Resist pattern swelling material, and method for patterning using same

Abstract

To provide a method for easily forming microscopic patterns exceeding the limit of exposure in the patterning technique utilizing the photolithography method in the vacuum deep ultraviolet ray region, a resist pattern swelling material is comprised by mixing a water-soluble or alkali-soluble composition comprising a resin and a cross linking agent and any one of a non-ionic interfacial active agent and an organic solvent selected from a group of the alcohol based, chain or cyclic ester based, ketone based, chain or cyclic ether based organic solvents.

What is claimed is:  
     
         1 . A resist pattern swelling material which comprises a water-soluble composition or alkali-soluble composition comprising a resin and a cross linking agent, and a non-ionic interfacial active agent.  
     
     
         2 . A resist pattern swelling material which comprises a water-soluble composition comprising a resin composition comprising at least a kind of resin selected from polyvinyl alcohol, polyvinyl acetal and polyvinyl acetate, and at least a cross linking agent selected from a group of the cross linking agents consisting of melamine derivative, urea derivative and uryl derivative, and at least an interfacial active agent selected from a group of the polyoxyethylene-polyoxypropylene condensation product based, polyoxyalkylenealkylether based, polyoxyethylenealkylether based, polyoxyethylene derivative based, solbitane fatty acid ether based, glycerine fatty acid ester based, primary alcohol ethoxylate based and phenol ethoxylate based interfacial active agents.  
     
     
         3 . A resist pattern swelling material which comprises a water-soluble or alkali-soluble composition comprising a resin and a cross linking agent, and at least a kind of organic solvent selected from the alcohol based, chain ester based, cyclic ester based, ketone based, chain ether based and cyclic ether based organic solvents.  
     
     
         4 . A resist pattern swelling material which comprises a water-soluble composition comprising a resin composition comprising at least a kind of resin selected from polyvinyl alcohol, polyvinyl acetal and polyvinyl acetate, and at least a cross linking agent selected from a group of the cross linking agents consisting of melamine derivative, urea derivative and uryl derivative, and at least a kind of organic solvent selected from alcohol based, chain ester based, cyclic ester based, ketone based, chain ether based and cyclic ether based organic solvents.  
     
     
         5 . The resist pattern swelling material according to  claim 4 , wherein the organic solvent is the cyclic ether based organic solvent.  
     
     
         6 . The resist pattern swelling material according to  claim 4  or  5 , wherein the uryl derivative is contained as a cross linking agent.  
     
     
         7 . A resist pattern swelling material which comprises a water-soluble composition comprising a mixed resin composition of polyvinyl alcohol, polyvinyl acetal and polyvinyl acetate, and at least a kind of cross linking agent selected from a group of the cross linking agents consisting of melamine derivative, urea derivative, and uryl derivative, and a phenol based resin.  
     
     
         8 . The resist pattern swelling material according to any one of  claims 1  to  6 , characterized in that the polyvinyl acetal of 5 to 40 wt % is contained, among the polyvinyl alcohol, polyvinyl acetal and polyvinyl acetate.  
     
     
         9 . A resist pattern swelling material which comprises a phenol based resin, at least a kind of cross linking agent selected from a group of the cross linking agents consisting of melamine derivative, urea derivative and uryl derivative, and a solvent which does not easily dissolve a resist material as the lower layer on which a pattern is already formed.  
     
     
         10 . The resist pattern swelling material according to  claim 9 , wherein the uryl derivative is contained as a cross linking agent.  
     
     
         11 . A method of forming a microscopic pattern comprising a step of swelling a resist pattern by coating of the resist pattern swelling material according to any one of  claims 1  to  10  to cover the surface of the resist pattern after formation thereof.  
     
     
         12 . The method of forming a microscopic pattern according to  claim 11 , characterized in that the resist pattern is the acryl based resist having the alicyclic group based functional group in the side chain.  
     
     
         13 . The method of forming a microscopic pattern according to  claim 12 , characterized in that the alicyclic group functional group is the adamantly based functional group or a norbornane based functional group.  
     
     
         14 . The method of forming a microscopic pattern according to  claim 11 , characterized in that the resist pattern is the COMA (cyclo-olefine maleic acid anhydride) based resist.  
     
     
         15 . A method of manufacturing a miniaturized device comprising the steps of swelling a resist pattern, after it is formed, by coating of the resist pattern swelling material according to any one of  claims 1  to  10  to cover the surface of the resist pattern and patterning the underlying layer with the dry etching method with the resist pattern after the swelling used as the mask.  
     
     
         16 . The method of manufacturing a miniaturized device according to  claim 15 , characterized in that the resist pattern is the acryl based resist having the alicyclic group functional group in the side chain.  
     
     
         17 . The method of manufacturing a miniaturized device according to  claim 16 , characterized in that the alicyclic group functional group is the adamantly based functional group or norbornane based functional group.  
     
     
         18 . The method of manufacturing a miniaturized device according to  claim 15 , characterized in that the resist pattern is the COMA (cyclo-olefine maleic acid anhydride) based resist.  
     
     
         19 . A method of manufacturing a semiconductor device comprising the steps of swelling a resist pattern, after it is formed, by coating of the resist pattern swelling material according to any one of  claims 1  to  10  to cover the surface of the resist pattern and patterning the underlying layer with the dry etching method with the resist pattern after the swelling used as the mask.  
     
     
         20 . The method of manufacturing a semiconductor device according to  claim 19 , characterized in that the resist pattern is the acryl based resist having the alicyclic group functional group in the side chain.  
     
     
         21 . The method of manufacturing a semiconductor device according to  claim 20 , characterized in that the alicyclic group functional group is the adamantly based functional group or the norbornane based functional group.  
     
     
         22 . The method of manufacturing a semiconductor device according to  claim 19 , characterized in that the resist pattern is the COMA (cyclo-olefine maleic acid anhydride) based resist.  
     
     
         23 . The method of manufacturing a semiconductor device according to  claim 19 , characterized in that the resist pattern is the cyclo-olefine based resist including the norbornene or adamantane in the main chain.  
     
     
         24 . A resist pattern swelling method comprising the steps of: 
 coating the surface of a resist pattern, after the resist pattern is formed, with an aqueous solution containing an interfacial active agent selected from a group of the polyoxyethylene-polyoxypropylene condensation product based, polyoxyalkylenealkylether based, polyoxyehtylenealkylether based, polyoxy-ethylene derivative based, solbitane fatty acid ester based, glycerine fatty acid ester based, primary alcohol ethoxylate based and phenol ethoxylate based interfacial active agents, and    coating the surface of the resist pattern with a water-soluble composition which comprises a resin composition comprising at least a kind of resin selected from polyvinyl alcohol, polyvinyl acetal and polyvinyl acetate and at least a cross linking agent selected from a group of the cross linking agents consisting of melamine derivative, urea derivative and uryl derivative.    
     
     
         25 . The resist pattern swelling method according to  claim 24 , further comprising, in addition to the above steps, a step of developing and removing the non-swelled layer of the resist pattern with water or the water-soluble alkali developer.  
     
     
         26 . The resist pattern swelling method according to  claim 25 , characterized in that the developing and removing process is carried out using the pure water.  
     
     
         27 . The resist pattern swelling method according to  claim 24 , characterized in that the resist is the acryl based resist having the alicryclic group functional group in the side chain.  
     
     
         28 . The resist pattern swelling method according to  claim 27 , characterized in that the alicyclic group functional group is the adamantyl based functional group or norbornane based functional group.  
     
     
         29 . The resist pattern swelling method according to  claim 24 , characterized in that the resist pattern is the COMA (cyclo-olefine maleic acid anhydride) based resist.  
     
     
         30 . The resist pattern swelling method according to any one of  claims 24  to  29 , wherein the uryl derivative as a cross linking agent.  
     
     
         31 . The resist pattern swelling method according to any one of  claims 24  to  30 , characterized in that the polyvinyl acetal of 5 to 40 wt % is contained, among the polyvinyl alcohol, polyvinyl acetal and polyvinyl acetate.  
     
     
         32 . A method of forming a microscopic pattern, comprising: 
 a step of swelling a resist pattern with the resist pattern swelling method according to any one of  claims 24  to  31 .    
     
     
         33 . A method of manufacturing a miniaturized device comprising a step of patterning the underlying layer with the dry etching method using the resist pattern before the swelling as the mask after the resist pattern swelling method according to any one of  claims 24  to  31 .  
     
     
         34 . A method of manufacturing a semiconductor device comprising a step of patterning the underlying layer with the dry etching method using the resist pattern after the swelling as the mask after the resist pattern swelling method according to any one of  claims 24  to  31 .  
     
     
         35 . The method of forming a microscopic pattern according to  claim 11 , wherein said resist pattern is formed by patterning a chemical amplified resist.  
     
     
         36 . The method of forming a microscopic pattern according to  claim 11 , wherein said resist pattern is formed by patterning a conventional type resist, which is not a chemical amplified resist.  
     
     
         37 . The method of forming a microscopic pattern according to  claim 11 , wherein said resist pattern is formed by patterning an Electron Beam exposurable resist.  
     
     
         38 . The method of forming a microscopic pattern according to  claim 11 , wherein said resist pattern is comprised from a plurality of resist layers.  
     
     
         39 . The method of manufacturing a miniaturized device according to  claim 15 , wherein said resist pattern is formed by patterning a chemical amplified resist.  
     
     
         40 . The method of manufacturing a miniaturized device according to  claim 15 , wherein said resist pattern is formed by patterning a conventional type resist, which is not a chemical amplified resist.  
     
     
         41 . The method of manufacturing a miniaturized device according to  claim 15 , wherein said resist pattern is formed by patterning an Electron Beam exposurable resist.  
     
     
         42 . The method of manufacturing a miniaturized device according to  claim 15 , wherein said resist pattern is comprised from a plurality of resist layers.  
     
     
         43 . The method of manufacturing a semiconductor device according to  claim 19 , wherein said resist pattern is formed by patterning a chemical amplified resist.  
     
     
         44 . The method of manufacturing a semiconductor device according to  claim 19 , wherein said resist pattern is a conventional type resist, which is not a chemical amplified resist.  
     
     
         45 . The method of manufacturing a semiconductor device according to  claim 19 , wherein said resist pattern is formed by pattering an Electron Beam exposurable resist.  
     
     
         46 . The method of manufacturing a semiconductor device according to  claim 19 , wherein said resist pattern is comprised from a plurality of resist layers.  
     
     
         47 . The resist pattern swelling method according to  claim 24 , wherein said resist pattern is formed by patterning a chemical amplified resist.  
     
     
         48 . The resist pattern swelling method according to  claim 24 , wherein said resist pattern is formed by patterning a conventional type resist, which is not a chemical amplified resist.  
     
     
         49 . The resist pattern swelling method according to  claim 24 , wherein said resist pattern is formed by patterning an Electron Beam exposurable resist.  
     
     
         50 . The resist pattern swelling method according to  claim 24 , wherein said resist pattern is comprised from a plurality of resist layers.