Novel fluorine-containing polymer having acid-reactive group and chemically amplifying type photoresist composition prepared from same

Abstract

There is provided a novel fluorine-containing polymer having an acid-reactive group which has a high transparency against energy rays (radioactive rays) in a vacuum ultraviolet region (157 nm), and further there are provided a material for fluorine-containing base polymer prepared from the polymer and suitable for a photoresist and a chemically amplifying type resist composition obtained therefrom. The polymer has a number average molecular weight of from 1,000 to 1,000,000 and represented by the formula: -(M1)-(M2)-(A)-, wherein M1 is a structural unit having an acid-labile or acid-degradable functional group, M2 is a structural unit of fluorine-containing acryl ester, A is a structural unit derived from other copolymerizable monomer, the percent by mole ratio M1/M2 is 1 to 99/99 to 1 and the polymer comprises from 1 to 99% by mole of the structural unit M1, from 1 to 99% by mole of the structural unit M2 and from 0 to 98% by mole of the structural unit A1. The material for fluorine-containing base polymer comprises a fluorine-containing polymer having an acid-reactive group such as the above-mentioned polymer and is suitable for a photoresist, and the chemically amplifying type resist composition is obtained from those polymer and material.

1 . A fluorine-containing polymer having a number average molecular weight of from 1,000 to 1,000,000 and represented by the formula (1):  
       -(M1)-(M2)-(A1)-  (1)  
     in which M1 is represented by:  
     
       
         
         
             
             
         
       
     
     M2 is represented by:  
     
       
         
         
             
             
         
       
     
     wherein X 1 , X 2 , X 4  and X 5  are the same or different and each is H or F; X 3  and X 6  are the same or different and each is H, Cl, CH 3 , F or CF 3 ; Y 1  is an acid-labile or acid-degradable functional group; R 1  is a divalent hydrocarbon group having 1 to 20 carbon atoms, a fluorine-containing alkylene group having 1 to 20 carbon atoms, a fluorine-containing alkylene group having 2 to 100 carbon atoms and ether bond or a fluorine-containing arylene group having 3 to 20 carbon atoms; Rf 1  is a fluorine-containing alkyl group having 1 to 20 carbon atoms, a fluorine-containing alkyl group having 2 to 100 carbon atoms and ether bond or a fluorine-containing aryl group having 3 to 20 carbon atoms; n1 is 0 or 1, 
 A1 is a structural unit derived from a monomer copolymerizable with the structural units M1 and M2,  
 when M1+M2 is assumed to be equal to 100% by mole, the percent by mole ratio M1/M2 is 1 to 99/1 to 99,  
 said fluorine-containing polymer comprises from 1 to 99% by mole of the structural unit M1, from 1 to 99% by mole of the structural unit M2 and from 0 to 98% by mole of the structural unit A1.  
 
   
   
       2 . The fluorine-containing polymer of  claim 1  having a number average molecular weight of from 1,000 to 1,000,000, wherein in the formula (1), when X 3  and X 6  are assumed to be F and M1+M2 is assumed to be equal to 100% by mole, the percent by mole ratio M1/M2 is 1 to 100/0 to 99 and said fluorine-containing polymer comprises from 1 to 100% by mole of the structural unit M1, from 0 to 99% by mole of the structural unit M2 and from 0 to 99% by mole of the structural unit A1.  
   
   
       3 . The fluorine-containing polymer of  claim 2 , wherein X 1 , X 2 , X 4  and X 5  are H, and X 3  and X 6  are F.  
   
   
       4 . The fluorine-containing polymer of  claim 1 , wherein the acid-labile or acid-degradable functional group Y 1  is:  
     
       
         
         
             
             
         
       
     
     wherein R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 14 , R 18 , R 19 , R 20 , R 21 , R 22 , R 24 , R 25 , R 26 , R 27 , R 28  and R 29  are the same or different and each is a hydrocarbon group having 1 to 10 carbon atoms; R 13 , R 15  and R 16  are H or hydrocarbon groups having 1 to 10 carbon atoms; R 7  and R 23  are divalent hydrocarbon groups having 2 to 10 carbon atoms.  
   
   
       5 . The fluorine-containing polymer of  claim 4 , wherein the acid-labile or acid-degradable functional group Y 1  is:  
     
       
         
         
             
             
         
       
     
     wherein R 30  is an alkyl group having 1 to 10 carbon atoms.  
   
   
       6 . A fluorine-containing polymer having a number average molecular weight of from 1,000 to 1,000,000 and represented by the formula (2):  
       -(M3)-(M4)-(M5)-(A2)-  (2)  
     in which M3 is represented by:  
     
       
         
         
             
             
         
       
     
     M4 is represented by:  
     
       
         
         
             
             
         
       
     
     M5 is represented by:  
     
       
         
         
             
             
         
       
     
     wherein X 7 , X 8 , X 9 , X 10 , X 11 , X 12 , X 13 , X 14 , X 16 , X 17  and X 18  are the same or different and each is H or F; X 15  is H, F or CF 3 ; Y is an acid-labile or acid-degradable functional group; Z 1  is a functional group which is not dissociated or degraded by an acid; Z 2  is H, F or Cl; R 2 , Rf 2  and Rf 3  are the same or different and each is a fluorine-containing alkylene group having 1 to 20 carbon atoms, a fluorine-containing alkylene group having 2 to 100 carbon atoms and ether bond or a fluorine-containing arylene group having 3 to 20 carbon atoms; n3, n4 and n5 are the same or different and each is 0 or an integer of 1 or 2; n6, n7, n8 and n10 are the same or different and each is 0 or 1; n9 is 1, 
 A2 is a structural unit derived from a monomer copolymerizable with the structural units M3 to M5,  
 when M3+M4+M5 is assumed to be equal to 100% by mole, the percent by mole ratio M3/M4/M5 is 1 to 100/0 to 99/0 to 99,  
 said fluorine-containing polymer comprises from 1 to 100% by mole of the structural unit M3, from 0 to 99% by mole of the structural unit M4, from 0 to 99% by mole of the structural unit M5 and from 0 to 99% by mole of the structural unit A2.  
 
   
   
       7 . A fluorine-containing polymer having a number average molecular weight of from 1,000 to 1,000,000 and represented by the formula (2a):  
       -(M3a)-(M4a)-(M5a)-(A2)-  (2a)  
     in which M3a is represented by:  
     
       
         
         
             
             
         
       
     
     M4a is represented by:  
     
       
         
         
             
             
         
       
     
     M5a is represented by:  
     
       
         
         
             
             
         
       
     
     wherein R 2a  is a divalent hydrocarbon group having 1 to 20 carbon atoms, a fluorine-containing alkylene group having 1 to 20 carbon atoms, a fluorine-containing alkylene group having 2 to 100 carbon atoms and ether bond or a fluorine-containing arylene group having 3 to 20 carbon atoms; n9 is 0 or 1; X 7 , X 8 , X 9 , X 10 , X 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 , X 18 , Y 1 , Z 1 , Z 2 , Rf 2 , Rf 3 , n3, n4, n5, n6, n7, n8 and n10 are as defined in said formula (2); at least one of X 13 , X 14  and Z 2  is For X 15  is For CF 3 , 
 A2 is a structural unit derived from a monomer copolymerizable with the structural units M3a to M5a,  
 when M3a+M4a+M5a is assumed to be equal to 100% by mole, the percent by mole ratio M3a/(M4a+M5a) is 1 to 90/10 to 99, said fluorine-containing polymer comprises from 1 to 90% by mole of the structural unit M3a, from 0 to 99% by mole of the structural unit M4a, from 0 to 99% by mole of the structural unit M5a and from 0 to 99% by mole of the structural unit A2.  
 
   
   
       8 . The fluorine-containing polymer of  claim 6 , wherein in the formula (2), X 7  and X 8  are H; X 9  and X 16  are F; and n3, n6 and n9 are 1.  
   
   
       9 . The fluorine-containing polymer of  claim 8 , wherein in the formula (2), X 10  and X 11  are H; X 12  and X 17  are F; n4 and n7 are 1; when M3+M4+M5 is assumed to be equal to 100% by mole, the percent by mole ratio M3/M4/M5 is 1 to 99/1 to 99/0 to 98, and said polymer comprises from 1 to 99% by mole of the structural unit M3, from 1 to 99% by mole of the structural unit M4, from 0 to 98% by mole of the structural unit M5 and from 0 to 98% by mole of the structural unit A2.  
   
   
       10 . The fluorine-containing polymer of  claim 6 , wherein in the formula (2), X 7 , X 8  and X 9  are F; n3 is 0; and n6 is 1.  
   
   
       11 . The fluorine-containing polymer of  claim 10 , wherein in the formula (2), X 10 , X 11  and X 12  are F; n4 is 0 and n7 is 1; when M3+M4+M5 is assumed to be equal to 100% by mole, the percent by mole ratio M3/M4/M5 is 1 to 99/1 to 99/0 to 98, and said polymer comprises from 1 to 99% by mole of the structural unit M3, from 1 to 99% by mole of the structural unit M4, from 0 to 98% by mole of the structural unit M5 and from 0 to 98% by mole of the structural unit A2.  
   
   
       12 . The fluorine-containing polymer of  claim 7 , wherein in the formula (2a), n5 is 0 or 1; n8 and n10 are 0; when M3a+M4a+M5a is assumed to be equal to 100% by mole, the percent by mole ratio M3a/(M4a+M5a) is 1 to 90/10 to 99 and the percent by mole ratio M3a/M4a/M5a is 1 to 90/0 to 98/1 to 99, and said polymer comprises from 1 to 99% by mole of the structural unit M3a, from 0 to 98% by mole of the structural unit M4a, from 1 to 99% by mole of the structural unit M5a and from 0 to 98% by mole of the structural unit A2.  
   
   
       13 . The fluorine-containing polymer of  claim 12 , wherein in the formula (2a), X 7  and X 8  are H; X 9  is F; R 2a  is a fluorine-containing alkylene group having 1 to 20 carbon atoms, a fluorine-containing alkylene group having 2 to 100 carbon atoms and ether bond or a fluorine-containing arylene group having 3 to 20 carbon atoms; and n3, n6 and n9 are 1.  
   
   
       14 . The fluorine-containing polymer of  claim 12 , wherein in the formula (2a), X 7  and X 8  are F; X 9  and X 16  are F; R 2a  is a fluorine-containing alkylene group having 1 to 20 carbon atoms, a fluorine-containing alkylene group having 2 to 100 carbon atoms and ether bond or a fluorine-containing arylene group having 3 to 20 carbon atoms; n3 is 0; and n6 and n9 are 1.  
   
   
       15 . The fluorine-containing polymer of  claim 6 , wherein the acid-labile or acid-degradable functional group Y 1  is:  
     
       
         
         
             
             
         
       
     
     wherein R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 14 , R 18 , R 19 , R 20 , R 21 , R 22 , R 24 , R 25 , R 26 , R 27 , R 28  and R 29  are the same or different and each is a hydrocarbon group having 1 to 10 carbon atoms; R 13 , R 15  and R 16  are H or hydrocarbon groups having 1 to 10 carbon atoms; R 17  and R 23  are divalent hydrocarbon groups having 2 to 10 carbon atoms.  
   
   
       16 . The fluorine-containing polymer of  claim 15 , wherein the acid-labile or acid-degradable functional group Y 1  is:  
     
       
         
         
             
             
         
       
     
     wherein R 30  is an alkyl group having 1 to 10 carbon atoms.  
   
   
       17 . The fluorine-containing polymer of  claim 6 , wherein the functional group Z 1  which is neither dissociated nor degraded by an acid is a group selected from the group consisting of CH 2 OH, COOH, CN and SO 3 H.  
   
   
       18 . A fluorine-containing polymer having a number average molecular weight of from 1,000 to 1,000,000 and represented by the formula (3):  
       -(M6)-(M7)-(A3)-  (3)  
     in which M6 is represented by:  
     
       
         
         
             
             
         
       
     
     M7 is represented by:  
     
       
         
         
             
             
         
       
     
     wherein X 19 , X 20 , X 23 , X 24 , X 25  and X 26  are the same or different and each is H or F; X 21  and X 22  are the same or different and each is H, F, Cl or CF 3 ; Rf 4  is a fluorine-containing alkylene group having 1 to 10 carbon atoms or a fluorine-containing alkylene group having 2 to 10 carbon atoms and ether bond; n12 is 0 or an integer of from 1 to 3; n11, n13, n14 and n15 are the same or different and each is 0 or 1; X 27 , X 28 , X 29  and X 30  are the same or different and each is H or F; Y 1  is an acid-labile or acid-degradable functional group; R 3  is a divalent hydrocarbon group having 1 to 20 carbon atoms, a fluorine-containing alkylene group having 1 to 20 carbon atoms, a fluorine-containing alkylene group having 2 to 100 carbon atoms and ether bond or a fluorine-containing arylene group having 3 to 20 carbon atoms; n16 is 0 or an integer of 1 or 2; n17 is 0 or 1, 
 A3 is a structural unit derived from a monomer copolymerizable with the structural units M6 and M7,  
 when M6+M7 is assumed to be equal to 100% by mole, the percent by mole ratio M6/M7 is 1 to 99/1 to 99,  
 said polymer comprises from 1 to 99% by mole of the structural unit M6, from 1 to 99% by mole of the structural unit M7 and from 0 to 98% by mole of the structural unit A3.  
 
   
   
       19 . The fluorine-containing polymer of  claim 18 , wherein in the formula (3), n11, n12 and n13 are 0; n14 and n15 are 1; and Rf 4  is (CF 2 ) or C(CF 3 ) 2 .  
   
   
       20 . The fluorine-containing polymer of  claim 18 , wherein in the formula (3), X 19 , X 20 , X 21 , X 22 , X 25  and X 26  are F; Rf 4  is (CF 2 ) 2  and each of n11, n13 and n14 is 1; and n12 and n15 are 0, or in the formula (3), X 19 , X 20 , X 21 , X 22 , X 23  and X 24  are F; Rf 4  is (CF 2 ) 2  and each of n11, n12 and n14 is 1; and n13 and n15 are 0.  
   
   
       21 . The fluorine-containing polymer of  claim 18 , wherein in the formula (3), X 19 , X 20 , X 21 , X 22 , X 23  and X 24  are the same or different and each is H or F; Rf 4  is CF 2  and each of n11, n12 and n14 is 1; and n13 and n15 are 0, 
 in the formula (3), X 19  and X 20  are the same or different and each is H or F; X 21 , X 22 , X 23  and X 24  are F; Rf 4  is CF 2  and each of n11, n12 and n15 is 1; and n13 and n14 are 0, or    in the formula (3), X 19  and X 20  are the same or different and each is H or F; X 21 , X 22 , X 25  and X 26  are F; Rf 4  is CF 2  and each of n11, n13 and n15 is 1; and n12 and n14 are 0.    
   
   
       22 . The fluorine-containing polymer of  claim 18 , wherein in the formula (3), R 3  is a fluorine-containing alkylene group having 1 to 20 carbon atoms, a fluorine-containing alkylene group having 2 to 100 carbon atoms and ether bond or a fluorine-containing arylene group having 3 to 20 carbon atoms.  
   
   
       23 . The fluorine-containing polymer of  claim 22 , wherein in the formula (3), X 27  and X 28  are H; X 29  and X 30  are F; and n16 and n17 are 1.  
   
   
       24 . The fluorine-containing polymer of  claim 22 , wherein in the formula (3), X 27  and X 28  are F; X is F; n16 is 0; and n17 is 1.  
   
   
       25 . The fluorine-containing polymer of  claim 18 , wherein in the formula (3), the acid-labile or acid-degradable functional group Y 1  is:  
     
       
         
         
             
             
         
       
     
     wherein R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 14 , R 18 , R 19 , R 20 , R 21 , R 22 , R 24 , R 25 , R 26 , R 27 , R 28  and R 29  are the same or different and each is a hydrocarbon group having 1 to 10 carbon atoms; R 13 , R 15  and R 16  are H or hydrocarbon groups having 1 to 10 carbon atoms; R 17  and R 23  are divalent hydrocarbon groups having 2 to 10 carbon atoms.  
   
   
       26 . The fluorine-containing polymer of  claim 25 , wherein the acid-labile or acid-degradable functional group Y 1  is:  
     
       
         
         
             
             
         
       
     
     wherein R 30  is an alkyl group having 1 to 10 carbon atoms  
   
   
       27 - 152 . (canceled)