Photosensitive polyimide compositions

Abstract

Embodiments in accordance with the present invention encompass photosensitive compositions containing a variety of soluble polyimide polymers and various additives including photoacid generator, photo radical generator and one or more photo crosslinking agents which are useful for forming films that can be patterned to create structures for microelectronic devices, microelectronic packaging, microelectromechanical systems, optoelectronic devices and displays. In some embodiments the compositions of this invention are shown to feature excellent hitherto unachievable mechanical properties. The negative images formed therefrom can be readily cured at lower temperatures than the conventional polyimides and exhibit improved thermo-mechanical properties, among other property enhancements.

What is claimed is: 
     
         1 . A photosensitive composition comprising:
 a) a polyimide of the formula (I):   
       
         
           
           
               
               
           
         
         wherein:
 m is an integer of at least 50; 
 X is one or more distinct tetravalent organic group; and 
 Y is one or more distinct divalent organic group; 
 
         b) a photo radical generator; 
         c) a photo acid generator; and 
         d) one or more crosslinking agents. 
       
     
     
         2 . The composition according to  claim 1 , wherein the polyimide is an end-capped polyimide selected from the group consisting of: 
       
         
           
           
               
               
           
         
         wherein 
            is a single bond or a double bond; 
         m is an integer of at least 50; 
         n is an integer from 1 to 12, inclusive; 
         X is one or more distinct tetravalent organic group; and 
         Y is one or more distinct divalent organic group; 
         R 1  and R 2  are the same or different and each independently of one another selected from the group consisting of hydrogen, linear or branched (C 1 -C 16 )alkyl, linear or branched (C 1 -C 16 )alkenyl, hydroxy(C 1 -C 12 )alkyl, perfluoro(C 1 -C 12 )alkyl, hydroxy(C 1 -C 12 )alkenyl, perfluoro(C 1 -C 12 )alkenyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl and (C 6 -C 10 )aryl(C 1 -C 3 )alkenyl; or 
         R 1  and R 2  taken together with the carbon atoms to which they are attached to form a 5 to 7 membered monocyclic ring, a 6 to 12 membered bicyclic ring or a 9 to 14 membered tricyclic ring, said rings optionally containing one or more heteroatoms selected from O, N and S, and said rings optionally substituted with one or more groups selected from the group consisting of linear or branched (C 1 -C 8 )alkyl, (C 6 -C 10 )aryl, halogen, hydroxy, linear or branched (C 1 -C 8 )alkoxy and (C 6 -C 10 )aryloxy; and 
         wherein one or more of hydrogens of (CH 2 ) is replaced with a group selected from the group consisting of halogen, hydroxy, linear or branched (C 1 -C 16 )alkyl, linear or branched hydroxy(C 1 -C 12 )alkyl, linear or branched perfluoro(C 1 -C 12 )alkyl, (C 6 -C 10 )aryl and (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, linear or branched (C 1 -C 16 )alkoxy and linear or branched perfluoro(C 1 -C 12 )alkoxy; and 
         each of R 3  is independently selected from the group consisting of hydrogen, halogen, hydroxy, methyl, ethyl, linear or branched (C 3 -C 6 )alkyl, trifluoromethyl, pentafluoroethyl, linear or branched perfluoro(C 3 -C 6 )alkyl, methoxy, ethoxy, linear or branched (C 3 -C 6 )alkyloxy, (C 2 -C 6 )acyl, (C 2 -C 6 )acyloxy, phenyl and phenoxy. 
       
     
     
         3 . The composition according to  claim 1 , wherein the polyimide is derived from one or more dianhydrides selected from the group consisting of: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
         4 . The composition according to  claim 1 , wherein the polyimide is derived from one or more diamines selected from the group consisting of: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
         5 . The composition according to  claim 2 , wherein the polyimide is of the formula (IA), wherein at least one end of the main chain of the polyimide of formula (IA) is end capped with a compound of formula (II): 
       
         
           
           
               
               
           
         
       
       wherein n, R 1  and R 2  are as defined in  claim 2 . 
     
     
         6 . The composition according to  claim 5 , wherein the compound of formula (II) is selected from the group consisting of: 
       
         
           
           
               
               
           
         
       
     
     
         7 . The composition according to  claim 2 , wherein the polyimide is of the formula (IB), wherein at least one end of the main chain of the polyimide of formula (IB) is end capped with a compound of formula (IV): 
       
         
           
           
               
               
           
         
       
       wherein R 3  is as defined in  claim 2 . 
     
     
         8 . The composition according to  claim 7 , wherein the compound of formula (IV) is selected from the group consisting of: 
       
         
           
           
               
               
           
         
       
     
     
         9 . The composition according to  claim 2 , wherein the polyimide is of the formula (IC), wherein at least one end of the main chain of the polyimide of formula (IC) is end capped with a compound of formula (V): 
       
         
           
           
               
               
           
         
       
       wherein  , R 1  and R 2  are as defined in  claim 2 . 
     
     
         10 . The composition according to  claim 9 , wherein the compound of formula (V) is selected from the group consisting of: 
       
         
           
           
               
               
           
         
       
     
     
         11 . The composition according to  claim 1 , wherein the polyimide is having a weight average molecular weight (M w ) of from 25,000 to 500,000. 
     
     
         12 . The composition according to  claim 1 , wherein the polyimide is soluble in an organic solvent selected from the group consisting of N-methyl-2-pyrrolidone (NMP), γ-butyrolactone (GBL), N,N-dimethylacetamide (DMAc), propylene glycol monomethyl ether acetate (PGMEA), dimethyl sulfoxide (DMSO), cyclopentanone, cyclohexanone, 2-butanone and 2-heptanone and mixtures in any combination thereof. 
     
     
         13 . The composition according to  claim 1 , wherein the polyimide is selected from the group consisting of:
 a polyimide formed from 5,5′-(perfluoropropane-2,2-diyl)bis(isobenzofuran-1,3-dione) (6FDA), 1H,3H-benzo[1,2-c:4,5-c′]difuran-1,3,5,7-tetraone (PMDA), 4,4′-([1,1′-biphenyl]-4,4′-diylbis(oxy))bis(3-(trifluoromethyl)aniline) (6BF), 2,2′-bis(trifluoromethyl)-[1,1′-biphenyl]-4,4′-diamine (PFMB);   a polyimide formed from 5,5′-(perfluoropropane-2,2-diyl)bis(isobenzofuran-1,3-dione) (6FDA), 1H,3H-benzo[1,2-c:4,5-c′]difuran-1,3,5,7-tetraone (PMDA), 4,4′-([1,1′-biphenyl]-4,4′-diylbis(oxy))bis(3-(trifluoromethyl)aniline) (6BF), 2,2′-bis(trifluoromethyl)-[1,1′-biphenyl]-4,4′-diamine (PFMB) and 1-(2-aminoethyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (DMMIEt-NH 2 );   a polyimide formed from 5,5′-(perfluoropropane-2,2-diyl)bis(isobenzofuran-1,3-dione) (6FDA), 1H,3H-benzo[1,2-c:4,5-c′]difuran-1,3,5,7-tetraone (PMDA), 4,4′-([1,1′-biphenyl]-4,4′-diylbis(oxy))bis(3-(trifluoromethyl)aniline) (6BF), 4,4′-methylenebis(2,6-dimethylaniline) (DO3) and 1-(2-aminoethyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (DMMIEt-NH 2 );   a polyimide formed from 5,5′-(perfluoropropane-2,2-diyl)bis(isobenzofuran-1,3-dione) (6FDA), 1H,3H-benzo[1,2-c:4,5-c′]difuran-1,3,5,7-tetraone (PMDA), 4,4′-([1,1′-biphenyl]-4,4′-diylbis(oxy))bis(3-(trifluoromethyl)aniline) (6BF), 2,2′-bis(trifluoromethyl)-[1,1′-biphenyl]-4,4′-diamine (PFMB) and 2-aminobenzenethiol (2-NH 2 PhSH);   a polyimide formed from 5,5′-(perfluoropropane-2,2-diyl)bis(isobenzofuran-1,3-dione) (6FDA), 1H,3H-benzo[1,2-c:4,5-c′]difuran-1,3,5,7-tetraone (PMDA), 4,4′-([1,1′-biphenyl]-4,4′-diylbis(oxy))bis(3-(trifluoromethyl)aniline) (6BF), 2,2′-bis(trifluoromethyl)-[1,1′-biphenyl]-4,4′-diamine (PFMB) and maleic anhydride (MA);   a polyimide formed from 5,5′-(perfluoropropane-2,2-diyl)bis(isobenzofuran-1,3-dione) (6FDA), 1H,3H-benzo[1,2-c:4,5-c′]difuran-1,3,5,7-tetraone (PMDA), 4,4′-([1,1′-biphenyl]-4,4′-diylbis(oxy))bis(3-(trifluoromethyl)aniline) (6BF), 2,2′-bis(trifluoromethyl)-[1,1′-biphenyl]-4,4′-diamine (PFMB) and dimethyl maleic anhydride (DMMA); and   a polyimide formed from 5,5′-(perfluoropropane-2,2-diyl)bis(isobenzofuran-1,3-dione) (6FDA), 1H,3H-benzo[1,2-c:4,5-c′]difuran-1,3,5,7-tetraone (PMDA), 4,4′-([1,1′-biphenyl]-4,4′-diylbis(oxy))bis(3-(trifluoromethyl)aniline) (6BF), 2,2′-bis(trifluoromethyl)-[1,1′-biphenyl]-4,4′-diamine (PFMB) and itaconic anhydride (IA).   
     
     
         14 . The composition according to  claim 1 , wherein the photo radical generator is selected from the group consisting of:
 a compound of formula (VI):   
       
         
           
           
               
               
           
         
         wherein 
         R 6  and R 7  are the same or different and each independently of one another selected from the group consisting of hydrogen, linear or branched (C 1 -C 8 )alkyl and (C 6 -C 10 )aryl; or 
         R 6  and R 7  taken together with the nitrogen atom to which they are attached to form a 5 to 7 membered monocyclic ring or 6 to 12 membered bicyclic ring, said ring optionally containing one or more heteroatoms selected from O and N, and said ring optionally substituted with linear or branched (C 1 -C 8 )alkyl, (C 6 -C 10 )aryl, halogen, hydroxy, linear or branched (C 1 -C 8 )alkoxy and (C 6 -C 10 )aryloxy; and 
         R 8 , R 9  and R 10  are the same or different and each independently of one another is selected from the group consisting of hydrogen, linear or branched (C 1 -C 16 )alkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, hydroxy, halogen, linear or branched (C 1 -C 12 )alkoxy and (C 6 -C 10 )aryloxy; and 
         a compound of formula (VII): 
       
       
         
           
           
               
               
           
         
         wherein 
         d is an integer from 0 to 3, inclusive; 
         R 11  is selected from the group consisting of hydrogen, linear or branched (C 1 -C 16 )alkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, hydroxy, halogen, linear or branched (C 1 -C 12 )alkoxy and (C 6 -C 10 )aryloxy; 
         R 12  is selected from the group consisting of linear or branched (C 1 -C 16 )alkyl, (C 3 -C 8 )cycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, (C 6 -C 10 )aryl(C 1 -C 6 )alkylphosphinate, (C 6 -C 10 )heterocycle(C 1 -C 3 )alkyl, a group of formula C(O)—(OCH 2 CH 2 ) e —OC(O)C(O)(C 6 -C 10 )aryl, where e is an integer from 2 to 4, inclusive, C(O)C(O)O(C 1 -C 3 )alkyl and a group of formula (C): 
       
       
         
           
           
               
               
           
         
         wherein 
         R 13  is linear or branched (C 1 -C 16 )alkyl; and 
         R 14  is (C 6 -C 10 )aryl; 
         and where each of said alkyl, cycloalkyl, aryl and heterocycle may additionally be substituted with one or more groups selected from the group consisting of hydroxy, linear or branched (C 1 -C 6 )alkyl, linear or branched (C 1 -C 6 )alkoxy and linear or branched thio(C 1 -C 6 )alkyl. 
       
     
     
         15 . The composition according to  claim 1 , wherein the photo radical generator is selected from the group consisting of: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
       and a mixture in any combination thereof. 
     
     
         16 . The composition according to  claim 1 , wherein the photoacid generator is selected from the group consisting of onium salts, diazomethane derivatives, glyoxime derivatives, beta-ketosulfone derivatives, disulfone derivatives, nitrobenzylsulfonate derivatives, sulfonate derivatives, imide-yl-sulfonate derivatives, oximesulfonate derivatives, iminosulfonate derivatives and triazine derivatives. 
     
     
         17 . The composition according to  claim 1 , which further comprises a photosensitizer of the formula (VIII): 
       
         
           
           
               
               
           
         
         wherein 
         R 15  and R 16  are the same or different and independently of each other selected from the group consisting of hydrogen, halogen, methyl, ethyl, linear or branched (C 3 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )bicycloalkyl, (C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, (C 1 -C 12 )alkoxy, (C 3 -C 12 )cycloalkoxy, (C 6 -C 12 )bicycloalkoxy, (C 7 -C 14 )tricycloalkoxy, (C 6 -C 10 )aryloxy(C 1 -C 3 )alkyl and (C 6 -C 10 )-aryloxy. 
       
     
     
         18 . The composition according to  claim 17 , wherein the photosensitizer is selected from the group consisting of: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
         19 . The composition according to  claim 1 , further comprising one or more crosslinking agents selected from the group consisting of: 
       
         
           
           
               
               
           
         
       
     
     
         20 . A microelectronic or optoelectronic device comprising one or more of a redistribution layer (RDL) structure, a chip-stack structure, a CMOS image sensor dam structure, where said structures comprising a composition according to  claim 1 .