Chemical amplification type positive photoresist composition and resist pattern forming method

Abstract

The present invention provides a chemical amplification type positive photoresist composition which is excellent in storage stability as a resist solution in a bottle A novolak resin or a hydroxystyrenic resin is reacted with a crosslinking agent to give a slightly alkali-soluble or alkali-insoluble resin having such a property that solubility in an aqueous alkali solution is enhanced in the presence of an acid, which is then dissolved in an organic solvent, together with (B) a compound generating an acid under irradiation with radiation to obtain a chemical amplification type positive photoresist composition wherein the content of an acid component is 10 ppm or less.

1 . A chemical amplification type positive photoresist composition prepared by dissolving: 
 (A′) an slightly alkali-soluble or alkali-insoluble polyhydroxystyrenic resin having a property that solubility in an aqueous alkali solution is enhanced in the presence of an acid, comprising either or both of a constituent unit (a′1) represented by the following general formula                          (IV):    wherein R 1  represents either an alkylene group having 1 to 10 carbon atoms which may have a substituent or a group represented by the following general formula (II)                          (wherein R 4  represents an alkylene group having 1 to 10 carbon atoms which may have a substituent and m represents 0 or 1), the alkylene group may have an oxygen bond (ether bond) in the main chain, and an intermolecular crosslinked moiety (a′2) represented by the following general formula (V):                          wherein R 1  represents either an alkylene group having 1 to 10 carbon atoms which may have a substituent or a group represented by the above general formula (II) (wherein R 4  represents an alkylene group having 1 to 10 carbon atoms which may have a substituent and m represents 0 or 1), the alkylene group may have an oxygen bond (ether bond) in the main chain; and    (B) a compound generating an acid under irradiation with radiation, in an organic solvent,    wherein said organic solvent is a non-ester solvent, and the content of an acid component in the photoresist composition is 10 ppm or less.    
     
     
         2 . The chemical amplification type positive photoresist composition according to  claim 1 , wherein the composition further comprises a storage stabilizer.  
     
     
         3 . The chemical amplification type positive photoresist composition according to  claim 2 , wherein the storage stabilizer is an antioxidant.  
     
     
         4 . The chemical amplification type positive photoresist composition according to  claim 1 , wherein the component (B) is a compound generating an acid under irradiation with i-rays (365 nm).  
     
     
         5 . The chemical amplification type positive photoresist composition according to  claim 1 , which further comprises a basic compound as the component (C).  
     
     
         6 . The chemical amplification type positive photoresist composition according to  claim 5 , which comprises the component (C) in the amount of 0.01 to 5 parts by weight based on 100 parts by weight of the resin component contained in the resist composition.  
     
     
         7 . The chemical amplification type positive photoresist composition according to  claim 1 , which comprises γ-butyrolactone in the amount of from 1 to 10 parts by weight based on the solid content of the resist composition.  
     
     
         8 . The chemical amplification type positive photoresist composition according to  claim 1 , which is used for a thick-film photolithography process used for forming a resist film having a thickness of about 2 to 7 μm.  
     
     
         9 . The chemical amplification type positive photoresist composition according to  claim 8 , wherein the thick-film photolithography process is used for forming a resist pattern for implantation.  
     
     
         10 . A chemical amplification type positive photoresist composition prepared by dissolving: 
 (A′) an slightly alkali-soluble or alkali-insoluble polyhydroxystyrenic resin having a property that solubility in an aqueous alkali solution is enhanced in the presence of an acid, comprising either or both of a constituent unit (a′1) represented by the following general formula                          (IV):    wherein R 1  represents either an alkylene group having 1 to 10 carbon atoms which may have a substituent or a group represented by the following general formula (II)                          (wherein R 4  represents an alkylene group having 1 to 10 carbon atoms which may have a substituent and m represents 0 or 1), the alkylene group may have an oxygen bond (ether bond) in the main chain, and an intermolecular crosslinked moiety (a′2) represented by the following general formula (V):                          wherein R 1  represents either an alkylene group having 1 to 10 carbon atoms which may have a substituent or a group represented by the above general formula (II) (wherein R 4  represents an alkylene group having 1 to 10 carbon atoms which may have a substituent and m represents 0 or 1), the alkylene group may have an oxygen bond (ether bond) in the main chain; and    (B) a compound generating an acid under irradiation with radiation, in an organic solvent,    wherein said organic solvent is an ester solvent and the content of an acid component is 10 ppm or less.    
     
     
         11 . The chemical amplification type positive photoresist composition according to  claim 10 , wherein the composition further comprises a storage stabilizer.  
     
     
         12 . The chemical amplification type positive photoresist composition according to  claim 11 , wherein the storage stabilizer is an antioxicant.  
     
     
         13 . The chemical amplification type positive photoresist composition according to  claim 11 , wherein the organic solvent is propylene glycol monomethyl ether acetate.  
     
     
         14 . The chemical amplification type positive photoresist composition according to  claim 10 , wherein the component (B) is a compound generating an acid under irradiation with i-rays (365 nm).  
     
     
         15 . The chemical amplification type positive photoresist composition according to  claim 10 , which further comprises a basic compound as the component (C).  
     
     
         16 . The chemical amplification type positive photoresist composition according to  claim 15 , which comprises the component (C) in the amount of 0.01 to 5 parts by weight based on 100 parts by weight of the resin component contained in the resist composition.  
     
     
         17 . The chemical amplification type positive photoresist composition according to  claim 10 , which comprises y-butyrolactone in the amount of from 1 to 10 parts by weight based on the solid content of the resist composition.  
     
     
         18 . The chemical amplification type positive photoresist composition according to  claim 10 , which is used for a thick-film photolithography process used for forming a resist film having a thickness of about 2 to 7 μm.  
     
     
         19 . The chemical amplification type positive photoresist composition according to  claim 18 , wherein the thick-film photolithography process is used for forming a resist pattern for implantation.  
     
     
         20 . A chemical amplification type positive photoresist composition prepared by dissolving: 
 (A′) an slightly alkali-soluble or alkali-insoluble polyhydroxystyrenic resin having a property that solubility in an aqueous alkali solution is enhanced in the presence of an acid, comprising either or both of a constituent unit (a′1) represented by the following general formula (IV):                          wherein R 1  represents either an alkylene group having 1 to 10 carbon atoms which may have a substituent or a group represented by the following general formula (II)                          (wherein R 4  represents an alkylene group having 1 to 10 carbon atoms which may have a substituent and m represents 0 or 1), the alkylene group may have an oxygen bond (ether bond) in the main chain, and an intermolecular crosslinked moiety (a′2) represented by the following general formula (V):                          wherein R 1 represents either an alkylene group having 1 to 10 carbon atoms which may have a substituent or a group represented by the above general formula (II) (wherein R 4  represents an alkylene group having 1 to 10 carbon atoms which may have a substituent and m represents 0 or 1), the alkylene group may have an oxygen bond (ether bond) in the main chain, and a styrenic constituent unit; and    (B) a compound generating an acid under irradiation with radiation, in an organic solvent,    wherein said organic solvent is a non-ester solvent and the content of an acid component is 10 ppm or less.    
     
     
         21 . The chemical amplification type positive photoresist composition according to  claim 20 , wherein the composition further comprises a storage stabilizer.  
     
     
         22 . The chemical amplification type positive photoresist composition according to  claim 21 , wherein the storage stabilizer is an antioxidant.  
     
     
         23 . The chemical amplification type positive photoresist composition according to  claim 20 , wherein the component (B) is a compound generating an acid under irradiation with i-rays (365 nm).  
     
     
         24 . The chemical amplification type positive photoresist composition according to  claim 20 , which further comprises a basic compound as the component (C).  
     
     
         25 . The chemical amplification type positive photoresist composition according to  claim 24 , which comprises the component (C) in the amount of 0.01 to 5 parts by weight based on 100 parts by weight of the resin component contained in the resist composition.  
     
     
         26 . The chemical amplification type positive photoresist composition according to  claim 20 , which comprises y-butyrolactone in the amount of from 1 to 10 parts by weight based on the solid content of the resist composition.  
     
     
         27 . The chemical amplification type positive photoresist composition according to  claim 20 , which is used for a thick-film photolithography process used for forming a resist film having a thickness of about 2 to 7 μm.  
     
     
         28 . The chemical amplification type positive photoresist composition according to  claim 27 , wherein the thick-film photolithography process is used for forming a resist pattern for implantation.  
     
     
         29 . A chemical amplification type positive photoresist composition prepared by dissolving: 
 (A′) an slightly alkali-soluble or alkali-insoluble polyhydroxystyrenic resin having a property that solubility in an aqueous alkali solution is enhanced in the presence of an acid, comprising either or both of a constituent unit (a′1) represented by the following general formula (IV):                          wherein R 1  represents either an alkylene group having 1 to 10 carbon atoms which may have a substituent or a group represented by the above general formula (II)                          (wherein R 4  represents an alkylene group having 1 to 10 carbon atoms which may have a substituent and m represents 0 or 1), the alkylene group may have an oxygen bond (ether bond) in the main chain, and an intermolecular crosslinked moiety (a′2) represented by the following general formula (V):                          wherein R 1  represents either an alkylene group having 1 to 10 carbon atoms which may have a substituent or a group represented by the above general formula (II) (wherein R 4  represents an alkylene group having 1 to 10 carbon atoms which may have a substituent and m represents 0 or 1), the alkylene group may have an oxygen bond (ether bond) in the main chain, and a styrenic constituent unit; and    (B) a compound generating an acid under irradiation with radiation, in an organic solvent,    wherein said organic solvent is an ester solvent and the content of an acid component is 10 ppm or less.    
     
     
         30 . The chemical amplification type positive photoresist composition according to  claim 29 , wherein the composition further comprises a storage stabilizer.  
     
     
         31 . The chemical amplification type positive photoresist composition according to  claim 29 , wherein the storage stabilizer is an antioxicant.  
     
     
         32 . The chemical amplification type positive photoresist composition according to  claim 30 , wherein the organic solvent is propylene glycol monomethyl ether acetate.  
     
     
         33 . The chemical amplification type positive photoresist composition according to  claim 29 , wherein the component (B) is a compound generating an acid under irradiation with i-rays (365 nm).  
     
     
         34 . The chemical amplification type positive photoresist composition according to  claim 29 , which further comprises a basic compound as the component (C).  
     
     
         35 . The chemical amplification type positive photoresist composition according to  claim 34 , which comprises the component (C) in the amount of 0.01 to 5 parts by weight based on 100 parts by weight of the resin component contained in the resist composition.  
     
     
         36 . The chemical amplification type positive photoresist composition according to  claim 29 , which comprises γ-butyrolactone in the amount of from 1 to 10 parts by weight based on the solid content of the resist composition.  
     
     
         37 . The chemical amplification type positive photoresist composition according to  claim 29 , which is used for a thick-film photolithography process used for forming a resist film having a thickness of about 2 to 7 μm.  
     
     
         38 . The chemical amplification type positive photoresist composition according to  claim 37 , wherein the thick-film photolithography process is used for forming a resist pattern for implantation.  
     
     
         39 . A chemical amplification type positive photoresist composition prepared by dissolving: 
 (A′) an slightly alkali-soluble or alkali-insoluble polyhydroxystyrenic resin having a property that solubility in an aqueous alkali solution is enhanced in the presence of an acid, comprising either or both of a constituent unit (a′1) represented by the following general formula (IV):                          wherein R 1  represents either an alkylene group having 1 to 10 carbon atoms which may have a substituent or a group represented by the following general formula (II)                          (wherein R 4  represents an alkylene group having 1 to 10 carbon atoms which may have a substituent and m represents 0 or 1), the alkylene group may have an oxygen bond (ether bond) in the main chain, and an intermolecular crosslinked moiety (a′2) represented by the following general formula (V):                          wherein R 1  represents either an alkylene group having 1 to 10 carbon atoms which may have a substituent or a group represented by the above general formula (II) (wherein R 4  represents an alkylene group having 1 to 10 carbon atoms which may have a substituent and m represents 0 or 1), the alkylene group may have an oxygen bond (ether bond) in the main chain; and    (B) a compound generating an acid under irradiation with radiation, in an organic solvent,    wherein said compound generating an acid under irradiation with radiation (B) is a compound represented by the following formula (vi):                          wherein Ar represents a substituted or unsubstituted phenyl group or a naphthyl group; R″. represents an alkyl group having 1 to 9 carbon atoms; and n′ represents an integer of 2 or 3.    
     
     
         40 . The chemical amplification type positive photoresist composition according to  claim 39 , wherein the composition further comprises a storage stabilizer.  
     
     
         41 . The chemical amplification type positive photoresist composition according to  claim 40 , wherein the storage stabilizer is an antioxidant.  
     
     
         42 . The chemical amplification type positive photoresist composition according to  claim 39 , which further comprises a basic compound as the component (C).  
     
     
         43 . The chemical amplification type positive photoresist composition according to  claim 42 , which comprises the component (C) in the amount of 0.01 to 5 parts by weight based on 100 parts by weight of the resin component contained in the resist composition.  
     
     
         44 . The chemical amplification type positive photoresist composition according to  claim 39 , which comprises γ-butyrolactone in the amount of from 1 to 10 parts by weight based on the solid content of the resist composition.  
     
     
         45 . The chemical amplification type positive photoresist composition according to  claim 39 , which is used for a thick-film photolithography process used for forming a resist film having a thickness of about 2 to 7 μm.  
     
     
         46 . The chemical amplification type positive photoresist composition according to  claim 45 , wherein the thick-film photolithography process is used for forming a resist pattern for implantation.