Copolymer for semiconductor lithography and producing method thereof, and composition

Abstract

In order to improve a resist pattern shape in a semiconductor lithography process, which is a factor largely affecting on a processing precision, an integration degree and yield, a copolymer for semiconductor lithography where a composition of a hydroxyl group-containing repeating unit in a low molecular weight region is controlled, and a method of producing the same are provided. According to the invention, in a copolymer for semiconductor lithography, which is obtained by copolymerizing a monomer having a hydroxyl group and a monomer having no hydroxyl group, when a copolymer of which composition of a hydroxyl group-containing repeating unit is controlled is used, the object can be achieved.

1 . A copolymer for semiconductor lithography obtained by copolymerizing a monomer having a hydroxyl group and a monomer having no hydroxyl group, wherein a molar composition of a hydroxyl group-containing repeating unit in a low molecular weight region corresponding to 5% of a copolymer total peak by gel permeation chromatography is within ±10% of an average molar composition of hydroxyl group-containing repeating units in a total of the copolymer. 
     
     
         2 . The copolymer for semiconductor lithography according to  claim 1 , wherein the monomer having a hydroxyl group is selected from the group consisting of a hydroxystyrene, a hydroxyhalogenoalkylstyrene, a carboxylic acid having an ethylenic double bond, a hydroxyalkyl ester of carboxylic acid having an ethylenic double bond, and a hydroxyhalogenoalkyl ester of carboxylic acid having an ethylenic double bond. 
     
     
         3 . The copolymer for semiconductor lithography according to  claim 2 , wherein the monomer having a hydroxyl group is a hydroxystyrene. 
     
     
         4 . The copolymer for semiconductor lithography according to  claim 2 , wherein the monomer having a hydroxyl group is a hydroxyhalogenoalkylstyrene. 
     
     
         5 . The copolymer for semiconductor lithography according to  claim 2 , wherein the monomer having a hydroxyl group is a carboxylic acid having an ethylenic double bond. 
     
     
         6 . The copolymer for semiconductor lithography according to  claim 2 , wherein the monomer having a hydroxyl group is a hydroxyalkyl ester of carboxylic acid having an ethylenic double bond. 
     
     
         7 . The copolymer for semiconductor lithography according to  claim 2 , wherein the monomer having a hydroxyl group is a hydroxyhalogenoalkyl ester of carboxylic acid having an ethylenic double bond. 
     
     
         8 . The copolymer for semiconductor lithography according to  claim 1 , wherein the monomer having no hydroxyl group is a monomer having a hydroxyl group that is protected with a protecting group, wherein the monomer having a hydroxyl group that is protected with a protecting group is selected from the group consisting of a hydroxystyrene, a hydroxyhalogenoalkylstyrene, a carboxylic acid having an ethylenic double bond, a hydroxyalkyl ester of carboxylic acid having an ethylenic double bond, and a hydroxyhalogenoalkyl ester of carboxylic acid having an ethylenic double bond, and wherein the protecting group is selected from the group consisting of a saturated hydrocarbon group having 1-20 carbon atoms and an oxygen-containing hydrocarbon group having 2-24 carbon atoms. 
     
     
         9 . The copolymer for semiconductor lithography according to  claim 8 , wherein the monomer having a hydroxyl group that is protected with a protecting group is a hydroxystyrene, and wherein the protecting group is selected from the group consisting of a saturated hydrocarbon group having 1-20 carbon atoms and an oxygen-containing hydrocarbon group having 2-24 carbon atoms. 
     
     
         10 . The copolymer for semiconductor lithography according to  claim 8 , wherein the monomer having a hydroxyl group that is protected with a protecting group is a hydroxyhalogenoalkylstyrene, and wherein the protecting group is selected from the group consisting of a saturated hydrocarbon group having 1-20 carbon atoms and an oxygen-containing hydrocarbon group having 2-24-carbon atoms. 
     
     
         11 . The copolymer for semiconductor lithography according to  claim 8 , wherein the monomer having a hydroxyl group that is protected with a protecting group is a carboxylic acid having an ethylenic double bond, and wherein the protecting group is selected from the group consisting of a saturated hydrocarbon group having 1-20 carbon atoms and an oxygen-containing hydrocarbon group having 2-24 carbon atoms. 
     
     
         12 . The copolymer for semiconductor lithography according to  claim 8 , wherein the monomer having a hydroxyl group that is protected with a protecting group is a hydroxyalkyl ester of carboxylic acid having an ethylenic double bond, and wherein the protecting group is selected from the group consisting of a saturated hydrocarbon group having 1-20 carbon atoms and an oxygen-containing hydrocarbon group having 2-24 carbon atoms. 
     
     
         13 . The copolymer for semiconductor lithography according to  claim 8 , wherein the monomer having a hydroxyl group that is protected with a protecting group is a hydroxyhalogenoalkyl ester of carboxylic acid having an ethylenic double bond, and wherein the protecting group is selected from the group consisting of a saturated hydrocarbon group having 1-20 carbon atoms and an oxygen-containing hydrocarbon group having 2-24 carbon atoms. 
     
     
         14 . A semiconductor lithography composition comprising the copolymer for semiconductor lithography according to  claim 1 . 
     
     
         15 . A copolymer for semiconductor lithography produced by a process comprising:
 copolymerizing a monomer having a hydroxyl group and a monomer having no hydroxyl group in a polymerization reaction solution comprising a polymerization solvent to produce the copolymer; and   bringing the copolymer, which is present in the polymerization reaction solution, into contact with a poor solvent comprising: a polar solvent having a hydroxyl group; and a nonpolar solvent having no hydroxyl group, to reprecipitate or wash the copolymer,   wherein a molar composition of a hydroxyl group-containing repeating unit in a low molecular weight region corresponding to 5% of a copolymer total peak by gel permeation chromatography is within ±10% of an average molar composition of hydroxyl group-containing repeating units in a total of the copolymer.   
     
     
         16 . The copolymer for semiconductor lithography according to  claim 15 , wherein the monomer having a hydroxyl group is selected from the group consisting of a hydroxystyrene, a hydroxyhalogenoalkylstyrene, a carboxylic acid having an ethylenic double bond, a hydroxyalkyl ester of carboxylic acid having an ethylenic double bond, and a hydroxyhalogenoalkyl ester of carboxylic acid having an ethylenic double bond. 
     
     
         17 . The copolymer for semiconductor lithography according to  claim 15 , wherein the monomer having no hydroxyl group is a monomer having a hydroxyl group that is protected with a protecting group, wherein the monomer having a hydroxyl group that is protected with a protecting group is selected from the group consisting of a hydroxystyrene, a hydroxyhalogenoalkylstyrene, a carboxylic acid having an ethylenic double bond, a hydroxyalkyl ester of carboxylic acid having an ethylenic double bond, and a hydroxyhalogenoalkyl ester of carboxylic acid having an ethylenic double bond, and wherein the protecting group is selected from the group consisting of a saturated hydrocarbon group having 1-20 carbon atoms and an oxygen-containing hydrocarbon group having 2-24 carbon atoms. 
     
     
         18 . A process for producing a copolymer for semiconductor lithography, wherein said process comprises:
 copolymerizing a monomer having a hydroxyl group and a monomer having no hydroxyl group in a polymerization reaction solution comprising a polymerization solvent to produce the copolymer; and   bringing the copolymer, which is present in the polymerization reaction solution, into contact with a poor solvent comprising: a polar solvent having a hydroxyl group; and a nonpolar solvent having no hydroxyl group, to reprecipitate or wash the copolymer,   wherein a molar composition of a hydroxyl group-containing repeating unit in a low molecular weight region corresponding to 5% of a copolymer total peak by gel permeation chromatography is within ±10% of an average molar composition of hydroxyl group-containing repeating units in a total of the copolymer.   
     
     
         19 . The process for producing a copolymer for semiconductor lithography according to  claim 18 , wherein the monomer having a hydroxyl group is selected from the group consisting of a hydroxystyrene, a hydroxyhalogenoalkylstyrene, a carboxylic acid having an ethylenic double bond, a hydroxyalkyl ester of carboxylic acid having an ethylenic double bond, and a hydroxyhalogenoalkyl ester of carboxylic acid having an ethylenic double bond. 
     
     
         20 . The process for producing a copolymer for semiconductor lithography according to  claim 18 , wherein the monomer having no hydroxyl group is a monomer having a hydroxyl group that is protected with a protecting group, wherein the monomer having a hydroxyl group that is protected with a protecting group is selected from the group consisting of a hydroxystyrene, a hydroxyhalogenoalkylstyrene, a carboxylic acid having an ethylenic double bond, a hydroxyalkyl ester of carboxylic acid having an ethylenic double bond, and a hydroxyhalogenoalkyl ester of carboxylic acid having an ethylenic double bond, and wherein the protecting group is selected from the group consisting of a saturated hydrocarbon group having 1-20 carbon atoms and an oxygen-containing hydrocarbon group having 2-24 carbon atoms.