Vinyl addition polycyclic olefin polymers prepared with non-olefinic chain transfer agents and uses thereof

A photoresist composition comprising a poly(cyclic olefin) polymer comprising,

• a first monomer unit according to Formula (I):
• wherein X is selected from —CH2—, —CH2—CH2—, O, S, and —NH—;
• m is an integer from 0 to 5;
• and each occurrence of R1, R2, R3 and R4 is independently selected from one of the following groups:
• a) H, halogen, linear, branched or cyclic C1 to C30 alkyl, aryl, aralkyl, alkaryl, alkenyl or alkynyl;
• b) linear or branched C1 to C24 halohydrocarbyls, —(CH2)nC(O)OR*, —(CH2)nC(O)OR′, —(CH2)nOR, —(CH2)nOC(O)R, —(CH2)nC(O)R, —(CH2)n—OC(O)OR′, —(CH2)nC(R)2CH(R)(C(O)OR**), —(CH2)n(CR2)nCH(R)(C(O)OR**), —(CH2)nC(OR***)(CF3)2, —(CR″2)nOR, —CH2—[O(CH2)n]m*—C(OR***)(CF3)2, —(CH2)nC(R)2CH(C(O)OR**)2, —(CH2)nC(O)OH, CH2)nC(R*)2CH(R*)(C(O)OH), —(CH2)n—C(O)—O—R18, —(CH2)n—C(CY3)2—OH, and —(CH2)nC(R*)2CH(C(O)OH)2;
• where each occurrence of R is independently selected from H and linear or branched C1 to C10 alkyl;
• R′ is a linear or branched C1 to C10 alkyl or alkylol;
• R″ is selected from H and halogen;
• n and m* are each an integer from 0 to 10;
• R* represents an acid labile group cleavable by a photoacid generator;
• R** is selected from R′ and R* as defined above and tertiary C4 to C20 alkyl and cycloalkyl, C1 to C6 trialkylsilyl groups, and C4 to C20 oxoalkyl;
• R*** is selected from H, —CH2OR′″, —C(O)OR′″ and —C(O)R′″, where R′″ is selected from methyl, ethyl, t-butyl, and C1 to C20 linear or branched cycloaliphatic, R18 is selected from H, and linear, branched or cyclic C1-C24 alkyl, aryl, aralkyl, and alkaryl, Y is selected from F and Cl and at least one occurrence of Y is F;
• c) C1 to C30 linear, branched, or cyclic alkyl, aryl, aralkyl, alkaryl, alkenyl or alkynyl containing one or more hetero atoms selected from O, N, and Si;
• d) a hydroxy alkyl ether according to Formula (IV):
• -A-O—[—(CR352—)q—O—]p—(CR352—)q—OH (IV)
• wherein A is a linking group selected from C1 to C6 linear, branched, or cyclic alkylene, each occurrence of R35 is independently selected from H, methyl, ethyl and a halide, q is from 1 to 5, and p is from 0 to 3;
• e) a group according to Formula (V):
• —R36—Z (V)
• where R36 is a linear, branched or cyclic C1 to C30, optionally partially or completely halogenated, alkylene, arylene, aralkylene, alkarylene, alkenylene or alkynylene linking group and Z is a functional group selected from hydroxyl, carboxylic acid, amine, thiol, isocyanate and epoxy;
• and
• f) CrX″2r+1, wherein X″ is independently a halogen selected from fluorine, chlorine, bromine or iodine and r is an integer from 1 to 20;
• and
• a third monomer unit according to Formula (III):
• wherein m is an integer from 0 to 5;
• X is —CH2—, —CH2—CH2—, O, S, or —NH—;
• R9 to R12 are independently selected from H, halogen, linear, branched or cyclic C1 to C30 alkyl, alkylol, aryl, aralkyl, alkaryl, alkenyl or alkynyl;
• a non-carboxylic acid group containing an active hydrogen with a pKa of 15 or less, and a carboxylic acid substituents selected from the group consisting of those in accordance with the formulas —(CH2)qC(O)OH, (CH2)qC(R25)2CH(R25)(C(O)OH) or —(CH2)qC(R25)2CH(C(O)OH)2, wherein q is an integer from 0 to 10 and each occurrence of R25 is independently selected from H, halogen, linear, branched or cyclic C1 to C10 alkyl, and linear, branched or cyclic C1 to C10 halogenated alkyl;
• and
• wherein at least one of R9 to R12 is a carboxylic acid substituent as described above.

A photoresist composition comprising a poly(cyclic olefin) polymer prepared by a method of polymerizing poly(cyclic)olefin monomers comprising:

• (a) combining a monomer composition comprising one or more poly(cyclic)olefin monomers, a non-olefinic chain transfer agent and an optional activator compound in a reaction vessel to form a mixture;
• and
• (b) adding a polymerization catalyst containing Ni and/or Pd, the catalyst causing the mixture to polymerize;
• wherein the non-olefinic chain transfer agent includes one or more compounds selected from the group consisting of H2, alkylsilanes, alkylalkoxysilanes, alkylgermanes, alkylalkoxygermanes, alkylstannanes and alkylalkoxystannanes.

A photoresist composition comprising a poly(cyclic olefin) polymer comprising a first monomer unit according to Formula (I):

• wherein X is selected from —CH2—, —CH2—CH2—, O, S, and —NH—;
• m is an integer from 0 to 5;
• and each occurrence of R1, R2, R3 and R4 is independently selected from one of the following groups:
• a) H, halogen, linear, branched or cyclic C1 to C30 alkyl, aryl, aralkyl, alkaryl, alkenyl or alkynyl;
• b) linear or branched C1 to C24 halohydrocarbyls, —(CH2)nC(O)OR*, —(CH2)nC(O)OR′, —(CH2)nOR, —(CH2)nOC(O)R, —(CH2)nC(O)R, —(CH2)n—OC(O)OR′, —(CH2)nC(R)2CH(R)(C(O)OR**), —(CH2)n(CR2)nCH(R)(C(O)OR**), —(CH2)nC(OR***)(CF3)2, —(CR″2)nOR, —CH2—[O(CH2)n]m*—C(OR***)(CF3)2, —(CH2)nC(R)2CH(C(O)OR**)2, —(CH2)nC(O)OH, CH2)nC(R*)2CH(R*)(C(O)OH), —(CH2)n—C(O)—O—R18, —(CH2)n—C(CY3)2—OH, and —(CH2)nC(R*)2CH(C(O)OH)2;
• where each occurrence of R is independently selected from H and linear or branched C1 to C10 alkyl;
• R′ is a linear or branched C1 to C10 alkyl or alkylol;
• R′ is selected from H and halogen;
• n and m* are each an integer from 0 to 10;
• R* represents an acid labile group cleavable by a photoacid generator;
• R** is selected from R′ and R* as defined above and tertiary C4 to C20 alkyl and cycloalkyl, C1 to C6 trialkylsilyl groups, and C4 to C20 oxoalkyl;
• R*** is selected from H, —CH2OR′″, —C(O)OR′″ and —C(O)R′″, where R′″ is selected from methyl, ethyl, t-butyl, and C1 to C20 linear or branched cycloaliphatic, R18 is selected from H, and linear, branched or cyclic C1-C24 alkyl, aryl, aralkyl, and alkaryl, Y is selected from F and Cl and at least one occurrence of Y is F;
• c) C1 to C30 linear, branched, or cyclic alkyl, aryl, aralkyl, alkaryl, alkenyl or alkynyl containing one or more hetero atoms selected from O, N, and Si;
• d) a hydroxy alkyl ether according to Formula (IV):
• -A-O—[—(CR352—)q—O—]p—(CR352—)q—OH (IV)
• wherein A is a linking group selected from C1 to C6 linear, branched, or cyclic alkylene, each occurrence of R35 is independently selected from H, methyl, ethyl and a halide, q is from 1 to 5, and p is from 0 to 3;
• e) a group according to Formula (V):
• —R36—Z (V)
• where R36 is a linear, branched or cyclic C1 to C30, optionally partially or completely halogenated, alkylene, arylene, aralkylene, alkarylene, alkenylene or alkynylene linking group and Z is a functional group selected from hydroxyl, carboxylic acid, amine, thiol, isocyanate and epoxy;
• and
• f) CrX″2r+1, wherein X″ is independently a halogen selected from fluorine, chlorine, bromine or iodine and r is an integer from 1 to 20.

A photoresist composition comprising a poly(cyclic olefin) polymer comprising,

• a first monomer unit according to Formula (I):
• wherein X is selected from —CH2—, —CH2—CH2—, O, S, and —NH—;
• m is an integer from 0 to 5;
• and each occurrence of R1, R2, R3 and R4 is independently selected from one of the following groups:
• a) H, halogen, linear, branched or cyclic C1 to C30 alkyl, aryl, aralkyl, alkaryl, alkenyl or alkenyl;
• b) linear or branched C1 to C24 halohydrocarbyls, —(CH2)nC(O)OR*, —(CH2)nC(O)OR′, —(CH2)nOR, —(CH2)nOC(O)R, —(CH2)nC(O)R, —(CH2)n—OC(O)OR′, —(CH2)nC(R)2CH(R)(C(O)OR**), —(CH2)n(CR2)nCH(R)(C(O)OR**), —(CH2)nC(OR***)(CF3)2, —(CR″2)nOR, —CH2—[O(CH2)n]m*—C(OR***)(CF3)2, —(CH2)nC(R)2CH(C(O)OR**)2, —(CH2)nC(O)OH, CH2)nC(R*)2CH(R*)(C(O)OH), —(CH2)n—C(O)—O—R18, —(CH2)n—C(CY3)2—OH, and —(CH2)nC(R*)2CH(C(O)OH)2;
• where each occurrence of R is independently selected from H and linear or branched C1 to C10 alkyl;
• R′ is a linear or branched C1 to C10 alkyl or alkylol;
• R″ is selected from H and halogen;
• n and m* are each an integer from 0 to 10;
• R* represents an acid labile group cleavable by a photoacid generator;
• R** is selected from R′ and R* as defined above and tertiary C4 to C20 alkyl and cycloalkyl, C1 to C6 trialkylsilyl groups, and C4 to C20 oxoalkyl;
• R*** is selected from H, —CH2OR′″, —C(O)OR′″ and —C(O)R′″, where R′″ is selected from methyl, ethyl, t-butyl, and C1 to C20 linear or branched cycloaliphatic, R18 is selected from H, and linear, branched or cyclic C1-C24 alkyl, aryl, aralkyl, and alkaryl, Y is selected from F and Cl and at least one occurrence of Y is F;
• c) C1 to C30 linear, branched, or cyclic alkyl, aryl, aralkyl, alkaryl, alkenyl or alkynyl containing one or more hetero atoms selected from O, N, and Si;
• d) a hydroxy alkyl ether according to Formula (IV):
• -A-O—[—(CR352—)q—O—]p—(CR352—)q—OH (IV)
• wherein A is a linking group selected from C1 to C6 linear, branched, or cyclic alkylene, each occurrence of R35 is independently selected from H, methyl, ethyl and a halide, q is from 1 to 5, and p is from 0 to 3;
• e) a group according to Formula (V):
• —R36—Z (V)
• where R36 is a linear, branched or cyclic C1 to C30, optionally partially or completely halogenated, alkylene, arylene, aralkylene, alkarylene, alkenylene or alkynylene linking group and Z is a functional group selected from hydroxyl, carboxylic acid, amine, thiol, isocyanate and epoxy;
• and
• f) CrX″2r+1, wherein X″ is independently a halogen selected from fluorine, chlorine, bromine or iodine and r is an integer from 1 to 20;
• and
• a second monomer unit according to Formula (II):
• wherein m is an integer from 0 to 5;
• X is selected from —CH2—, —CH2—CH2—, O, S, and —NH—;
• R5 to R8 are independently selected from H, —(CH2)n—C(O)OR″, —(CH2)n—OR′, Si(OR′)3, —(CB2)n—OC(O)R″, —(CH2)n—OC(O)OR″, —(CH2)n—C(O)R′, —(CH2)nC(R*)2CH(R*)(C(O)OR**), —(CH2)nC(R*)2CH(C(O)OR**)2, —C(O)O—(CH2)n—OR′ and —(CH2)n—O—(CH2)n—OR′, wherein n is independently an integer from 0 to 10;
• B is hydrogen or a halogen;
• R* and R are independently hydrogen, a halogen, C1 to C10 linear or branched alkyl or cycloalkyl, or C1 to C10 linear or branched halogenated alkyl or cycloalkyl;
• R** is independently C1 to C10 linear or branched alkyl or cycloalkyl or C1 to C10 linear or branched halogenated alkyl cycloalkyl;
• and R″ is independently C1 to C10 linear or branched alkyl or halogenated alkyl, C4 to C20 monocyclic or polycyclic cycloaliphatic or halogenated cycloalkyl moiety, a cyclic ether, a cyclic ketone or a cyclic ester (lactone), wherein each of the cyclic ether, ketone and ester can be halogenated or not.

A positive tone photoresist composition comprising,

• (a) a solvent,
• (b) a photosensitive acid generator;
• and
• (c) one or more positive tone imaging polymers, wherein the positive tone imaging polymers contain a functional group containing moiety that contains a group that can be cleaved when exposed to radiation, rendering the polymer more soluble to a developer than the unexposed polymer,
• wherein the positive tone imaging polymer is prepared by a method of polymerizing poly(cyclic)olefin monomers comprising:
• (a) combining a monomer composition comprising one or more poly(cyclic)olefin monomers, a non-olefinic chain transfer agent and an optional activator compound in a reaction vessel to form a mixture;
• and
• (b) adding a polymerization catalyst containing Ni and/or Pd, the catalyst causing the mixture to polymerize;
• wherein the non-olefinic chain transfer agent includes one or more compounds selected from the group consisting of H2, alkylsilanes, alkylalkoxysilanes, alkylgermanes, alkylalkoxygermanes, alkylstannanes and alkylalkoxystannanes.