Negative-working photoresist compositions for laser ablation and use thereof

Abstract

A composition crosslinkable by broad band UV radiation, which after cross-linking is capable of cold ablation by a UV Excimer Laser emitting between 222 nm and 308 nm, where the composition is comprised of a negative tone resist developable in aqueous base comprising and is also comprised of a conjugated aryl additive absorbing ultraviolet radiation strongly in a range between from about 220 nm to about 310 nm. The present invention also encompasses a process comprising steps a), b) and c) a) coating the composition of claim 1 on a substrate; b) cross-linking the entire coating by irradiation with broadband UV exposure; c) forming a pattern in the cross-linked coating by cold laser ablating with a UV excimer laser emitting between 222 nm and 308 nm. Finally the present invention also encompasses The present invention also encompasses a process comprising steps a′), b′) c′) and d′) a) coating the composition of claim 1 on a substrate; b) cross-linking part of the coating by irradiation with broadband UV exposure through a mask; c) developing the coating with aqueous base removing the unexposed areas of the film, thereby forming a first pattern; d) forming a second pattern in the first pattern by laser cold laser ablating of the first pattern with a UV excimer laser emitting between 222 nm and 308 nm.

1 . A composition for a negative tone, aqueous base developable, broadband UV resist which is also sensitive in the areas exposed to broadband irradiation to subsequent cold laser ablation by an UV Excimer Laser emitting between 222 nm and 308 nm wherein the composition is comprised of components of type a), b), and a solvent;
 a) components for imparting negative tone, aqueous base developable, broadband UV resist behavior comprised of
 i) a polymeric resin containing phenolic moieties, carboxylic acid moieties or a combination of both types moieties such that the resin dissolves in aqueous base 
 ii) at least one cross-linker; and 
 iii) at least one photo-initiator sensitive to broadband irradiation; 
   wherein a) is further selected from the group consisting of (VIV) and (X) wherein,   (VIV) is comprised of:   a-1) at least one alkali-soluble polymeric resin wherein the alkali-soluble polymer comprises a least one unit of structure (IV)   
       
         
           
           
               
               
           
         
         wherein each R′ is independently selected from the group consisting of hydroxyl, (C1-C4) alkyl, chlorine, and bromine; and m′ is chosen from an integer from 1 to 4; 
         b-1 at least one monomer of structure 4; 
       
       
         
           
           
               
               
           
         
         wherein, W is a multivalent linking group, R 1a  to R 6a  are independently selected from the group consisting of hydrogen, hydroxy, (C1-C20)alkyl and chlorine; X 1  and X 2  are each oxygen; and n′ is an integer equal to or greater than 1; and 
         c-1) at least one photoinitiator and and further wherein the monomer of structure 4 comprises an acid-cleavable group and the alkali soluble polymer further comprises at least one acid-cleavelable group; 
         (X) is comprised of: 
         a-2) at least one polymeric resin comprising a structure of the following formula: 
       
       
         
           
           
               
               
           
         
         
           wherein each of R 1b -R 5b  is independently selected from the group consisting of H, F and CH 3 , R 6b  is selected from the group consisting of a substituted aryl, unsubstituted aryl, substituted heteroaryl and unsubstituted heteroaryl group; R 7b  is a substituted or unsubstituted benzyl group; R 8b  is selected from the group consisting of a linear or branched C 2 -C 10  hydroxy alkyl group and a C 2 -C 10  hydroxy alkyl acrylate; R 9b  is an acid cleavable group, v=10-40 mole %, w=0-35 mole %, x=0-60 mole %, y=10-60 mole % and z=0-45 mole %: 
         
         b-2) one or more free radical initiators activated by actinic radiation, 
         c-2) one or more crosslinkable acrylated monomers capable of undergoing free radical crosslinking wherein the acrylate functionality is greater than 1, 
         and further wherein the said polymeric resin comprises from about 30 wt % to about 80 wt % of the composition; 
         b) a cold laser ablation excimer laser sensitizer component system comprised of at least one conjugated aryl additive absorbing ultraviolet radiation strongly in a range between from about 220 nm to about 310, wherein the molar absorptivity the conjugated aryl additive between these wavelengths is between about 100 and 1000 m 2 /mol, and further wherein this said conjugated aryl additive is selected from the group consisting of consisting of (I), (II), (III), (IV), (V), (VI), and VII; 
       
       
         
           
           
               
               
           
         
         wherein each R 1 , R 2 , R 3 , R 4 , R 5  and R 6  are independently selected from the group consisting of hydrogen, an alkyl group, an alkylenefluoroalkyl group, an alkylene aryl group, and an alkyleneoxyalkyl group; R 7  is selected from the group consisting of an alkyl group, an alkylenefluoroalkyl group, an alkylene aryl group, and an alkyleneoxyalkyl group; each R 8  is independently selected from the group consisting of hydrogen, an alkyl group, an alkylenefluoroalkyl group, an alkylene aryl group, an alkyleneoxyalkyl group, a hydroxy group, a hydroxyalkylene group, and an alkoxy group; X 3  is selected from the group consisting of Cl, Br or I; each n, na, nb, m, ma and mb is independently chosen from an integer from 1 to 4; mc is chosen from an integer from 1 to 9, and md is chosen from an integer from 1 to 10 and further wherein the said cold laser ablation excimer laser sensitizer component system comprises from 2 to 10 wt % of the composition, 
         and further wherein the composition is one which can be coated to a thickness from 30 to 60 microns. 
       
     
     
         2 . The composition of  claim 1  wherein the conjugated aryl additive absorbing ultraviolet radiation strongly from about 222 nm to about to about 310 nm is selected from the group consisting of (I), (II), (III), (IV), and (V). 
     
     
         3 . The composition of  claim 1  wherein the components for imparting negative tone, aqueous base developable, broadband UV resist behavior is (X). 
     
     
         4 . The composition of  claim 1  wherein the conjugated aryl additive is selected from the group consisting of (I) and (II). 
     
     
         5 . The composition of  claim 1  wherein the conjugated aryl additive is (I). 
     
     
         6 . The composition of  claim 1  wherein the conjugated aryl additive is (II). 
     
     
         7 . (canceled) 
     
     
         8 . (canceled) 
     
     
         9 . The composition of  claim 1  wherein the components for imparting negative tone, aqueous base developable, broadband UV resist behavior is (VIV). 
     
     
         10 . The composition of  claim 1  wherein the components for imparting negative tone, aqueous base developable, broadband UV resist behavior is (VIV) and where the conjugated aryl additive is selected from the group consisting of (I) and (II). 
     
     
         11 . The composition of  claim 1  wherein the components for imparting negative tone, aqueous base developable, broadband UV resist behavior are (X). 
     
     
         12 . The composition of  claim 1  wherein the components for imparting negative tone, aqueous base developable, broadband UV resist behavior are (X) and wherein the conjugated aryl additive is selected from the group consisting of (I) and (II). 
     
     
         13 . The composition of  claim 1  wherein the conjugated aryl additive has between the wavelengths of 220 nm and 310 nm a molar absorptivity of between about 200 and 1000 m 2 /mol. 
     
     
         14 . The composition of  claim 1  wherein the conjugated aryl additive has a molar absorptivity at 248 nm between 200 and 1000 m 2 /mol. 
     
     
         15 . The composition of  claim 1  wherein the conjugated aryl additive has a molar absorptivity at 308 nm between 200 and 1000 m 2 /mol. 
     
     
         16 . The composition of  claim 1  wherein the conjugated aryl additive is (I), and further where R 2  and R 1  are independently selected from the group consisting of hydrogen and an alkyl group. 
     
     
         17 . The composition of  claim 1  wherein the conjugated aryl additive is (II), R 3  is an alkyl group, and X is Cl. 
     
     
         18 . The composition of  claim 1  wherein the conjugated aryl additive is (V), and where at least one R 8  is independently selected from the group consisting of an alkoxy group, a hydroxyalkylene, and a hydroxy group. 
     
     
         19 . The composition of  claim 1  wherein the conjugated aryl additive is (VI), and where at least one R 8  is independently selected from the group consisting of an alkoxy group, a hydroxyalkylene, and a hydroxy group. 
     
     
         20 . A process comprising steps a), b) and c)
 a) coating the composition of  claim 1  on a substrate;   b) cross-linking the entire coating by blanket irradiation with broadband UV exposure; and   c) forming a pattern in the cross-linked coating by cold laser ablating with a UV excimer laser emitting between 222 nm and 308 nm.   
     
     
         21 . The process of  claim 20  where the broadband UV exposure is between 350 and 450 nm. 
     
     
         22 . The process of  claim 20  where the excimer laser emits at 248 nm. 
     
     
         23 . The process of  claim 20  where the excimer laser emits at 308 nm. 
     
     
         24 . A process comprising steps a), b), c) and d)
 a) coating the composition of  claim 1  on a substrate;   b) cross-linking part of the coating by irradiation with broadband UV exposure through a mask;   c) developing the coating with aqueous base removing the unexposed areas of the coating, thereby forming a first pattern;   d) forming a second pattern in the first pattern by cold laser ablating of the first pattern with a UV excimer laser emitting between 222 nm and 308 nm.   
     
     
         25 . The process of  claim 24  where the excimer laser emits at 248 nm. 
     
     
         26 . The process of  claim 24  where the excimer laser emits at 308 nm. 
     
     
         27 . A composition for a negative tone, aqueous base developable, broadband UV resist which is also sensitive in the areas exposed to broadband irradiation to subsequent cold laser ablation by an UV Excimer Laser emitting between 222 nm and 308 nm wherein the composition is comprised of components of type a) b), and a solvent;
 a) components for imparting negative tone, aqueous base developable, broadband UV resist behavior comprised of
 i) a polymeric resin containing phenolic moieties, carboxylic acid moieties or a combination of both types moieties such that the resin dissolves in aqueous base 
 ii) at least one cross-linker; and 
 iii) at least one photo-initiator sensitive to broadband irradiation; 
   wherein a) is further selected from-the group consisting of (VIII), (VIV) and (X), and further wherein,   (VIII) is comprised of
 a) a phenolic film forming polymeric resin having a ring bonded hydroxy group; 
 b) a photoacid generator that forms an acid upon exposure to radiation, in an amount sufficient to initiate crosslinking of the film-forming polymeric binder resin; 
 c) a first crosslinking agent that forms a carbonium ion upon exposure to the acid formed by the photoacid generator, and which comprises an etherified amino-plast polymer or oligomer; 
 d) a second crosslinking agent that forms a carbonium ion upon exposure to the acid formed by the photoacid generator, and which comprises dihydroxyalkyl-(tetra)-phenol, wherein the combined amount of the first and second crosslinkers is an effective crosslinking amount; and 
   (VIV) is comprised of:   a-1) at least one alkali-soluble polymeric resin wherein the alkali-soluble polymer comprises a least one unit of structure (IV)   
       
         
           
           
               
               
           
         
         Wherein, each R′ is independently selected from the group consisting of hydroxyl, (C 1 -C 4 ) alkyl, chlorine, and bromine; and m′ is chosen from an integer from 1 to 4; 
         b-1) at least one monomer of structure 4; 
       
       
         
           
           
               
               
           
         
         wherein, W is a multivalent linking group, R 1a  to R 6a  are independently selected from the group consisting of hydrogen, hydroxy, (C 1 -C 20 )alkyl and chlorine; X 1  and X 2  are each oxygen; and n′ is an integer equal to or greater than 1; and 
         c-1) at least one photoinitiator and further where the monomer of structure 4 comprises an acid-cleavable group and the alkali soluble polymer further comprises at least one acid-cleavelable group; 
         (X) is comprised of: 
         a-2) at least one polymeric resin comprising a structure of the following formula: 
       
       
         
           
           
               
               
           
         
         
           wherein each of R 1b -R 5b  is independently selected from the group consisting of H, F and CH 3 , R 6b  is selected from the group consisting of a substituted aryl, unsubstituted aryl, substituted heteroaryl and unsubstituted heteroaryl group; R 7b  is a substituted or unsubstituted benzyl group; R 8b  is selected from the group consisting of a linear or branched C 2 -C 10  hydroxy alkyl group and a C 2 -C 10  hydroxy alkyl acrylate; R 9b  is an acid cleavable group, v=10-40 mole %, w=0-35 mole %, x=0-60 mole %, y=10-60 mole % and z=0-45 mole %; 
         
         b-2) one or more free radical initiators activated by actinic radiation, 
         c-2) one or more crosslinkable acrylated monomers capable of undergoing free radical crosslinking wherein the acrylate functionality is greater than 1; 
         b) a cold laser ablation excimer laser sensitizer component system comprised of at least one conjugated aryl additive absorbing ultraviolet radiation strongly in a range between from about 220 nm to about 310, wherein the molar absorptivity the conjugated aryl additive between these wavelengths is between about 100 and 1000 m 2 /mol, and further wherein this said conjugated aryl additive is selected from the group consisting of consisting of (I), (III), (IV), (V), (VI), and VII; 
       
       
         
           
           
               
               
           
         
         wherein, each R 1 , R 2 , R 3 , R 4 , R 5  and R 6  are independently selected from the group consisting of hydrogen, an alkyl group, an alkylenefluoroalkyl group, an alkylene aryl group, and an alkyleneoxyalkyl group; R 7  is selected from the group consisting of an alkyl group, an alkylenefluoroalkyl group, an alkylene aryl group, and an alkyleneoxyalkyl group; each R 8  is independently selected from the group consisting of hydrogen, an alkyl group, an alkylenefluoroalkyl group, an alkylene aryl group, an alkyleneoxyalkyl group, a hydroxy group, a hydroxyalkylene group, and an alkoxy group; X 3  is selected from the group consisting of Cl, Br or I; each n, na, nb, m, ma and mb is independently chosen from an integer from 1 to 4; mc is chosen from an integer from 1 to 9, and md is chosen from an integer from 1 to 10 and further wherein the said cold laser ablation excimer laser sensitizer component system comprises from 2 to 10 wt % of the composition. 
         and further wherein the composition is one which can be coated to a thickness from 30 to 60 microns. 
       
     
     
         28 ) The composition of  claim 27  wherein the conjugated aryl additive absorbing ultraviolet radiation strongly from about 222 nm to about to about 310 nm is selected from the group consisting of (I), (II), (III), (IV), and (V).