# US 8,772,376 B2 · Near-infrared absorbing film compositions > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 8,772,376 B2 - Document ID: US8772376B2 - Status: Granted - Kind: B2 - Application number: 12/542,970 - Filed: 2009-08-18 - Published: 2011-02-24 - Granted: 2014-07-08 - Earliest claimed: 2009-08-18 - Assignees: International Business Machines Corporation - Applicants: Wu-Song Huang; Martin Glodde; Dario L. Goldfarb; Wai-Kin Li; Sen Liu; Libor Vyklicky - Inventors: Wu-Song Huang; Martin Glodde; Dario L. Goldfarb; Wai-Kin Li; Sen Liu; Libor Vyklicky - Web page: https://patentgrep.com/patent/US8772376B2 ## CPC - G03F 7/0388: {with ethylenic or acetylenic bands in the side chains of the photopolymer} - G03F 7/038: Macromolecular compounds which are rendered insoluble or differentially wettable (G03F7/075 takes precedence; macromolecular azides G03F7/012; macromolecular diazonium compounds G03F7/021) - G03F 7/091: {characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement} - G03F 7/11: having cover layers or intermediate layers, e.g. subbing layers {(G03F7/091 - G03F7/093, B41N3/03 take precedence)} - H10K 30/87: Light-trapping means - Y02E 10/549: Organic PV cells - G03F: PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR; (phototypographic composing devices B41B; photosensitive materials or processes for photographic purposes G03C; electrophotography, sensitive layers or processes therefor G03G) - H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES - Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION ## Abstract A curable liquid formulation comprising: (i) one or more near-infrared absorbing polymethine dyes; (ii) one or more crosslinkable polymers; and (iii) one or more casting solvents. The invention is also directed to solid near-infrared absorbing films composed of crosslinked forms of the curable liquid formulation. The invention is also directed to a microelectronic substrate containing a coating of the solid near-infrared absorbing film as well as a method for patterning a photoresist layer coated on a microelectronic substrate in the case where the near-infrared absorbing film is between the microelectronic substrate and a photoresist film. ## Claims ### Claim 1 A curable liquid formulation comprising: (i) at least one near-infrared absorbing polymethine dye; (ii) at least one crosslinkable polymer, which is a copolymer, terpolymer, or higher order polymer comprised of one or more epoxy-containing units selected from: and further comprised of one or more units selected from: wherein n is a value of at least 1; (iii) one or more casting solvents; and (iv) an acid generator selected from: and triethylammonium nonafluorobutane sulfonate. ### Claim 2 (depends on 1) The liquid formulation of claim 1 further comprising one or more inter-polymer crosslinking agents. ### Claim 3 (depends on 1) The liquid formulation of claim 1 further comprising one or more surfactants. ### Claim 4 (depends on 1) The liquid formulation of claim 1 wherein the at least one polymethine dye absorbs electromagnetic radiation within a wavelength range of 500 nm to 1200 nm. ### Claim 5 (depends on 1) The liquid formulation of claim 1, wherein the at least one polymethine dye has a formula within the following generic formula: wherein R1 or a cyclic interconnection of R1 and R2 represents a nitrogen-, oxygen-, and/or sulfur-containing monocyclic ring or polycyclic ring system, or a hydrocarbon group derivatized with an acyclic amino group; R6 or a cyclic interconnection of R5 and R6 represents a nitrogen-, oxygen-, and/or sulfur-containing monocyclic ring or polycyclic ring system, or a hydrocarbon group derivatized with an acyclic amino group; R2, R3, R4, and R5 are each independently selected from (i) a hydrogen atom, or (ii) halide atom, or (iii) cyanide group, or (iv) hydroxy group, or (v) a hydrocarbon group containing at least one carbon atom, wherein a hydrocarbon group optionally includes one or more heteroatoms selected from nitrogen, oxygen, sulfur, and halides, or (vi) a group of formula —XR8 wherein X is O or S and R8 is a hydrocarbon group optionally containing one or more heteroatoms selected from oxygen, nitrogen, and sulfur atoms, or (vii) a group of formula —NR9R10 wherein R9 and R10 are each independently a hydrogen atom or hydrocarbon group optionally containing one or more heteroatoms selected from oxygen, nitrogen, and sulfur atoms; wherein when any two of R2, R3, R4, and R5 are hydrocarbon groups, they can interconnect to form a five- or six-membered ring; and subscript n is a value of at least 1 and up to 16; and wherein one or more of the nitrogen, oxygen, or sulfur atoms are either in a neutral or positively charged state, and if in a positive state, an anion is associated with the polymethine dye. ### Claim 6 (depends on 5) The liquid formulation of claim 5, wherein the at least one polymethine dye has a formula within the following generic formula: wherein R1 or a cyclic interconnection of R1 and R2 represents a nitrogen-, oxygen-, and/or sulfur-containing monocyclic ring or polycyclic ring system, or a hydrocarbon group derivatized with an acyclic amino group; R6 or a cyclic interconnection of R5 and R6 represents a nitrogen-, oxygen-, and/or sulfur-containing monocyclic ring or polycyclic ring system, or a hydrocarbon group derivatized with an acyclic amino group; R7 is selected from (i) a hydrogen atom, or (ii) halide atom, or (iii) cyanide group, or (iv) hydroxy group, or (v) a hydrocarbon group containing at least one carbon atom, wherein a hydrocarbon group optionally includes one or more heteroatoms selected from nitrogen, oxygen, sulfur, and halides, or (vi) a group of formula —XR8 wherein X is O or S and R8 is a hydrocarbon group optionally containing one or more heteroatoms selected from oxygen, nitrogen, and sulfur atoms, or (vii) a group of formula —NR9R10 wherein R9 and R10 are each independently a hydrogen atom or hydrocarbon group optionally containing one or more heteroatoms selected from oxygen, nitrogen, and sulfur atoms; and subscript r can be a value of 1 or 2. ### Claim 7 (depends on 5) The liquid formulation of claim 5, wherein the at least one polymethine dye has a formula within the following generic formula: wherein R1 or a cyclic interconnection of R1 and R11 represents a nitrogen-, oxygen-, and/or sulfur-containing monocyclic ring or polycyclic ring system; R6 or a cyclic interconnection of R6 and R12 represents a nitrogen-, oxygen-, and/or sulfur-containing monocyclic ring or polycyclic ring system; R2, R3, R4, R11, and R12 are each independently selected from (i) a hydrogen atom, or (ii) halide atom, or (iii) cyanide group, or (iv) hydroxy group, or (v) a hydrocarbon group containing at least one carbon atom, wherein a hydrocarbon group optionally includes one or more heteroatoms selected from nitrogen, oxygen, sulfur, and halides, or (vi) a group of formula —XR8 wherein X is O or S and R8 is a hydrogen atom or a hydrocarbon group optionally containing one or more heteroatoms selected from oxygen, nitrogen, and sulfur atoms, or (vii) a group of formula —NR9R10 wherein R9 and R10 are each independently a hydrocarbon group optionally containing one or more heteroatoms selected from oxygen, nitrogen, and sulfur atoms; wherein when any two of R2, R3, and R4 are hydrocarbon groups, they can interconnect to form a five- or six-membered ring; and subscripts n1 and n2 each independently have a value of 0 or a number of 1 to 6. ### Claim 8 (depends on 5) The liquid formulation of claim 5, wherein the at least one polymethine dye has a formula within the following generic formula: wherein R1 or a cyclic interconnection of R1 and R11 represents a nitrogen-, oxygen-, and/or sulfur-containing monocyclic ring or polycyclic ring system; R6 or a cyclic interconnection of R6 and R12 represents a nitrogen-, oxygen-, and/or sulfur-containing monocyclic ring or polycyclic ring system; R3, R11, and R12 are each independently selected from (i) a hydrogen atom, or (ii) halide atom, or (iii) cyanide group, or (iv) hydroxy group, or (v) a hydrocarbon group containing at least one carbon atom, wherein a hydrocarbon group optionally includes one or more heteroatoms selected from nitrogen, oxygen, sulfur, and halides, or (vi) a group of formula —XR8 wherein X is O or S and R8 is a hydrocarbon group optionally containing one or more heteroatoms selected from oxygen, nitrogen, and sulfur atoms, or (vii) a group of formula —NR9R10 wherein R9 and R10 are each independently a hydrogen atom or hydrocarbon group optionally containing one or more heteroatoms selected from oxygen, nitrogen, and sulfur atoms; subscript r can be a value of 1 or 2; and subscripts n1 and n2 each independently have a value of 0 or a number of 1 to 6. ### Claim 9 (depends on 1) The liquid formulation of claim 1, wherein said acid generator comprises triethylammonium nonafluorobutane sulfonate. ### Claim 10 (depends on 1) The liquid formulation of claim 1, wherein said at least one crosslinkable polymer is a copolymer, terpolymer, or higher order polymer comprised of one or more epoxy-containing units selected from: and further comprised of one or more units selected from: wherein n is a value of at least 1. ### Claim 11 (depends on 10) The liquid formulation of claim 10, wherein the acid generator comprises triethylammonium nonafluorobutane sulfonate. ### Claim 12 (depends on 1) The liquid formulation of claim 1, wherein said at least one crosslinkable polymer is a copolymer selected from: ### Claim 13 (depends on 12) The liquid formulation of claim 12, wherein the acid generator comprises triethylammonium nonafluorobutane sulfonate.