Silicon-containing polymer, process for its production, resist composition employing it, pattern-forming method and electronic device fabrication method

Abstract

A silicon-containing polymer having a tetrafunctional siloxane portion as the basic skeleton, and containing a carboxylic acid group-containing triorganosiloxane portion and a carboxylic acid derivative group-containing triorganosiloxane portion in a specific proportion. It may be advantageously used as a negative non-chemical amplification resist polymer or a positive chemical amplification resist polymer.

1 . A process for production of a silicon-containing polymer comprising the structure presented by formula 1 below as a main structural unit  
       
         
           
           
               
               
           
         
       
       where R 1  represents a monovalent organic group, R 2  represents a direct bond or a divalent organic group, R 3  represents a monovalent organic group of an organosilyl group, any of which groups may be of different types, X represents hydrogen, a monovalent organic group or an organosilyl group, which groups may be of different types, k and l are positive integers, m and n are 0 or positive integers, and these subscripts satisfy the following relationship  
       
         
           
             
               
                 0 
                 < 
                 
                   1 
                   
                     1 
                     + 
                     m 
                     + 
                     n 
                   
                 
                 ≦ 
                 0.8 
               
               ⁢ 
               
                   
               
             
           
         
         
           
             
               
                 0 
                 < 
                 
                   m 
                   
                     1 
                     + 
                     m 
                   
                 
                 < 
                 0.2 
               
               , 
             
           
         
       
       wherein tetraethoxysilane is used as the starting silicone monomer for formation of the polymer skeleton during production of the silicon-containing polymer, and a carboxyl group-containing compound is added that does not react with the starting silicone monomer or the resulting silicon-containing polymer in the synthesis solvent.  
     
     
         2 . The process for production of a silicon-containing polymer according to  claim 1 , wherein at least some of the X groups are triorganosilyl groups.  
     
     
         3 . The process for production of a silicon-containing polymer according to  claim 2 , wherein said triorganosilyl groups include photosensitive crosslinkable groups.  
     
     
         4 . The process for production of a silicon-containing polymer according to  claim 1 , wherein R 8  is —(CH 2 ) a — and a is an integer of 1-10.  
     
     
         5 . A process for production of a silicon-containing polymer comprising the structure represented by formula 2 below as a main structural unit  
       
         
           
           
               
               
           
         
       
       where R 1  represents a monovalent organic group, R 2  represents a direct bond or a divalent organic group, R 3  represents a monovalent organic group of an organosilyl group, any of which groups may be of different types, X represent hydrogen, a monovalent organic group or an organosilyl group, which groups may be of different types, wherein at least some of the X group and wherein the photosensitive crosslinkable group is chloromethylphenylethyl, wherein R 4 , R 5  and R 6  may be one or more different types of organic groups, k, l and o are positive integers, m and n are 0 or positive integers, and these subscripts satisfy the following relationships  
       
         
           
             
               0 
               < 
               
                 1 
                 
                   1 
                   + 
                   m 
                   + 
                   n 
                   + 
                   o 
                 
               
               ≦ 
               0.8 
             
           
         
         
           
             
               
                 0 
                 < 
                 
                   1 
                   
                     1 
                     + 
                     m 
                     + 
                     n 
                   
                 
                 ≦ 
                 0.8 
               
               ⁢ 
               
                   
               
             
           
         
         
           
             
               
                 0 
                 < 
                 
                   m 
                   
                     1 
                     + 
                     m 
                   
                 
                 < 
                 0.2 
               
               , 
             
           
         
       
       wherein tetraethoxysilane is used as the starting silicone monomer for formation of the polymer skeleton during production of the silicon-containing polymer, and a carboxyl group-containing compound is added that does not react with the starting silicone monomer or the resulting silicon-containing polymer in the synthesis solvent.  
     
     
         6 . The process for production of a silicon-containing polymer according to  claim 5 , wherein R 8  is —(CH 2 ) a — and a is an integer of 1-10.  
     
     
         7 . A process for production of a silicon-containing polymer comprising the structure presented by formula 3 below as a main structural unit  
       
         
           
           
               
               
           
         
       
       where R 1  represents a monovalent organic group, R 2  represents a direct bond or a divalent organic group, R 7  and R 8  each independently represent a monovalent organic group or an organosilyl group, any of which groups may be of different types, X represents hydrogen, a monovalent organic group or an organosilyl group, which groups may be of different types, k and q are positive integers, l, n, and p are 0 or positive integers, and these subscripts satisfy the following relationship:  
       
         
           
             
               
                 0 
                 < 
                 
                   1 
                   
                     1 
                     + 
                     n 
                     + 
                     p 
                     + 
                     q 
                   
                 
                 ≦ 
                 0.8 
               
               ⁢ 
               
                   
               
             
           
         
         
           
             
               
                 0 
                 < 
                 
                   q 
                   
                     1 
                     + 
                     n 
                     + 
                     p 
                     + 
                     q 
                   
                 
                 < 
                 0.2 
               
               , 
             
           
         
       
       wherein tetraethoxysilane is used as the starting silicone monomer for formation of the polymer skeleton during production of the silicon-containing polymer, and a carboxyl group-containing compound is added that does not react with the starting silicone monomer or the resulting silicon-containing polymer in the synthesis solvent.  
     
     
         8 . The process for production of a silicon-containing polymer according to  claim 7 , wherein at least some of the X groups are triorganosily groups.  
     
     
         9 . The process for production of a silicon-containing polymer according to  claim 7 , wherein R 8  is a functional group that is eliminated by an acid catalyst.  
     
     
         10 . The process for production of a silicon-containing polymer according to  claim 7 , wherein R 8  is —(CH 2 ) a — and a is an integer of 1-10.