Photoresist compositions comprising polycyclic polymers with acid labile pendant groups

Abstract

The present invention relates to a radiation sensitive photoresist composition comprising a photoacid initiator and a polycyclic polymer comprising repeating units that contain pendant acid labile groups. Upon exposure to an imaging radiation source the photoacid initiator generates an acid which cleaves the pendant acid labile groups effecting a polarity change in the polymer. The polymer is rendered soluble in an aqueous base in the areas exposed to the imaging source.

We claim:  
     
         1 . A photoresist composition comprising a photoacid initiator, an optional dissolution inhibitor, and a polymer comprising polycyclic repeating units at least a portion of which contain pendant acid labile groups.  
     
     
         2 . The composition of  claim 1  wherein said polymer is polymerized from one or more acid labile group substituted polycyclic monomer(s) in optional combination with a monomer selected from the group consisting of a neutral group substituted polycyclic monomer, a carboxylic acid group substituted polycyclic monomer, an alkyl substituted polycyclic monomer, and mixtures thereof wherein said acid labile group monomer is represented by the structure:  
       
         
           
           
               
               
           
         
       
       wherein R 1  to R 4  independently represent a substituent selected from the group consisting of hydrogen, linear and branched (C 1  to C 10 ) alkyl, and the group —(CH 2 ) n —C(O)OR*, —(CH 2 ) n —C(O)OR, —(CH 2 ) n —OR, —(CH 2 ) n —OC(O)R, —(CH 2 ) n —OC(O)OR, or —(CH 2 ) n —C(O)R, —(CH 2 ) n C(R) 2 CH(R)(C(O)OR**), and —(CH 2 ) n C(R) 2 CH(C(O)OR**) 2 , subject to the proviso that at least one of R 1  to R 4  is selected from the acid labile group —(CH 2 ) n —C(O)OR*, R represents hydrogen or linear and branched (C 1  to C 10 ) alkyl, m is an integer from 0 to 5 and n is an integer from 0 to 10, and R* represents a moiety that is cleavable by a photoacid initiator selected from the group consisting of —C(CH 3 ) 3 , —Si(CH 3 ) 3 , isobornyl, 2-methyl-2-adamantyl, tetrahydrofuranyl, tetrahydropyranyl 3-oxocyclohexanyl, mevalonic lactonyl, dicyclopropylmethyl, and dimethylpropylmethyl, R** independently represents R and R*; wherein said neutral group substituted monomer is represented by the structure:  
       
         
           
           
               
               
           
         
       
       wherein R 5  to R 8  independently represent a neutral substituent selected from the group —(CH 2 ) n —C(O)OR″, —(CH 2 ) n —OR″, —(CH 2 ) n —OC(O)R″, —(CH 2 ) n —OC(O)OR″, —(CH 2 ) n —C(O)R″, —(CH 2 ) n C(R) 2 CH(R)(C(O)OR″), and —(CH 2 ) n C(R) 2 CH(C(O)OR″) 2 , wherein R represents hydrogen or linear and branched (C 1  to C 10 ) alkyl, R″ represents hydrogen or linear and branched (C 1  to C 10 ) alkyl, monocyclic and polycyclic (C 4  to C 20 )cycloaliphatic moieties, cyclic esters, cyclic ketones, and cyclic ethers subject to the proviso that when R″ is hydrogen at least one of the remaining R 5  to R 8  groups contains a substituent where R″ is (C 1  to C 10 ) alkyl, p is an integer from 0 to 5, and n is an integer from 0 to 10; wherein said carboxylic group containing monomer is represented by the structure:  
       
         
           
           
               
               
           
         
       
       wherein R 9  to R 12  independently represent hydrogen, linear and branched (C 1  to C 10 ) alkyl and a carboxylic substituent represented by the formula —(CH 2 ) n C(O)OH, with the proviso that at least one of R 9  to R 12  is a carboxylic substituent, q is an integer from 0 to 5, and n is an integer from 0 to 10; and wherein said alkyl substituted monomer is represented by the structure:  
       
         
           
           
               
               
           
         
       
       wherein R 13  to R 16  independently represent hydrogen or linear or branched (C 1  to C 10 ) alkyl, with the proviso that at least one of R 13  to R 16  is (C 1  to C 10 ) alkyl, and r is an integer from 0 to 5.  
     
     
         3 . The composition of  claim 2  wherein said monomers are polymerized by ring-opening polymerization to obtain a ring-opened polymer.  
     
     
         4 . The composition of  claim 3  wherein said ring-opened polymer is hydrogenated.  
     
     
         5 . The composition of  claim 2  wherein said monomers are polymerized by free radical polymerization.  
     
     
         6 . The composition of  claim 2  wherein said monomers are polymerized in the presence of a catalyst selected from the group consisting of a single component or multicomponent catalyst system each comprising a Group VIII metal ion source wherein said single component catalyst is represented by the formulae:  
       E n Ni(C 6 F 5 ) 2  [L y MX z ][CA] a  Pd[R 27 CN] 4 [CA − ] 2    
       wherein in the formulae above, E represents a neutral 2 electron donor ligand, n is 1 or 2; L represents a ligand containing between 1, 2, or 3 π-bonds; M represents palladium or nickel; X represents a ligand containing 1 σ-bond and between 0 to 3 π-bonds; y is 0, 1, or 2 and z is 0 or 1, and wherein y and z cannot both be 0 at the same time, and when z is 0, a is 2, and when z is 1, a is 1; R 27  independently represents linear and branched (C 1  to C 10 )alkyl; and CA is a counteranion selected from the group consisting of BF 4   − ; PF 6   − , AlF 3 O 3 SCF 3   − ;, SbF 6   − ; SbF 5 SO 3 F − , AsF 6   − , perfluoroacetate (CF 3 CO 2   − ), perfluoropropionate (C 2 F 5 CO 2   − ), perfluorobutyrate (CF 3 CF 2 CF 2 CO 2   − ), perchlorate (ClO 4   − .H 2 O), p-toluene-sulfonate (p-CH 3 C 6 H 4 SO 3   − ) and tetraphenylborates represented by the formula:  
       
         
           
           
               
               
           
         
       
       wherein R″ independently represents hydrogen, fluorine and trifluoromethyl and n is 1 to 5; and wherein said multicomponent catalyst comprises: 
 (a) a Group VIII metal ion source in combination with one or both of;  
 (b) an organometal cocatalyst compound;  
 (c) a third component selected from the group consisting of Lewis acids, strong Brønsted acids, halogenated compounds, electron donating compounds selected from aliphatic and cycloaliphatic diolefins, and mixtures thereof.  
 
     
     
         7 . The composition of  claim 6  wherein said Lewis acids are selected from the group consisting of BF 3 -etherate, TiCl 4 , SbF 5 , BCl 3 , B(OCH 2 CH 3 ) 3 , and tris(perfluorophenyl) boron, said strong Brønsted acids are selected from the group consisting of HSbF 6 , HPF 6 , CF 3 CO 2 H, FSO 3 H.SbF 5 , H 2 C(SO 2 CF 3 ) 2 , CF 3 SO 3 H and paratoluenesulfonic acid; and said halogenated compounds are selected from the group consisting of hexachloroacetone, hexafluoroacetone, 3-butenoic acid-2,2,3,4,4-pentachlorobutyl ester, hexafluoroglutaric acid, hexafluoroisopropanol and chloranil; wherein said electron donating compounds are selected from aliphatic and cycloaliphatic diolefins, phosphines and phosphites, and mixtures thereof.  
     
     
         8 . The composition of  claim 6  wherein the organometal compound is selected from the group consisting organoaluminum compounds, dialkyl zinc compounds, dialkyl magnesium, alkyllithium compounds, and mixtures thereof.  
     
     
         9 . The composition of  claim 6  wherein E is selected from the group consisting of toluene, benzene, mesitylene, THF, and dioxane.  
     
     
         10 . The composition of  claim 9  wherein the catalyst is selected from the group consisting of (toluene)bis(perfluorophenyl) nickel, (benzene)bis(perfluorophenyl) nickel, (mesitylene)bis(perfluorphenyl) nickel bis(tetrahrydrofuran)bis(perfluorophenyl) nickel, and bis(dioxane)bis(perfluorophenyl) nickel.  
     
     
         11 . The composition of  claim 1  wherein said polymer comprises repeating units selected from the structure:  
       
         
           
           
               
               
           
         
       
       wherein R 1  to R 4  independently represent a substituent selected from the group consisting of hydrogen, linear and branched (C 1  to C 10 ) alkyl, and the group —(CH 2 ) n —C(O)OR*, —(CH 2 ) n —C(O)OR, —(CH 2 ) n —OR, —(CH 2 ) n —OC(O)R, —(CH 2 ) n —OC(O)OR, —(CH 2 ) n —C(O)R, —(CH 2 ) n C(R) 2 CH(R)(C(O)OR**), and —(CH 2 ) n C(R) 2 (CH(C(O)OR**) 2 , subject to the proviso that at least one of R 1  to R 4  is selected from the acid labile group —(CH 2 ) n —C(O)OR*, R represents hydrogen or linear and branched (C 1  to C 10 ) alkyl m is an integer from 0 to 5 and n is an integer from 0 to 10, and R* represents a moiety that is cleavable by a photoacid initiator selected from the group consisting of —C(CH 3 ) 3 , —Si(CH 3 ) 3 , isobornyl, 2-methyl-2-adamantyl, tetrahydrofuranyl, tetrahydropyranyl, 3-oxocyclohexanyl, mevalonic lactonyl, dicyclopropylmethyl, and dimethylpropylmethyl, R** independently represents R and R*.  
     
     
         12 . The composition of  claim 11  wherein said polymer further comprises at least one repeating unit selected from the group represented as follows:  
       
         
           
           
               
               
           
         
       
       wherein R 5  to R 8  independently represent a neutral substituent selected from the group —(CH 2 ) n —C(O)OR″, —(CH 2 ) n —OR″, —(CH 2 ) n —OC(O)R″, —(CH 2 ) n —OC(O)OR″, —(CH 2 ) n —C(O)R″, —(CH 2 ) n C(R) 2 CH(R)(C(O)OR″), and —(CH 2 ) n C(R) 2 CH(C(O)OR″) 2 , wherein R represents hydrogen or linear and branched (C 1  to C 10 ) alkyl, R″ represents hydrogen or linear and branched (C 1  to C 10 ) allyl, monocyclic and polycyclic (C 4  to C 20 ) cycloaliphatic moieties, cyclic esters, cyclic ketones, and cyclic ethers subject to the proviso that when R″ is hydrogen at least one of the remaining R 5  to R 8  groups contains a substituent where R″ is (C 1  to C 10 ) alkyl p is an integer from 0 to 5, and n is an integer from 0 to 10; R 9  to R 12  independently represent hydrogen, linear and branched (C 1  to C 10 ) alkyl and a carboxylic substituent represented by the formula —(CH 2 ) n C(O)OH, with the proviso that at least one of R 9  to R 12  is a carboxylic substituent, q is an integer from 0 to 5, and n is an integer from 0 to 10; and R 13  to R 16  independently represent hydrogen or linear or branched (C 1  to C 10 ) alkyl, with the proviso that at least one of R 13  to R 16  is (C 1  to C 10 ) alkyl, and r is an integer from 0 to 5.  
     
     
         13 . The composition of  claim 9  wherein said monomers are polymerized in the presence of a catalyst selected from the group consisting of (toluene)bis(perfluorophenyl) nickel, (mesitylene)bis(perfluorophenyl) nickel, (benzene)bis(perfluorophenyl) nickel, bis(tetrahydrofuran)bis(perfluorophenyl) nickel, and bis(dioxane)bis(perfluorophenyl) nickel.  
     
     
         14 . The composition of  claim 1  wherein said polymer comprises repeating units selected from the structure:  
       
         
           
           
               
               
           
         
       
       wherein R 1  to R 4  independently represent a substituent selected from the group consisting of hydrogen, linear and branched (C 1  to C 10 ) alkyl, and the group —(CH 2 ) n —C(O)OR*, —(CH 2 ) n —C(O)OR, —(CH 2 ) n —OR, —(CH 2 ) n —OC(O)R, —(CH 2 ) n —OC(O)OR, —(CH 2 ) n —C(O)R, —(CH 2 ) n C(R) 2 CH(R)(C(O)OR**), and —(CH 2 ) n C(R) 2 CH(C(O)OR**) 2  subject to the proviso that at least one of R 1  to R 4  is selected from the acid labile group —(CH 2 ) n C(O)OR*, R represents hydrogen or linear and branched (C 1  to C 10 ) alkyl, m is an integer from 0 to 5 and n is an integer from 0 to 10, and R* represents a moiety that is cleavable by a photoacid initiator selected from the group consisting of —C(CH 3 ) 3 , —Si(CH 3 ) 3 , isobornyl, 2-methyl-2-adamantyl, tetrahydrofuranyl, tetrahrydopyranyl, 3-oxocyclohexanyl, mevalonic lactonyl, dicyclopropylmethyl, and dimethylpropylmethyl, R** independently represents R and R*.  
     
     
         15 . The composition of  claim 14  wherein said polymer further comprises at least one repeating unit selected from the group represented as follows:  
       
         
           
           
               
               
           
         
       
       wherein R 5  to R 8  independently represent a neutral substituent selected from the group —(CH 2 ) n —C(O)OR″, —(CH 2 ) n —OR″, —(CH 2 ) n —OC(O)R″, —(CH 2 ) n —OC(O)OR″, —(CH 2 ) n —C(O)R″, —(CH 2 ) n C(R) 2 CH(R)(C(O)OR″), and —(CH 2 ) n C(R) 2 CH(C(O)OR″) 2 , wherein R represents hydrogen or linear and branched (C 1  to C 10 ) alkyl, R″ represents hydrogen or linear and branched (C 1  to C 10 ) alkyl, monocyclic and polycyclic (C 4  to C 20 )cycloaliphatic moieties, cyclic esters, cyclic ketones, and cyclic ethers subject to the proviso that when R″ is hydrogen at least one of the remaining R 5  to R 8  groups contains a substituent where R″ is (C 1  to C 10 ) alkyl, p is an integer from 0 to 5, and n is an integer from 0 to 10; R 9  to R 12  independently represent hydrogen, linear and branched (C 1  to C 10 ) alkyl, and a carboxylic substituent represented by the formula —(CH 2 )C(O)OH, with the proviso that at least one of R 9  to R 12  is a carboxylic substituent, q is an integer from 0 to 5, and n is an integer from 0 to 10; and R 13  to R 16  independently represent hydrogen or linear or branched (C 1  to C 10 ) alkyl, with the proviso that at least one of R 13  to R 16  is (C 1  to C 10 ) alkyl, and r is an integer from 0 to 5.  
     
     
         16 . The composition of  claim 1 ,  2 ,  11 ,  12 ,  14  or  15  wherein said polymer has a pendant perfluorophenyl group at at least one terminal end thereof.  
     
     
         17 . The composition of  claim 1  wherein said polymer comprises repeating units selected from the structure:  
       
         
           
           
               
               
           
         
       
       wherein R 1  to R 4  independently represent a substituent selected from the group consisting of hydrogen, linear and branched (C 1  to C 10 ) alkyl, and the group —(CH 2 ) n —C(O)OR*, —(CH 2 ) n —C(O)OR, —(CH 2 ) n —OR, —(CH 2 ) n —OC(O)R, —(CH 2 ) n OC(O)OR, or —(CH 2 ) n C(O)R, —(CH 2 ) n C(R) 2 CH(R)(C(O)OR**), and —(CH 2 ) n C(R) 2 CH(C(O)OR**) 2 , subject to the proviso that at least one of R 1  to R 4  is selected from the acid labile group —(CH 2 ) n —C(O)OR*, R represents hydrogen or linear and branched (C 1  to C 10 ) alkyl, m is an integer from 0 to 5 and n is an integer from 0 to 10, and R* represents a moiety that is cleavable by a photoacid initiator selected from the group consisting of —C(CH 3 ) 3 , —Si(CH 3 ) 3 , isobornyl, 2-methyl-2-adamantyl, tetrahydrofuranyl, tetrahydropyranyl, 3-oxocyclohexanyl, mevalonic lactonyl dicyclopropylmethyl and dimethylpropylmethyl R** independently represents R and R*.  
     
     
         18 . The composition of  claim 17  wherein said polymer further comprises at least one repeating unit selected from the group represented as follows:  
       
         
           
           
               
               
           
         
       
       wherein R 5  to R 8  independently represent a neutral substituent selected from the group —(CH 2 ) n —C(O)OR″, —(CH 2 ) n —OR″, —(CH 2 ) n —OC(O)R″, —(CH 2 ) n —OC(O)OR″, —(CH 2 ) n —C(O)R″, —(CH 2 ) n C(R) 2 CH(R)(C(O)OR″), and —(CH 2 ) n C(R) 2 CH(C(O)OR″) 2 , wherein R represents hydrogen or linear and branched (C 1  to C 10 ) alkyl, R″ represents hydrogen or linear and branched (C 1  to C 10 ) alkyl monocyclic and polycyclic (C 4  to C 20 )cycloaliphatic moieties, cyclic esters, cyclic ketones, and cyclic ethers subject to the proviso that when R″ is hydrogen at least one of the remaining R 5  to R 8  groups contains a substituent where R″ is (C 1  to C 10 ) alkyl, p is an integer from 0 to 5, and n is an integer from 0 to 10; R 9  to R 12  independently represent hydrogen, linear and branched (C 1  to C 10 ) alkyl and a carboxylic substituent represented by the formula —(CH 2 ) n C(O)OH, with the proviso that at least one of R 9  to R 12  is a carboxylic substituent, q is an integer from 0 to 5, and n is an integer from 0 to 10; and R 13  to R 16  independently represent hydrogen or linear or branched (C 1  to C 10 ) alkyl, with the proviso that at least one of R 13  to R 16  is (C 1  to C 10 ) alkyl and r is an integer from 0 to 5.  
     
     
         19 . The composition of  claim 18  wherein the said polymer comprises repeating units represented by the following structures:  
       
         
           
           
               
               
           
         
       
       R represents hydrogen or linear and branched (C 1  to C 10 ) alkyl, m and m′ idependently represent an integer from 0 to 5 and n is an integer from 0 to 10, R* represents a moiety that is cleavable by a photoacid initiator selected from the group consisting of —C(CH 3 ) 3 , —Si(CH 3 ) 3 , isobornyl, 2-methyl-2-adamantyl, tetrahydrofuranyl, tetrahydropyranyl, 3-oxocyclohexanyl, mevalonic lactonyl, dicyclopropylmethyl and dimethylpropylmethyl.  
     
     
         20 . The composition of  claim 19  wherein m is 0, m′ is 1, and n is 0.  
     
     
         21 . The composition of calim  20  wherein said polymer composition comprises repeating units represented as follows:  
       
         
           
           
               
               
           
         
       
     
     
         22 . The polymer of  claim 17 ,  18 ,  19 ,  20 , or  21  wherein the unsaturation in the backbone of said polymer is hydrogenated in excess of 90 percent.  
     
     
         23 . The polymer of  claim 22  wherein the unsaturation in the backbone of said polymer is hydrogenated in excess of 95 percent.  
     
     
         24 . The polymer of  claim 23  wherein the unsaturation in the backbone of said polymer is essentially 100 percent hydrogenated.  
     
     
         25 . The composition of  claim 1 ,  2 ,  3 ,  4 ,  5 ,  11 ,  12 ,  13 ,  14 ,  15 ,  16 ,  17 ,  18 ,  19 ,  20 , or  21  wherein said polymer contains 5 to 100 mole % of repeating units containing said acid labile groups.  
     
     
         26 . The composition of  claim 25  wherein said polymer contains 20 to 90 mole % of repeating units containing said acid labile groups.  
     
     
         27 . The composition of  claim 26  wherein said polymer contains 30 to 70 mole % of repeating units containing said acid labile groups.  
     
     
         28 . The composition of  claim 24  wherein said polymer contains 5 to 100 mole % of repeating units containing said acid labile groups.  
     
     
         29 . A polymer composition including polymer chains comprising adjacent polycyclic monomeric units that are linked together in 2,7-repeating unit enchainment, at least some of said polycyclic units having pendant tertiary butylesters of carboxylic acid.  
     
     
         30 . The polymer composition of  claim 29  comprising repeating units of tert-butylester of 5-norbornene carboxylic acid.  
     
     
         31 . The polymer composition of  claim 29  comprising repeating units of the tert-butylester of 5-norbornene carboxylic acid and the linear (C 1  to C 5 ) alkyl ester of 5-norbornene carboxylic acid.  
     
     
         32 . A polymer composition comprising polymer chains having repeating units represented as follows:  
       
         
           
           
               
               
           
         
       
       wherein R 1  to R 4  independently represent a substituent selected from the group consisting of hydrogen, linear and branched (C 1  to C 10 ) alkyl, and the group —(CH 2 ) n —C(O)OR*, —(CH 2 ) n —C(O)OR, —(CH 2 ) n —OR, —(CH 2 ) n —OC(O)R, —(CH 2 ) n —OC(O)OR, —(CH 2 ) n —C(O)R, —(CH 2 ) n C(R) 2 CH(R)(C(O)OR**), and —(CH 2 ) n C(R) 2 CH(C(O)OR**) 2 , subject to the proviso that at least one of R 1  to R 4  is selected from the acid labile group —(CH 2 ) n —C(O)OR*, R represents hydrogen or linear and branched (C 1  to C 10 ) alkyl, m is an integer from 0 to 5 and n is an integer from 0 to 10, and R* represents a moiety that is cleavable by a photoacid initiator selected from the group consisting of —C(CH 3 ) 3 , —Si(CH 3 ) 3 , isobornyl 2-methyl-2-adamantyl, tetrahydrofuranyl, tetrahydropyranyl, 3-oxocyclohexanyl, mevalonic lactonyl, dicyclopropylmethyl, and dimethylpropylmethyl, R** independently represents R and R*.  
     
     
         33 . The composition of  claim 31  wherein said polymer further comprises at least one repeating unit selected from the group represented as follows  
       
         
           
           
               
               
           
         
       
       wherein R 5  to R 8  independently represent a neutral substituent selected from the group —(CH 2 ) n —C(O)OR″, —(CH 2 ) n —OR″, —(CH 2 ) n —OC(O)R″, —(CH 2 ) n —OC(O)OR″, —(CH 2 ) n —C(O)R″, —(CH 2 ) n C(R) 2 CH(R)C(O)OR″), and —(CH 2 ) n C(R) 2 CH(C(O)OR″) 2 , wherein R represents hydrogen or linear and branched (C 1  to C 10 ) alkyl, R″ represents hydrogen or linear and branched (C 1  to C 10 ) alkyl monocyclic and polycyclic (C 4  to C 20 ) cycloaliphatic moieties, cyclic esters, cyclic ketones, and cyclic ethers subject to the proviso that when R″ is hydrogen at least one of the remaining R 5  to R 8  groups contains a substituent where R″ is (C 1  to C 10 ) alkyl, p is an integer from 0 to 5, and n is an integer from 0 to 10; R 9  to R 12  independently represent hydrogen, linear and branched (C 1  to C 10 ) alkyl and a carboxylic substituent represented by the formula —(CH 2 ) n C(O)OH, with the proviso that at least one of R 9  to R 12  is a carboxylic substituent, q is an integer from 0 to 5, and n is an integer from 0 to 10; and R 13  to R 16  independently represent hydrogen or linear or branched (C 1  to C 10 ) alkyl, with the proviso that at least one of R 13  to R 16  is (C 1  to C 10 ) alkyl, and r is an integer from 0 to 5.  
     
     
         34 . The polymer composition of  claim 33  comprising repeating units having the following structures:  
       
         
           
           
               
               
           
         
       
       wherein m and p independently represent 0 or 1, R* represents a moiety that is cleavable by a photoacid initiator selected from the group consisting of —C(CH 3 ) 3 , —Si(CH 3 ) 3 , isobornyl 2-methyl-2-adamantyl, tetrahydrofuranyl, tetrahydropyranyl, 3-oxocyclohexanyl, mevalonic lactonyl dicyclopropylmethyl and dimethylpropylmethyl and R′ represents the group (CH 2 ) n —C(O)OR″, —(CH 2 ) n —OC(O)R″, —(CH 2 ) n OC(O)OR″, where n independently is 0 to 5, R″ represents hydrogen or linear and branched (C 1  to C 10 ) alkyl, monocyclic and polycyclic (C 4  to C 20 ) cyclo-aliphatic moieties, cyclic esters, cyclic ketones, and cyclic ethers.  
     
     
         35 . The polymer of  claim 34  comprising repeating units having the following structures:  
       
         
           
           
               
               
           
         
       
       wherein R 8  represents the group —(CH 2 ) n —C(O)OR″, —(CH 2 ) n —OC(O)R″, —(CH 2 ) n —OC(O)OR″, n is 0 to 5, and R″ represents hydrogen linear (C 1  to C 10 ) alkyl.  
     
     
         36 . The polymer of  claim 35  wherein R 8  is C(O)OR″ wherein R″ is selected from the group consisting of methyl, ethyl, propyl, butyl and pentyl.  
     
     
         37 . The polymer of  claim 29 ,  30 ,  31 ,  32 ,  34 ,  35 , or  37  wherein said polymer has a pendant perfluorophenyl group at least one terminal end thereof.  
     
     
         38 . A polymer produced by polymerizing a monomer composition comprising a polycyclic monomer and a solvent in the presence of a single component catalyst having the formula:  
       E n Ni(C 6 F 5 ) 2    
       wherein E is a neutral 2 electron donor ligand and n is 1 or 2, and wherein said polycyclic monomer is selected from a monomer having the following formula:  
       
         
           
           
               
               
           
         
       
       wherein R 1  to R 4  independently represent a substituent selected from the group consisting of hydrogen, linear and branched (C 1  to C 10 ) alkyl, and the group —(CH 2 ) n —C(O)OR*, —(CH 2 ) n —C(O)OR, —(CH 2 ) n —OR, —(CH 2 ) n —OC(O)R, —(CH 2 ) n —OC(O)OR, or —(CH 2 ) n —C(O)R, —(CH 2 ) n C(R) 2 CH(R)(C(O)OR**), and —(CH 2 ) n C(R) 2 CH(C(O)OR**) 2 , subject to the proviso that at least one of R 1  to R 4  is selected from the acid labile group —(CH 2 ) n —C(O)OR*, R represents hydrogen or linear and branched (C 1  to C 10 ) alkyl m is an integer from 0 to 5 and n is an integer from 0 to 10, and R* represents a moiety that is cleavable by a photoacid initiator selected from the group consisting of —C(CH 3 ) 3 , —Si(CH 3 ) 3 , isobornyl, 2-methyl-2-adamantyl, tetrahydrofuranyl, tetrahydropyranyl, 3-oxocyclohexanyl, mevalonic lactonyl, dicyclopropylmethyl, and dimethylpropylmethyl, R** independently represents R and R*.  
     
     
         39 . The polymer of  claim 38  wherein said monomer coposition further comprises a polycyclic monomer of the formula:  
       
         
           
           
               
               
           
         
       
       wherein R 5  to R 8  independently represent a neutral substituent selected from the group —(CH 2 ) n C(O)OR″, —(CH 2 ) n —OR″, —(CH 2 ) n —OC(O)R″, —(CH 2 ) n —OC(O)OR″, —(CH 2 ) n —C(O)R″, —(CH 2 ) n C(R) 2 CH(R)(C(O)OR″), and —(CH 2 ) n C(R) 2 CH(C(O)OR″) 2 , wherein R represents hydrogen or linear and branched (C 1  to C 10 ) alkyl, R″ represents hydrogen or linear and branched (C 1  to C 10 ) alkyl monocyclic and polycyclic (C 4  to C 20 )cycloaliphatic moieties, cyclic esters, cyclic ketones, and cyclic ethers subject to the proviso that when R″ is hydrogen at least one of the remaining R 5  to R 8  groups contains a substituent where R″ is (C 1  to C 10 ) alkyl, p is an integer from 0 to 5, and n is an integer from 0 to 10.  
     
     
         40 . The polymer of  claim 39  wherein said monomer composition comprises monomers of the formulae:  
       
         
           
           
               
               
           
         
       
       wherein R 8  represents the group —(CH 2 ) n —C(O)OR″, —(CH 2 ) n —OC(O)R″, —(CH 2 ) n —OC(O)OR″, n is 0 to 5, and R″ represents hydrogen linear (C 1  to C 10 ) alkyl.  
     
     
         41 . The polymer of  claim 38 ,  39 , or  40  comprising 2, 7-linked polycyclic repeating units.  
     
     
         42 . The polymer of  claim 1 ,  2 ,  38 ,  39 ,  40 , or  41  wherein said polymer has a pendant perfluorophenyl group at least one terminal end thereof.  
     
     
         43 . The polymer of  claim 38  wherein n is 1 and ligand E in said catalyst composition is selected from the group consisting of benzene, mesitylene, and toluene.  
     
     
         44 . The polymer of  claim 38  wherein n is 2 and ligand E in said catalyst composition is selected from the group consisting of THF, dioxane, and diethylether.  
     
     
         45 . A photoresist composition comprising a photoacid initiator, an optional dissolution inhibitor, and a polymer including polymer chains comprising adjacent polycyclic monomeric units that are linked together in 2,7-repeating unit enchainment, at least some of said polycyclic units having pendant tertiary butylesters of carboxylic acid or a copolymer thereof.  
     
     
         46 . The photoresist composition of  claim 45  wherein said polymer comprises repeating units of the tert-butylester of 5-norbornene carboxylic acid and the linear (C 1  to C 5 ) alkyl ester of 5-norbornene carboxylic acid.