Method of controlling the differential dissolution rate of photoresist compositions, polycyclic olefin polymers and monomers used for making such polymers

A photoresist composition comprising a polycyclic olefin based polymer having a desired dissolution rate, said polymer comprising at least one repeat unit derived from a polycyclic olefin monomer having a fluorinated carbinol pendent group as represented by Formula A:

• where for Formula A m is an integer from 0 to 5;
• and Z represents —(CH2)p—, where p is equal to 1;
• and where one of R1 to R4 is a fluorinated carbinol pendent group represented by the following formula:
• —(CH2)n—C(CF3)2—OR′
• wherein n is an integer from 0 to 5, and R′ is selected from hydrogen or an acid labile group, and the remaining three of R1, R2, R3 and R4 are each hydrogen, and where such at least one type of repeat unit has an exo isomer mole percent for the fluorinated carbinol pendent group that is greater than or less than an expected exo isomer mole percent for the polycyclic olefin monomer, such expected exo isomer mole percent based on the thermodynamic equilibrium of the isomers of such polycyclic olefin monomer that are obtained from a Diels-Alder reaction used to form such monomer and
• wherein said exo isomer mole percent for said fluorinated carbinol pendent group is selected from less than about 15 mole percent and greater than about 25 mole percent, based on total moles of exo isomer and endo isomer.

A photoresist composition comprising a polymer consisting essentially of norbomene-type repeat units where such repeat units are derived from one or more types of norbomene-type monomers each having a reactive pendent group, where at least one such norbomene-type monomer is represented by Formula A and other norbomene-type monomers are represented by Forumlae B and/or C:

• where for Formula A, m is an integer from 0 to 5;
• and Z represents —(CH2)p—, where p is equal to 1;
• and where one of R1 to R4 is independently a fluorinated carbinol pendent group represented by the following formula:
• —(CH2)n—C(CF3)2—OR′
• wherein n is an integer from 0 to 5, and R′ is selected from hydrogen or an acid labile group, and the remaining three of R1, R2, R3 and R4 are each hydrogen, and where such at least one type of repeat unit has an exo isomer mole percent for the fluorinated carbinol pendent group that is greater than or less than an expected exo isomer mole percent for the polycyclic olefin monomer, such expected exo isomer mole percent based on the thermodynamic equilibrium of the isomers of such polycyclic olefin monomer that are obtained from a Diels-Alder reaction used to form such monomer, and wherein said exo isomer mole percent for the fluorinated carbinol pendent group is selected from less than about 15 mole percent and greater than about 25 mole percent, based on total moles of exo isomer and endo isomer;
• where for Formula B, m is an integer from 0 to 5, and Z represents —(CH2)p— wherein p is equal to 1 or 2, and where each of R5, R6, R7 and R8, independently, are H, a halogen, a linear, branched or cyclic C1 to C30 alkyl, an alkylol, an aryl, an aralkyl, an alkaryl, an alkenyl or an alkynyl;
• with the proviso that at least one of R5, R6, R7 and R8 is a crosslinkable functional group represented by Formulae B1, B2, B3 or B4:
• -A—O—[—(CR**2)q—O—]p—(CR**2)q—OH Formula B1
• —R***-Q Formula B2
• —(CH2)nC(O)OR# Formula B3
• —(CH2)t—C(CF3)2—O—(CH2)t—CO—(OR##) Formula B4
• where for Formula B 1, A is a linking group selected from C1 to C6 linear, branched, or cyclic alkylene, each occurrence of R** is independently selected from H, methyl and ethyl, q is independently an integer from 1 to 5 and p is an integer from 0 to 3;
• where for Formula B2, R*** is a linear, branched or cyclic C1 to C30 alkylene, arylene, aralkylene, alkarylene, alkenylene or alkynylene linking group that is partially or completely halogenated, and Q is a functional group selected from hydroxyl, carboxylic acid, amine, thiol, isocyanate and epoxy;
• where for Formula B3, n is an integer from 1 to 5 and R# represents an acid labile group cleavable by a photoacid generator;
• where for Formula B4, each occurrence of t is independently an integer from 1 to 6 and R## is a C1-C8 linear or branched alkyl moiety;
• where for Formula C, m is an integer from 0 to 5, and Z represents —(CH2)p— wherein p is equal to 1 or 2, and where each of R9, R10, R11 and R12, is independently a neutral substituent selected from halogens, —(CH2)n—C(O)OR21, —(CH2)n—(CM2)n—OR18, —(CM2)n—OC(O)R17, —(CH2)n—OC(O)OR17, —(CH2)n—C(O)R18, —(CH2)nC(R19)2CH(R19)(C(O)OR20), —(CH2)n—NH—(SO2)—CF3, —(CH2)nC(R19)2CH(C(O)OR20)2, —C(O)O—(CH2)n—OR18 and —(CH2)n—O—(CH2)n—OR18, —(CH2)n—(O—(CH2)n)n—C(CF3)2OR21 where each occurrence of n is independently an integer from 0 to 5, M is hydrogen or a halogen, R18 and R19 are independently a hydrogen, a halogen, a linear or branched C1 to C10 alkyl group or cycloalkyl group or a linear or branched C1 to C10 halogenated alkyl group or halogenated cycloalkyl group, R20 is not readily cleavable by a photoacid generator and is independently a linear or branched C1 to C10 alkyl group or cycloalkyl group or a linear or branched C1 to C10 halogenated alkyl group or halogenated cycloalkyl group, R17 is not readily cleavable by a photoacid generator and is a linear or branched C1 to C10 alkyl or halogenated alkyl, a monocyclic or polycyclic C4 to C20 cycloaliphatic or halogenated cycloalkyl moiety, a cyclic ether, a cyclic ketone or a cyclic ester, where each of the cyclic ether, ketone and ester is halogenated or not and R21 is defined as R17 plus hydrogen.