NEGATIVE-WORKING PHOTORESIST COMPOSITIONS FOR LASER ABLATION AND USE THEREOF
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IPC분류정보
국가/구분
United States(US) Patent
공개
국제특허분류(IPC7판)
G03F-007/038
G03F-007/004
G03F-007/20
G03F-007/32
G03F-007/031
G03F-007/16
출원번호
US-0628711
(2017-06-21)
공개번호
US-0285475
(2017-10-05)
발명자
/ 주소
Chen, Chunwei
Liu, Weihong
Lu, Ping-Hung
출원인 / 주소
Chen, Chunwei
인용정보
피인용 횟수 :
0인용 특허 :
0
초록▼
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 conju
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.
대표청구항▼
1. A process comprising steps a), b) and c) a) coating on a substrate 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 n
1. A process comprising steps a), b) and c) a) coating on a substrate 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 where the composition is comprised of components of type a1) and b1); a1) components for imparting negative tone, aqueous base developable, broadband UV resist behavior comprised ofi) a 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; andiii) at least one photo-initiator sensitive to broadband irradiation; andb1) 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 nm on a substrate;b) cross-linking the entire coating by blanket irradiation with broadband UV exposure; andc) forming a pattern in the cross-linked coating by cold laser ablating with a UV excimer laser emitting between 222 nm and 308 nm. 2. The process of claim 1 wherein b1) 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), (V), (VI) and (VII); where each R1, R2, R3, R4, R5 and R6 are independently selected from the group consisting of hydrogen, an alkyl group, an alkylenefluoroalkyl group, an alkylene aryl group, and an alkyleneoxyalkyl group; R7 is selected from the group consisting of an alkyl group, an alkylenefluoroalkyl group, an alkylene aryl group, and an alkyleneoxyalkyl group; each R8 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; X3 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 and is chosen from an integer from 1 to 10. 3. The process of claim 1 wherein, a1), the components for imparting negative tone, aqueous base developable, broadband UV resist behavior are selected from the group consisting of (VIII), (VIV) and (X) where, (VIII) is comprised of a) a phenolic film forming polymeric binder 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 am ino-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; ande) a photoresist solvent;(VIV) is comprised of:a-1) at least one alkali-soluble polymer where the alkali-soluble polymer comprises a least one unit of structure (VIVa) where 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; where, W is a multivalent linking group, R1a to R6a are independently selected from the group consisting of hydrogen, hydroxy, (C1-C20)alkyl and chlorine; X1 and X2 are each oxygen; and n′ is an integer equal to or greater than 1; and c-1) at least one photoinitiator andd-1) a photoresist solvent,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 polymer comprising a structure of the following formula: wherein each of R1b-R5b is independently selected from the group consisting of H, F and CH3, R6b is selected from the group consisting of a substituted aryl, unsubstituted aryl, substituted heteroaryl and unsubstituted heteroaryl group; R7b is a substituted or unsubstituted benzyl group; R8b is selected from the group consisting of a linear or branched C2-C10 hydroxy alkyl group and a C2-C10 hydroxy alkyl acrylate; R9b 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, andd-2) a photoresist solvent. 4. The process of claim 2 wherein, b1), the conjugated aryl additive is selected from the group consisting of (I) and (II). 5. The process of claim 2 wherein, b1), the conjugated aryl additive is (I). 6. The process of claim 2 wherein, b1), the conjugated aryl additive is (II). 7. The process of claim 3 wherein, a1), the components for imparting negative tone, aqueous base developable, broadband UV resist behavior are (VIII). 8. The process of claim 3 wherein, a1), the components for imparting negative tone, aqueous base developable, broadband UV resist behavior are (VIII) and the conjugated aryl additive is selected from the group consisting of (I) and (II). 9. The process of claim 3 wherein, b1), the conjugated aryl additive is (VIV). 10. The process of claim 3 wherein, b1), the conjugated aryl additive is (VIV) and where the components, a1) for imparting negative tone, aqueous base developable, broadband UV resist behavior are selected from the group consisting of (I) and (II). 11. The process of claim 3 wherein, a1), the components for imparting negative tone, aqueous base developable, broadband UV resist behavior are (X). 12. The process of claim 3 wherein, a1), the components for imparting negative tone, aqueous base developable, broadband UV resist behavior are (X) and where the conjugated aryl additive is selected from the group consisting of (I) and (II). 13. The process of claim 3 wherein, b1) the conjugated aryl additive has between the wavelengths of 220 nm and 310 nm a molar absorptivity of between about 10 and 1000 m2/mol. 14. The process of claim 3 wherein, b1), the conjugated aryl additive has a molar absorptivity at 248 nm between 10 and 1000 m2/mol. 15. The process of claim 3 wherein, b1), the conjugated aryl additive has a molar absorptivity at 308 nm between 10 and 1000 m2/mol. 16. The process of claim 3 wherein, b1), the conjugated aryl additive is (I), and further where R2 and R1 are independently selected from the group consisting of hydrogen and an alkyl group. 17. The process of claim 3 wherein, b1), the conjugated aryl additive is (II), R3 is an alkyl group, and X is Cl. 18. The composition of claim 3 wherein, b1) the conjugated aryl additive is (V), and where at least one R8 is independently selected from the group consisting of an alkoxy group, a hydroxyalkylene, and a hydroxy group. 19. The Process of claim 3 where the conjugated aryl additive is (VI), and where at least one R8 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; andc) 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 1 where the broadband UV exposure is between 350 and 450 nm. 21. The process of claim 1 where the excimer laser emits at 248 nm. 22. The process of claim 1 where the excimer laser emits at 308 nm. 23. A process comprising steps a2), b2), c2) and d2) a) coating on a substrate 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 where the composition is comprised of components of type a1) and b1); a1) components for imparting negative tone, aqueous base developable, broadband UV resist behavior comprised ofi) a 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; andiii) at least one photo-initiator sensitive to broadband irradiation; andb1) 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 nm 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. 24. The process of claim 23 where the excimer laser emits at 248 nm. 26. The process of claim 23 where the excimer laser emits at 308 nm. 27. The process of claim 23 wherein b1) 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), (V), (VI) and (VII); where each R1, R2, R3, R4, R5 and R6 are independently selected from the group consisting of hydrogen, an alkyl group, an alkylenefluoroalkyl group, an alkylene aryl group, and an alkyleneoxyalkyl group; R7 is selected from the group consisting of an alkyl group, an alkylenefluoroalkyl group, an alkylene aryl group, and an alkyleneoxyalkyl group; each R8 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; X3 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 and is chosen from an integer from 1 to 10. 28. The process of claim 1 wherein, a1), the components for imparting negative tone, aqueous base developable, broadband UV resist behavior are selected from the group consisting of (VIII), (VIV) and (X) where, (VIII) is comprised of a) a phenolic film forming polymeric binder 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 am ino-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; ande) a photoresist solvent;(VIV) is comprised of:a-1) at least one alkali-soluble polymer where the alkali-soluble polymer comprises a least one unit of structure (VIVa) where 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; where, W is a multivalent linking group, R1a to R6a are independently selected from the group consisting of hydrogen, hydroxy, (C1-C20)alkyl and chlorine; X1 and X2 are each oxygen; and n′ is an integer equal to or greater than 1; and c-1) at least one photoinitiator andd-1) a photoresist solvent,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 polymer comprising a structure of the following formula: wherein each of R1b-R5b is independently selected from the group consisting of H, F and CH3, R6b is selected from the group consisting of a substituted aryl, unsubstituted aryl, substituted heteroaryl and unsubstituted heteroaryl group; R7b is a substituted or unsubstituted benzyl group; R8b is selected from the group consisting of a linear or branched C2-C10 hydroxy alkyl group and a C2-C10 hydroxy alkyl acrylate; R9b 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, andd-2) a photoresist solvent. 29. The process of claim 2 wherein, b1), the conjugated aryl additive is selected from the group consisting of (I) and (II). 30. The process of claim 2 wherein, b1), the conjugated aryl additive is (I). 31. The process of claim 27 wherein, b1), the conjugated aryl additive is (II). 32. The process of claim 28 wherein, a1), the components for imparting negative tone, aqueous base developable, broadband UV resist behavior are (VIII). 33. The process of claim 28 wherein, a1), the components for imparting negative tone, aqueous base developable, broadband UV resist behavior are (VIII) and the conjugated aryl additive is selected from the group consisting of (I) and (II). 34. The process of claim 28 wherein, b1), the conjugated aryl additive is (VIV). 35. The process of claim 28 wherein, b1), the conjugated aryl additive is (VIV) and where the components, a1) for imparting negative tone, aqueous base developable, broadband UV resist behavior are selected from the group consisting of (I) and (II). 36. The process of claim 28 wherein, a1), the components for imparting negative tone, aqueous base developable, broadband UV resist behavior are (X). 37. The process of claim 28 wherein, a1), the components for imparting negative tone, aqueous base developable, broadband UV resist behavior are (X) and where the conjugated aryl additive is selected from the group consisting of (I) and (II). 38. The process of claim 28 wherein, b1) the conjugated aryl additive has between the wavelengths of 220 nm and 310 nm a molar absorptivity of between about 10 and 1000 m2/mol. 39. The process of claim 28 wherein, b1), the conjugated aryl additive has a molar absorptivity at 248 nm between 10 and 1000 m2/mol. 40. The process of claim 28 wherein, b1), the conjugated aryl additive has a molar absorptivity at 308 nm between 10 and 1000 m2/mol. 41. The process of claim 28 wherein, b1), the conjugated aryl additive is (I), and further where R2 and R1 are independently selected from the group consisting of hydrogen and an alkyl group. 42. The process of claim 28 wherein, b1), the conjugated aryl additive is (II), R3 is an alkyl group, and X is Cl. 43. The composition of claim 28 wherein, b1) the conjugated aryl additive is (V), and where at least one R8 is independently selected from the group consisting of an alkoxy group, a hydroxyalkylene, and a hydroxy group. 44. The Process of claim 28 where the conjugated aryl additive is (VI), and where at least one R8 is independently selected from the group consisting of an alkoxy group, a hydroxyalkylene, and a hydroxy group
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