Ether monomers and polymers having multi-ring structures, and photosensitive polymers and resist compositions obtained from the same

A photosensitive terpolymer including an α-fluorinated acrylate monomer, a first alkenyl ether monomer and a second alkenyl ether monomer having the formula II

• 66
• wherein
• m+n equals 1;
• 0.01≦m/(m+n)≦0.8;
• R1 and R2 are independently selected from a group consisting of hydrogen and methyl;
• R3, R4, R8 and R9 are independently selected from a group consisting of hydrogen, hydroxy, alkyl, cycloalkyl, haloalkyl, alkoxy, carboxyl, carbonyl, ester and acid labile groups;
• and
• R5 is selected from a group consisting of hydrogen, hydroxy, alkyl, cycloalkyl, haloalkyl, alkoxy, carboxyl, carbonyl, ester and acid labile groups;
• and
• further wherein
• the terpolymer includes at least one acid labile group and the first alkenyl ether monomer and the second alkenyl ether monomer are different.

A photosensitive terpolymer including an α-fluorinated acrylate monomer, an alkenyl ether monomer and a dihydropyran having the formula III

• 67
• wherein
• x is 1 or 2;
• m+n equals 1;
• 0.3≦m/(m+n)≦0.8;
• and wherein
• R1 and R2 are independently selected from a group consisting of hydrogen and methyl;
• R3 and R4 are independently selected from a group consisting of hydrogen, hydroxy, alkyl, cycloalkyl, haloalkyl, alkoxy, carboxyl, carbonyl, ester and acid labile groups;
• and
• R5 is selected from a group consisting of hydrogen, hydroxy, alkyl, cycloalkyl, haloalkyl, alkoxy, carboxyl, carbonyl, ester and acid labile groups;
• and
• further wherein
• at least one of R3, R4 and R5 includes an acid labile group.

A photosensitive terpolymer including first and second α-fluorinated acrylate monomers and an alkenyl ether monomer having the formula IIB

• 68
• wherein
• m+n equals 1;
• 0.01≦m/(m+n)≦0.8
• R1 and R2 are independently selected from a group consisting of hydrogen and methyl;
• R3 and R4 are independently selected from a group consisting of hydrogen, hydroxy, alkyl, cycloalkyl, haloalkyl, alkoxy, carboxyl, carbonyl, ester and acid labile groups;
• and
• R5 and R10 are independently is selected from a group consisting of hydrogen, hydroxy, alkyl, cycloalkyl, haloalkyl, alkoxy, carboxyl, carbonyl, ester and acid labile groups;
• further wherein
• the terpolymer includes at least one acid labile group and the first α-fluorinated acrylate monomer and the second α-fluorinated acrylate monomer are different.

A photosensitive tetrapolymer including first and second α-fluorinated acrylate monomers and first and second alkenyl ether monomers having the formula IV

• 69
• wherein
• m+n+q+r=1;
• m+q=n+r;
• 0.01≦m (m+q)≦0.8;
• 0.01≦n (n+r)≦0.8;
• R1 and R2 are independently selected from a group consisting of hydrogen and methyl;
• R3, R4, R8 and R9 are independently selected from a group consisting of hydrogen, hydroxy, alkyl, cycloalkyl, haloalkyl, alkoxy, carboxyl, carbonyl, ester and acid labile groups;
• and
• R5 and R10 are independently selected from a group consisting of hydrogen, hydroxy, alkyl, cycloalkyl, haloalkyl, alkoxy, carboxyl, carbonyl, ester and acid labile groups;
• and
• further wherein
• the tetrapolymer includes at least one monomer that includes an acid labile group, the first alkenynl ether monomer and the second alkenynl ether monomer are different, and
• the first and second α-fluorinated acrylate monomers are different.

A photosensitive pentapolymer including first and second α-fluorinated acrylate monomers, first and second alkenyl ether monomers and a dihydrofuran having the formula V:

• 70
• wherein
• x is 1 or 2;
• m+n+q+r+s 1;
• m+q+s=n+r;
• 0.01≦m (m+q+s)≦0.8;
• 0.01≦n/(n+r)≦0.8;
• 0.01≦q (m+q+s)≦0.8;
• and
• R1 and R2 are independently selected from a group consisting of hydrogen and methyl;
• R3, R4, R8 and R9 are independently selected from a group consisting of hydrogen, hydroxy, alkyl, cycloalkyl, haloalkyl, alkoxy, carboxyl, carbonyl, ester and acid labile groups;
• and
• R5 and R10 are independently selected from a group consisting of hydrogen, hydroxy, alkyl, cycloalkyl, haloalkyl, alkoxy, carboxyl, carbonyl, ester and acid labile groups;
• and
• further wherein
• the tetrapolymer includes at least one monomer that includes an acid labile group, the first alkenyl ether monomer and the second alkenyl ether monomer are different, and
• the first and second α-fluorinated acrylate monomers are different.

A method of forming a photosensitive polymer comprising:

• combining at least one alkenyl ether monomer selected from the group consisting of alkenyl ether monomers represented by the formulas:
• 71
• wherein
• y is 0, 1 or 2;
• R6 is selected from a group consisting of alkyls and substituted alkyls having at least one and no more than 20 carbon atoms;
• and
• R7 is an acid labile group including a hydrocarbon or a substituted hydrocarbon having at least 4 and no more then 20 carbons;
• and
• a substituted or unsubstituted α-fluorinated acrylate monomer selected from the group represented by the formulas:
• 72
• in a solvent to form a polymerization solution, the polymerization solution being substantially free of heavy metals;
• heating the polymerization solution to a polymerization temperature for a polymerization period sufficient to cause the radical polymerization of the α-fluorinated acrylate and alkenyl ether monomers.

A photoresist composition suitable for forming patterns having a line/space pattern of less than 0.25 μm when exposed to light having a wavelength of 157 nm comprising:

• a photosensitive polymer represented by a formula selected from a group consisting of
• 73 74
• wherein
• x is 1 or 2;
• m+q+s=n+r
• R1 and R2 are independently selected from a group consisting of hydrogen and methyl;
• R3, R4, R8 and R9 are independently selected from a group consisting of hydrogen, hydroxy, alkyl, cycloalkyl, haloalkyl, alkoxy, carboxyl, carbonyl, ester and acid labile groups;
• and
• R5 and R10 are independently selected from a group consisting of hydrogen, hydroxy, alkyl, cycloalkyl, haloalkyl, alkoxy, carboxyl, carbonyl, ester and acid labile groups;
• and
• further wherein the polymer includes at least one monomer including an acid labile group;
• and
• a solvent.

A photosensitive polymer including at least one α-fluorinated acrylate monomer and at least one alkenyl ether monomer having the formula V:

• 75
• wherein
• x is 1 or 2;
• m+n+q+r+s=1;
• m+q+s=n+r;
• 0.01≦m/(m+q+s)≦0.8;
• 0.01≦n/(n+r)≦0.8;
• 0≦q/(m+q+s)≦0.8;
• and
• 0≦n/(n+r)≦0.8;
• 0≦s/(m+q+s)≦0.8;
• and
• R1 and R2 are independently selected from a group consisting of hydrogen and methyl;
• R3, R4, R8 and R9 are independently selected from a group consisting of hydrogen, hydroxy, alkyl, cycloalkyl, haloalkyl, alkoxy, carboxyl, carbonyl, ester and acid labile groups;
• and
• R5 and R10 are different and are independently selected from a group consisting of hydrogen, hydroxy, alkyl, cycloalkyl, haloalkyl, alkoxy, carboxyl, carbonyl, ester and acid labile groups;
• and
• further wherein
• the photosensitive polymer includes at least one monomer that includes an acid labile group.