1. A low polydispersity copolymer comprising: a. a repeat unit derived from an acrylic monomer selected from the group consisting of MAdA, HAdA, PinAc, PinMAc, and CH 2 ═C(CH 2 OH)CO 2 R′″, wherein R′″ is a C 1 -C 25 alkyl group, optionally substituted by one or more hydroxy, halogen, ether oxygen, ester or ketone carbonyl groups; b. a repeat unit derived from an unsaturated polycyclic monomer; and c. a functional group selected from the group of fluoroalcohol, protected fluoroalcohol and protected acid group; wherein at least 40 mole % of the repeat units of the low polydispersity copolymer are derived from acrylic monomers and the polydispersity is 1.05-2.0.
2. The low polydispersity copolymer of claim 1 , wherein the repeat unit derived from an unsaturated polycyclic monomer comprises a fluoroalcohol functional group or a protected fluoroalcohol functional group.
3. The low polydispersity copolymer of claim 1 , wherein the repeat unit derived from an unsaturated polycyclic monomer comprises a fluoroalcohol functional group, -X r (CH 2 ) q C(R f )(R f ′)OH, or a protected fluoroalcohol group functional group, -X r (CH 2 ) q C(R f )(R f ′)OR a, 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.
4. The low polydispersity copolymer of claim 1 , wherein the unsaturated polycyclic monomer is NB-F-OH.
5. The low polydispersity copolymer of claim 1 , further comprising a fluoro-olefin.
6. The low polydispersity copolymer of claim 1 , wherein the fluoro-olefin is tetrafluoroethylene.
wherein: s is 0, 1 or 2; a and b are independently 1, 2 or 3, except that a is not 1 when b is 2 or vice versa; and R 7 to R 16 and R 17 to R 20 are the same or different and each represents a hydrogen atom, a halogen atom, a carboxyl group, a C 3 to C 14 secondary or tertiary alkyl carboxylate, a hydrocarbon group or a substituted hydrocarbon group.
v is 0, 1, or2; A is O (oxygen) or NR 27 ; R 27 is selected from the group of H; C 1 -C 10 alkyl or alkoxy, optionally substituted by halogen or ether oxygens; C 6 -C 20 aryl; Y; C(R f )(R f ″)OR 28 ; R 29 Y; and OR 29 Y; R 28 is a C 1 -C 10 alkyl group; R 29 is a C 1 -C 20 alkylene group, optionally substituted by halogen or ether oxygen; Y is COZ′ or SO 2 Z′; Z′ is OH, halogen, R 30 or OR 30 ; R 30 is a C 1 -C 20 alkyl group, optionally substituted by halogen or ether oxygens; or C 6 -C 20 aryl; R f and R f ′ are the same or different fluoroalkyl groups of 1 to 10 carbon atoms or taken together are (CF 2 ) n where n is 2 to 10; and R 21 and R 22 are independently selected from the group of H; halogen; C 1 -C 10 alkyl or alkoxy, optionally substituted by halogen or ether oxygen; C 6 -C 20 aryl; Y; C(R f )(R f ′)OR 28 ; R 29 Y; and OR 29 Y; or R 21 and R 22 taken together are =C(R f )(R f ′) or C 2 -C 9 alkylene, optionally substituted by halogen or incorporating an ether oxygen.
w is 0, 1, or 2; R 23 , R 24 and R 25 are independently selected from the group of H; halogen; C 1 -C 10 alkyl or alkoxy, optionally substituted by halogen or ether oxygen; C 6 -C 20 aryl; Y; C(R f )(R f ′)OR 28 ; R 29 Y; and OR 29 Y; or R 24 and R 25 taken together are part of a double bond; R 26 is hydrogen or an acid-labile protecting group; R 28 is a C 1 -C 10 alkyl group; R 29 is a C 1 -C 20 alkylene group, optionally substituted by halogen or ether oxygen; Y is COZ′ or SO 2 Z′; Z′ is OH, halogen, R 30 or OR 30; R 30 is a C 1 -C 20 alkyl group, optionally substituted by halogen or ether oxygens; or C 6 -C 20 aryl; and R f and R f ′ are the same or different fluoroalkyl groups of 1 to 10 carbon atoms or taken together are (CF 2 )p where n is 2 to 10.
w is 0, 1, or 2; R 23 , R 24 and R 25 are independently selected from the group of H; halogen; C 1 -C 10 alkyl or alkoxy, optionally substituted by halogen or ether oxygen; C 6 -C 20 aryl; Y; C(R f )(R f ′)OR 28 ; R 29 Y; and OR 29 Y; or R 24 and R 25 taken together are part of a double bond; R 26 is hydrogen or an acid-labile protecting group; R 28 is a C 1 -C 10 alkyl group; R 29 is a C 1 -C 20 alkylene group, optionally substituted by halogen or ether oxygen; Y is COZ′ or SO 2 Z′; Z′ is OH, halogen, R 30 or OR 30 ; R 30 is a C 1 -C 20 alkyl group, optionally substituted by halogen or ether oxygens; or C 6 -C 20 aryl; and R f and R f ′ are the same or different fluoroalkyl groups of 1 to 10 carbon atoms or taken together are (CF 2 ) n where n is 2 to 10; and c. a functional group selected from the group of fluoroalcohol, protected fluoroalcohol and protected acid group; wherein at least 40 mole% of the repeat units of the low polydispersity copolymer are derived from acrylic monomers and the polydispersity is 1.05-2.0.
11. The low polydispersity copolymer of claim 10 , wherein the acrylic monomer is CH 2 ═CR′CO 2 R″; R′ is H, F, an alkyl group of 1 to 5 carbon atoms, or a fluoroalkyl group of 1 to 5 carbon atoms; R″ is a C 1 -C 20 acyclic aliphatic group; a polycyclic C 5 -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; 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.
12. The low polydispersity copolymer of claim 10 , further comprising a fluoro-olefin.
13. The low polydispersity copolymer of claim 12 , wherein the fluoro-olefin is tetrafluoroethylene.
14. A photoresist comprising: a. a photoactive component; and b. a low polydispersity copolymer comprising: a repeat unit derived from an acrylic monomer selected from the group consisting of MAdA, HAdA, PinAc, PinMAc, and CH 2 ═C(CH 2 OH)CO 2 R′″, wherein R′″ is a C 1 -C 25 alkyl group. optionally substituted by one or more hydroxy, halogen, ether oxygen, ester or ketone carbonyl groups; ii. a repeat unit derived from an unsaturated polycyclic monomer; and iii. a functional group selected from the group of fluoroalcohol, protected fluoroalcohol, and protected acid groups; wherein at least 40 mole% of the repeat units of the low polydispersity copolymer are derived from acrylic monomers and the polydispersity is 1.05-2.0.
15. The photoresist of claim 14 , wherein the low-polydispersity copolymer further comprises a fluoro-olefin.
16. The photoresist of claim 15 , wherein the fluoro-olefin is tetrafluoroethylene.
w is 0, 1, or 2; R 23 , R 24 and R 25 are independently selected from the group of H; halogen; C 1 -C 10 alkyl or alkoxy, optionally substituted by halogen or ether oxygen; C 6 -C 20 aryl; Y; C(R f )(R f ′)OR 28 ; R 29 Y; and OR 29 Y; or R 24 and R 25 taken together are part of a double bond; R 26 is hydrogen or an acid-labile protecting group; R 28 is a C 1 -C 10 alkyl group; R 29 is a C 1 -C 20 alkylene group, optionally substituted by halogen or ether oxygen; Y is COZ′ or SO 2 Z′; Z′ is OH, halogen, R 30 or OR 30 ; R 30 is a C 1 l -C 20 alkyl group, optionally substituted by halogen or ether oxygens; or C 6 -C 20 aryl; and R f and R f ′ are the same or different fluoroalkyl groups of 1 to 10 carbon atoms or taken together are (CF 2 ) n where n is 2 to 10; and iii. a functional group selected from the group of fluoroalcohol, protected fluoroalcohol, and protected acid groups; wherein at least 40 mole% of the repeat units of the low polydispersity copolymer are derived from acrylic monomers and the polydispersity is 1.05-2.0.
18. The photoresist of claim 17 , wherein the low-polydispersity copolymer further comprises a fluoro-olefin.
19. The photoresist of claim 18 , wherein the fluoro-olefin is tetrafluoroethylene.
20. A process for forming a coated substrate, comprising: A. coating a substrate with a mixture comprising: 1. a low-polydispersity polymer of claim 1 or 10 , 2. a photoactive component, and 3. a solvent; and B. evaporating the solvent.
21. The process of claim 20 , wherein low polydispersity copolymer further comprises a fluoro-olefin.
22. The process of claim 21 , wherein the fluoro-olefin is tetrafluoroethylene.
23. A process for forming a photoresist image on a substrate, comprising: A. forming a photoresist layer on a substrate, wherein the photoresist comprises: 1. a photoactive component, and 2. a low polydispersity copolymer of claim 1 or 10 ; B. imagewise exposing the photoresist layer to actinic radiation to form imaged and non-imaged areas; and C. developing the exposed photoresist layer having imaged and non-imaged areas to form the photoresist image on the substrate.
24. The process of claim 23 wherein the low polydispersity copolymer further comprises a fluoro-olefin.
25. The process of claim 24 , wherein the fluoro-olefin is tetrafluoroethylene.
wherein: R=alkyl, alkenyl, aryl, aralkyl, substituted alkyl, substituted aryl, carbocyclic or heterocyclic ring, alkylthio, alkoxy, or dialkylamino; and Z=H, alkyl, aryl, aralkyl, substituted alkyl, substituted aryl, carbocyclic or heterocyclic ring, alkylthio, arylthio, alkoxycarbonyl, aryloxycarbonyl, carboxy, acyloxy, carbamoyl, cyano, dialkyl- or diaryl-phosphonato, or dialkyl- or diaryl-phosphinato.
27. The process of claim 26 , wherein the monomer mix further comprises a fluoro-olefin.
28. The process of claim 27 , wherein the fluoro-olefin is tetrafluoroethylene.
29. The process of claim 26 , wherein Z is alkylthio.
30. The process of claim 26 , wherein the chain transfer agent is S-cyanomethyl-S-dodecyltrithiocarbonate or 4-cyano-4(dodecylsulfanylthiocarbonyl)sulfanyl pentanoic acid.
31. The process of claim 26 , wherein the acrylic monomer is selected from the group consisting of MAdA, HAdA, PinAc and PinMAc.
33. The process of claim 26 , wherein the unsaturated polycyclic monomer is NB-F-OH.