeric system having any chain architecture.  
     
     
         82 . The composition of  claim 81 , wherein said polymer is one of linear, networked, branched, and dendrimeric.  
     
     
         83 . The composition of  claim 81 , wherein said polymer has an acyclic main chain.  
     
     
         84 . The composition of  claim 83 , wherein said polymer is selected from the group consisting of poly(dienes), poly(alkenes), poly(acrylics), poly(methacrylics), poly(acrylamides), poly(methacrylamides), poly(vinylethers), poly(vinyl alcohols), poly(ketones), poly(acetals), poly(vinylesters), poly(vinylhalides), poly(vinylnitriles), poly(styrenes), poly(vinyl pyridines), poly(vinyl pyrrolidones), poly(vinyl imidazoles), and poly(vinylheterocyclics).  
     
     
         85 . The composition of  claim 81 , wherein said polymer has a carbon containing backbone.  
     
     
         86 . The composition of  claim 81 , wherein said polymer has a carbocyclic main chain.  
     
     
         87 . The composition of  claim 81 , wherein said polymer is a poly(phenylene).  
     
     
         88 . The composition of  claim 81 , wherein said polymer is a main chain acyclic hetroatom polymer.  
     
     
         89 . The composition of  claim 88 , wherein said polymer is selected from the group consisting of poly(oxides), poly(carbonates), poly(esters), poly(anhydrides), poly(urethanes), poly(sulfonates), poly(siloxanes), poly(sulfides), poly(thioethers), poly(thioesters), poly(sulfones), poly(sufonamides), poly(amides), poly(imines), poly(ureas), poly(phosphazenes), poly(silanes), poly(siloxanes), poly(silazanes), and poly(nitriles).  
     
     
         90 . The composition of  claim 81 , wherein said polymer is a main chain heterocyclic polymer.  
     
     
         91 . The composition of  claim 90 , wherein said polymer is selected from the group consisting of: poly(imides), poly(oxazoles), poly(benzoxazoles), poly(thiazoles), poly(pyrazoles), poly(triazoles), poly(thiophenes), poly(oxadiazoles), poly(thiazines), poly(thiazoles), poly(quionoxalines), poly(benzimidazoles), poly(oxindoles), poly(indolines), poly(pyridines) poly(triazines), poly(piperazines), poly(pyridines), poly(piperdines), poly(pyrrolidines), poly(carboranes), poly(fluoresceins), poly(acetals), and poly(anhydrides).  
     
     
         92 . The composition of  claim 81 , wherein said polymer is a step growth polymer.  
     
     
         93 . The composition of  claim 92 , wherein said polymer is selected from the group consisting of: poly(oxides), poly(carbonates), poly(esters), poly(anhydrides), poly(urethanes), poly(sulfonates), poly(siloxanes), poly(sulfides), poly(thioethers), poly(thioesters), poly(sulfones), poly(sufonamides), poly(amides), poly(imines), poly(ureas), poly(phosphazenes), poly(silanes), poly(siloxanes), poly(silazanes), poly(nitriles), poly(imides), poly(oxazoles), poly(benzoxazoles), poly(thiazoles), poly(pyrazoles), poly(triazoles), poly(thiophenes), poly(oxadiazoles), poly(thiazines), poly(thiazoles), poly(quionoxalines), poly(benzimidazoles), poly(oxindoles), poly(indolines), poly(pyridines) poly(triazines), poly(piperazines), poly(pyridines), poly(piperdines), poly(pyrrolidines), poly(carboranes), poly(fluoresceins), poly(acetals), and poly(anhydrides).  
     
     
         94 . The composition of  claim 81 , wherein said polymer contains at least one monomeric unit.  
     
     
         95 . A composition for selectively coating a pattern on a substrate, said composition comprising: 
 a carrier material for application to said substrate; and    a polymer in said carrier having reactive functional groups that covalently bond to regions of said substrate having first chemical characteristics.