Low-polydispersity photoimageable acrylic polymers, photoresists and processes for microlithography

1. An acrylic polymer having a polydispersity in the range of 1.05 to 1.3, said polymer consisting essentially of:

a repeat unit derived from an acrylic monomer selected from the group consisting of acrylate and methacrylate esters,

wherein at least one of said repeat units has a functional group selected from the group consisting of fluoroalcohol and protected fluoroalcohol groups, wherein the mole percent of said repeat units having the functional groups is from 28.8 to 75.4 mole percent based on the moles of repeat units of said acrylic polymer; and

wherein said polymer has a weight average molecular weight of 14,600 or less from 3,250 to 14,600.

2. The acrylic polymer of claim 1 , wherein the acrylic monomer is CH 2 ═CR′CO 2 R″ and

R′ is H, F, an alkyl group of 1 to 5 carbon atoms, or a fluoroalkyl group of 1 to 5 carbon atoms; and

R″ is a C 1 -C 20 acyclic aliphatic group cyclic C 5 -C 50 or a polycyclic C 7 -C 50 alkyl group, optionally containing at least one hydroxy functional group, or a functional group of the formula —C(R 1 )(R 2 )—[C(R 3 )(R 4 )]m-C(R 5 )(R 6 )—OH, wherein m=0, 1, 2, 3, 4 or 5;

R 1 and R 2 are independently C 1 -C 6 alkyl, C 1 -C 6 alkyl substituted with an ether oxygen, or R 1 and R 2 taken together form a 3- to 8-membered ring, optionally substituted with an ether oxygen, provided that the carbon attached to R 1 and R 2 is not at a bridgehead position;

R 3 and R 4 are independently H, C 1 -C 6 alkyl, C 1 -C 6 alkyl substituted with an ether oxygen, or R 3 and R 4 taken together form a 3- to 8-membered ring, optionally substituted with an ether oxygen;

R 5 and R 6 are independently H, C 1 -C 6 alkyl, C 1 -C 6 alkyl substituted with an ether oxygen, or R 5 and R 6 taken together form a 3- to 8-membered ring, optionally substituted with an ether oxygen; or

R 1 and R 5 taken together with —[C(R 3 )(R 4 )] m — form a 4- to 8-membered ring, provided that the carbon attached to R 1 and R 2 is not at a bridgehead position.

3. The acrylic polymer of claim 1 , wherein the acrylic monomer is selected from the group consisting of PinMAc (2-methyl-2-propenoic acid, 2-hydroxy-1,1,2-trimethylpropyl ester); PinAc; 2-methyl-2-adamantyl (meth)acrylate; 2-ethyl-2-adamantyl-(meth)acrylate; 2-propyl-2-adamantyl-(meth)acrylate; 2-(1-adamantyl)-2-propyl(meth)acrylate; α-(γ-butyrolactone)-(meth)acrylate; β-(γ-butyrolactone)-(meth)acrylate; 3-hydroxy-1-adamantyl-(meth)acrylate; 8-methyltricyclo-[5.2.1]decan-8-yl-(meth)acrylate; 8-ethyltricyclo[5.2.1]decan-8-yl-(meth)acrylate; 2-(4-methoxybutyl)-2-adamantyl-(meth)acrylate; mevalonic lactone-(meth)acrylate; PinAc; PinMAc; 4-hydroxy-1-methylcyclohexyl-(meth)acrylate; 1-methylcyclopentyl-(meth)acrylate; 1-ethylcyclopentyl-(meth)acrylate; 3-(2,2-bis(trifluoromethyl)-2-hydroxyethyl)-endo-2-(2-methylpropenoyl)-bicyclo[2.2.1]heptane; 3-(2,2-bis(trifluoromethyl)-2-hydroxyethyl)-endo-2-(propenoyl)-bicyclo[2.2.1]-heptane; and 5-(meth)acryloyloxy-2,6-norbornanecarbolactone.

4. The acrylic polymer of claim 1 , wherein the functional group is a fluoroalcohol functional group having the structure:

—X r (CH 2 ) q C(R f )(R f ′)OH

wherein R f and R f ′ are the same or different fluoroalkyl groups of from 1 to 10 carbon atoms, or taken together are (CF 2 ) n ; n is an integer from 2 to 10; X is selected from the group consisting of S, O, N, and P; and q=0 and r=0; or q=1 and r=0 or 1.

5. The acrylic polymer of claim 1 , wherein the functional group is a protected fluoroalcohol having the structure:

—X r (CH 2 ) q C(R f )(R f ′)OCH 2 OR b

wherein R f and R f ′ are the same or different fluoroalkyl groups of from 1 to 10 carbon atoms, or taken together are (CF 2 ) n ; n is an integer from 2 to 10; X is selected from the group consisting of S, O, N, and P;

q=0 and r=0; or q=1 and r=0 or 1; and

R b is C 1 -C 11 alkyl.