Self-topcoating resist for photolithography

1. A resist composition comprising:

a) a photoresist polymer that does not comprise a silsesquioxane polymer;

b) at least one photoacid generator;

c) a solvent; and

d) a resist additive compound including a polymer, oligomer or cage structure having the following structure A:

wherein,

each Z 1 , Z 2 , and Z 3 independently represents a member selected from the group consisting of linear, branched, or cyclic alkylene, and linear, branched or cyclic heteroalkylene;

n 1 , n 2 and n 3 independently represent the number of repeat units of each type in the polymer, oligomer, or cage structure; and n 1 +n 2 +n 3 ≧2;

X 1 , X, and X 3 independently represents a member selected from the group consisting of linear, branched, or cyclic alkylene, linear, branched or cyclic heteroalkylene, carboxyl, and carbonyl;

R 1 is a moiety containing a fluoroalcohol group that is unprotected or partially or fully protected with an acid-labile group; and

R 2 is selected from H, or a moiety containing carboxylic acid, sulfonamide, fluoroalcohol, or sulfonic acid, that is unprotected or partially or fully protected with an acid-labile group; and

R 3 is a nonfluorinated or partially fluorinated or perfluorinated functionality, other than a fluorinated ether, that is acid-labile or non-acid labile, wherein the functionality does not comprise an unsaturated hydrocarbon group;

provided that

the resist additive compound contains a fluorocarbyl moiety other than a fluorinated ether;

if Z 1 , Z 2 and/or Z 3 is

then X 1 and R 1 together, X 2 and R 2 together, and/or X 3 and R 3 together can represent hydrogen;

if Z 1 , Z 2 and/or Z 3 is

and X 1 , X 2 and/or X 3 is alkylene, then R 1 , R 2 and R 3 are not —C(CF 3 ) 2 —OH;

if X 1 , X 2 and/or X 3 is carboxyl, then R 1 , R 2 and R 3 are not norbornyl substituted by —CH 2 —C(CF 3 ) 2 —OH; and

If Z 1 , Z 2 and/or Z 3 is linear alkylene, and X 1 , X 2 and/or X 3 is methylene, then R 1 , R 2 and R 3 are not —C(CF 3 ) 2 —OH;

and provided that the compound does not comprise a structure selected from the group consisting of:

2. The resist composition according to claim 1 , wherein the compound is soluble in an aqueous alkaline developer.

3. The resist composition according to claim 1 , wherein the compound has a high surface activity.

4. The resist composition according to claim 1 , wherein the compound includes a polymer or an oligomer having the structure A1:

wherein

R 4 , R 5 , and R 6 are independently H, alkyl, or fluoroalkyl;

R 7 is a linear, branched, or cyclic alkylene, linear, branched or cyclic heteroalkylene group containing one or more fluoroalcohol groups that are unprotected or partially or fully protected with an acid-labile group; and

R 8 is selected from H or linear, branched, or cyclic alkylene, linear, branched or cyclic heteroalkylene groups containing one or more carboxylic acid, sulfonamide, fluoroalcohol, or sulfonic acid moieties, that are unprotected or partially or fully protected with an acid-labile group; and

R 9 is a nonfluorinated or partially fluorinated or perfluorinated functionality, other than a fluorinated ether, that is acid-labile or non-acid labile;

n 4 , n 5 , and n 6 are integers such that n 4 +n 5 +n 6 is greater than or equal to 2.

5. The resist composition according to claim 1 , wherein the compound includes a polymer or oligomer having the structure A2:

wherein

X 4 is a member selected from the group consisting of linear, branched, or cyclic alkylene, linear, branched or cyclic heteroalkylene, carboxyl, and carbonyl;

R 10 and R 11 are independently selected from H and linear, branched, or cyclic alkylene, linear, branched or cyclic heteroalkylene groups containing one or more carboxylic acid, sulfonamide, fluoroalcohol, or sulfonic acid moieties, that are unprotected or partially or fully protected with an acid-labile group, or a nonfluorinated or partially fluorinated or perfluorinated functionality, other than a fluorinated ether, that is acid-labile or non-acid labile, provided that one of R 10 and R 11 is a partially fluorinated or perfluorinated functionality, other than a fluorinated ether, that is acid-labile or non-acid labile;

n 7 is an integer greater than or equal to 2.

6. The resist composition according to claim 1 , wherein the compound includes a polymer or oligomer having the structure A3:

wherein

X 5 represents a member selected from the group consisting of linear, branched, or cyclic alkylene, linear, branched or cyclic heteroalkylene, carboxyl, and carbonyl;

R 12 is selected from H, carboxylic acid, sulfonamide, fluoroalcohol, or sulfonic acid, that is unprotected or partially or fully protected with an acid-labile group, or a nonfluorinated or partially fluorinated or perfluorinated functionality (other than a fluorinated ether) that is acid-labile or non-acid labile; and

R 13 is a linear, branched, or cyclic alkylene, linear, branched or cyclic heteroalkylene group containing one or more fluoroalcohol groups that are unprotected or partially or fully protected with an acid-labile group; and

R 14 is selected from H and linear, branched, or cyclic alkylene, linear, branched or cyclic heteroalkylene groups containing one or more carboxylic acid, sulfonamide, fluoroalcohol, or sulfonic acid moieties, that are unprotected or partially or fully protected with an acid-labile group, or a nonfluorinated or partially fluorinated or perfluorinated functionality (other than a fluorinated ether) that is acid-labile or non-acid labile, provided one of R 12 and R 14 is a fluorocarbyl moiety other than a fluorinated ether;

n 8 , n 9 , n 10 are integers such that n 8 +n 9 +n 10 is greater than or equal to 2.

7. A method forming a patterned material layer on a substrate, the method comprising the following steps:

a) providing a substrate having a material layer on a surface thereof;

b) coating the substrate with the resist composition according to claim 1 , thereby forming a coated substrate;

c) patternwise exposing the coated substrate to imaging irradiation;

d) optionally post-exposure baking the said exposed layer;

e) contacting the coated substrate with an aqueous alkaline developer, wherein a portion of the resist composition is removed, thereby forming a pattern in the resist composition on the material layer; and

f) transferring the pattern in the resist composition to the material layer.

8. The method according to claim 7 , which is carried out under immersion lithography conditions.

9. The method of claim 8 , wherein the additive rises to the surface of the resist composition, thereby inhibiting the leaching of unwanted material into immersion fluid.

10. The method according to claim 7 , wherein the compound of the resist composition includes a polymer or an oligomer having the structure A1:

wherein

R 4 , R 5 , and R 6 are independently H, alkyl, or fluoroalkyl;

R 7 is a linear, branched, or cyclic alkylene, linear, branched or cyclic heteroalkylene group containing one or more fluoroalcohol groups that are unprotected or partially or fully protected with an acid-labile group; and

R 8 is selected from H or linear, branched, or cyclic alkylene, linear, branched or cyclic heteroalkylene groups containing one or more carboxylic acid, sulfonamide, fluoroalcohol, or sulfonic acid moieties, that are unprotected or partially or fully protected with an acid-labile group; and

R 9 is a nonfluorinated or partially fluorinated or perfluorinated functionality, other than a fluorinated ether, that is acid-labile or non-acid labile;

n 4 , n 5 , and n 6 are integers such that n 4 +n 5 +n 6 is greater than or equal to 2.

11. The method according to claim 7 , wherein the compound of the resist composition includes a polymer or oligomer having the structure A2:

wherein

X 4 is a member selected from the group consisting of linear, branched, or cyclic alkylene, linear, branched or cyclic heteroalkylene, carboxyl, and carbonyl;

R 10 and R 11 are independently selected from H and linear, branched, or cyclic alkylene, linear, branched or cyclic heteroalkylene groups containing one or more carboxylic acid, sulfonamide, fluoroalcohol, or sulfonic acid moieties, that are unprotected or partially or fully protected with an acid-labile group, or a nonfluorinated or partially fluorinated or perfluorinated functionality, other than a fluorinated ether, that is acid-labile or non-acid labile, provided that one of R 10 and R 11 is a partially fluorinated or perfluorinated functionality, other than a fluorinated ether, that is acid-labile or non-acid labile;

n 7 is an integer greater than or equal to 2.

12. The method according to claim 7 , wherein the compound of the resist composition includes a polymer or oligomer having the structure A3:

wherein

X 5 represents a member selected from the group consisting of linear, branched, or cyclic alkylene, linear, branched or cyclic heteroalkylene, carboxyl, and carbonyl;

R 12 is selected from H, carboxylic acid, sulfonamide, fluoroalcohol, or sulfonic acid, that is unprotected or partially or fully protected with an acid-labile group, or a nonfluorinated or partially fluorinated or perfluorinated functionality (other than a fluorinated ether) that is acid-labile or non-acid labile; and

R 13 is a linear, branched, or cyclic alkylene, linear, branched or cyclic heteroalkylene group containing one or more fluoroalcohol groups that are unprotected or partially or fully protected with an acid-labile group; and

R 14 is selected from H and linear, branched, or cyclic alkylene, linear, branched or cyclic heteroalkylene groups containing one or more carboxylic acid, sulfonamide, fluoroalcohol, or sulfonic acid moieties, that are unprotected or partially or fully protected with an acid-labile group, or a nonfluorinated or partially fluorinated or perfluorinated functionality (other than a fluorinated ether) that is acid-labile or non-acid labile, provided one of R 12 and R 14 is a fluorocarbyl moiety other than a fluorinated ether;

n 8 , n 9 , n 10 are integers such that n 8 +n 9 +n 10 is greater than or equal to 2.

13. A substrate composition comprising:

a) a substrate having a material layer on a surface thereof; and

b) a layer of the resist composition according to claim 1 formed on the material layer.

14. A resist composition comprising:

a) a photoresist polymer;

b) at least one photoacid generator;

c) a solvent; and

d) a resist additive compound having one of the following structures:

wherein a:b=2-98 mole %: 98-2 mole %, and a+b=100 mole %;

wherein c:d=2-98 mole %:98-2 mole %, and c+d=100 mole %;

wherein e:f=2-98 mole %:98-2 mole %, and e+f=100 mole %;

wherein g:h=2-98 mole %:98-2 mole %, and g+h=100 mole %;

wherein i:j=2-98 mole %:98-2 mole %, and i+j=100 mole %;

wherein k:l=2-98 mole %:98-2 mole %, and k+l=100 mole %;

wherein m:n:o=2-96 mole %:96-2 mole %:2-96 mole %, and m+n+o=100 mole %;

wherein p:q=2-98 mole %:98-2 mole %, and p+q=100 mole %;

wherein r:s=2-98 mole %:98-2 mole %, and r+s=100 mole %;

wherein t:u:v=2-96 mole %:96-2 mole %:2-96 mole %, and t+u+v=100 mole %;

wherein w:x=2-98 mole %:98-2 mole %, and w+x=100 mole %;

wherein mm:nn=2-98 mole %:98-2 mole %, and mm+nn=100 mole %;

wherein qq:rr=2-98 mole %:98-2 mole %, and qq+rr=100 mole %;

wherein ss:tt=2-98 mole %:98-2 mole %, and ss+tt=100 mole %;

wherein uu:vv:ww=2-96 mole %:96-2 mole %:2-96 mole %, and uu+vv+ww=100 mole %; and

wherein xx:yy:zz=2-96 mole %:96-2 mole %:2-96 mole %, and xx+yy+zz=100 mole %.

15. A method forming a patterned material layer on a substrate, the method comprising the following steps:

a) providing a substrate having a material layer on a surface thereof;

b) coating the substrate with the resist composition according to claim 14 , thereby forming a coated substrate;

c) patternwise exposing the coated substrate to imaging irradiation;

d) optionally post-exposure baking the said exposed layer;

e) contacting the coated substrate with an aqueous alkaline developer, wherein a portion of the resist composition is removed, thereby forming a pattern in the resist composition on the material layer; and

f) transferring the pattern in the resist composition to the material layer.

16. A substrate composition comprising:

a) a substrate having a material layer on a surface thereof; and

b) a layer of the resist composition according to claim 14 formed on the material layer.