# US 10,246,634 B2 · Quantum dot having polymeric outer layer, photosensitive compositions including the same, and quantum dot polymer composite pattern produced therefrom > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,246,634 B2 - Document ID: US10246634B2 - Status: Granted - Kind: B2 - Application number: 15/333,417 - Filed: 2016-10-25 - Published: 2017-06-08 - Granted: 2019-04-02 - Earliest claimed: 2015-10-26 - Assignees: Samsung Electronics Co., Ltd. - Applicants: Samsung Electronics Co., Ltd. - Inventors: Hyeyeon Yang; Shang Hyeun Park; Shin Ae Jun; Eun Joo Jang - Web page: https://patentgrep.com/patent/US10246634B2 ## CPC - C09K 11/025: {non-luminescent particle coatings or suspension media} - C09K 11/70: containing phosphorus - G03F 7/0007: {Filters, e.g. additive colour filters; Components for display devices} - G03F 7/0042: {with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists (G03F7/075 takes precedence)} - G03F 7/033: the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers - G03F 7/105: having substances, e.g. indicators, for forming visible images - B82Y 99/00: Subject matter not provided for in other groups of this subclass - C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE - 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) - B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES ## Abstract A photosensitive composition including a quantum dot complex having a polymeric outer layer, a carboxylic acid group-containing binder, a photopolymerizable monomer having a carbon-carbon double bond, a photoinitiator, and a solvent, wherein the polymeric outer layer includes a copolymer including: a first repeating unit having a moiety capable of interacting with a surface of the quantum dot, an organic ligand compound bonded to the surface of the quantum dot, or a combination thereof, and a second repeating unit having a reactive moiety. ## Claims ### Claim 1 A photosensitive composition comprising: a quantum dot complex comprising a polymeric outer layer; a carboxylic acid group-containing binder; a photopolymerizable monomer comprising a carbon-carbon double bond; a photoinitiator; and a solvent, wherein the polymeric outer layer comprises a copolymer comprising: a first repeating unit comprising: a moiety capable of interacting with a surface of the quantum dot, an organic ligand compound bonded to the surface of the quantum dot, or a combination thereof, and a second repeating unit comprising a reactive moiety selected from the group consisting of a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, an epoxy group, a thiol group, an anhydride group represented by Chemical Formula 4, an imide group represented by Chemical Formula 5, a group represented by any of Chemical Formula 6 to Chemical Formula 12, and a combination thereof: wherein, in the chemical formulae, R is H, a C1 to C10 alkyl group, or a C6 to C20 aryl group, and * is a linking portion to an adjacent atom present in a backbone of the copolymer. ### Claim 2 (depends on 1) The photosensitive composition of claim 1, wherein the polymeric outer layer of the quantum dot further comprises an intermolecular or intramolecular crosslinking moiety that links the reactive moieties of the copolymer. ### Claim 3 (depends on 2) The photosensitive composition of claim 2, wherein the crosslinking moiety is represented by Chemical Formula 1 or Chemical Formula 2: wherein, each A is the same or different and is independently an amide group, an ester group, a thioester group, an ether group, a thioester group, a C1to C20 alkylene group, a C3 to C20 alkenylene group, or a combination thereof, L is a C1to C20 aliphatic hydrocarbon group, a C3 to C40alicyclic hydrocarbon group, or C6 to C40 aromatic hydrocarbon group, * is a linking portion to the reactive moiety of the copolymer, and n is an integer ranging from 2 to 7, wherein n is less than or equal to valence of L, wherein, each A is the same or different and is independently an amide group, an ester group, a thioester group, an ether group, a thioether group, a C1 to C20 alkylene group, a C3 to C20 alkenylene group, or a combination thereof, each L is the same or different and is independently a C1 to C20 aliphatic hydrocarbon group or a C6 to C40 aromatic hydrocarbon group, * is a linking portion to the reactive moiety of the copolymer, and m is an integer ranging from 1 to 10. ### Claim 4 (depends on 1) The photosensitive composition of claim 1, wherein the first repeating unit comprises a moiety in a backbone or as a pendant group of the copolymer, which is capable of interacting with the surface of the quantum dot, the organic ligand compound bonded to the surface of the quantum dot, or a combination thereof. ### Claim 5 (depends on 1) The photosensitive composition of claim 1, wherein the moiety capable of interacting with the organic ligand compound bonded to the surface of the quantum dot is a monovalent or divalent aliphatic hydrocarbon group, a monovalent or divalent aromatic hydrocarbon group, or a monovalent or divalent fluorinated aliphatic hydrocarbon group. ### Claim 6 (depends on 1) The photosensitive composition of claim 1, wherein the first repeating unit is represented by Chemical Formula 3: wherein, R1, R2, R3, and R4are each independently hydrogen, C1 to C20 alkyl group, a C1 to C20 alkyl group substituted with a functional group capable of bonding to the surface of the quantum dot, a C6 to C40 aryl group, a C6 to C40 aryl group substituted with a functional group capable of bonding to the surface of the quantum dot, a C7 to C40 arylalkyl group, a C7 to C40 arylalkyl group substituted with a functional group capable of bonding to the surface of the quantum dot, a C1 to C30 fluoroalkyl group, a C1 to C30 fluoroalkyl group substituted with a functional group capable of bonding to the surface of the quantum dot, a C1 to C30 perfluoroalkyl group, or a C1 to C30 perfluoroalkyl group substituted with a functional group capable of bonding to the surface of the quantum dot, provided that R1, R2, R3and R4are not simultaneously hydrogen. ### Claim 7 (depends on 1) The photosensitive composition of claim 1, wherein the reactive moiety of the second repeating unit is present in a backbone or as a pendant group of the copolymer. ### Claim 8 (depends on 1) The photosensitive composition of claim 1, wherein the copolymer is a random copolymer. ### Claim 9 (depends on 1) The photosensitive composition of claim 1, wherein the copolymer is a styrene-maleic anhydride copolymer, a styrene-maleimide copolymer, or a combination thereof. ### Claim 10 (depends on 1) The photosensitive composition of claim 1, wherein the organic ligand compound comprises RCOOH, RNH2, R2NH, R3N, RSH, R3PO, R3P, ROH, RCOOR′, RPO(OH)2, R2POOH (wherein, R and R′ are independently a C5 to C24aliphatic hydrocarbon group or a C6 to C20 aromatic hydrocarbon group), or a combination thereof. ### Claim 11 (depends on 1) The photosensitive composition of claim 1, wherein the quantum dot comprises Group II-VI compound, Group III-V compound, Group IV-VI compound, Group IV element or compound, Group I-III-VI compound, Group I-II-IV-VI compound, or a combination thereof. ### Claim 12 (depends on 1) The photosensitive composition of claim 1, wherein the carboxylic acid group-containing binder has an acid value of greater than or equal to about 50 milligrams of KOH per gram. ### Claim 13 (depends on 1) The photosensitive composition of claim 1, wherein the photosensitive composition is developable by an alkali aqueous solution after exposure. ### Claim 14 (depends on 1) The photosensitive composition of claim 1, wherein the photosensitive composition comprises: about 1 percent by weight to about 40 percent by weight of the quantum dot complex comprising a polymeric outer layer; about 0.5 percent by weight to about 35 percent by weight of the carboxylic acid group-containing binder; about 0.5 percent by weight to about 20 percent by weight of the photopolymerizable monomer; and about 0.01 percent by weight to about 10 percent by weight of the photoinitiator; and a balance amount of the solvent based on the total weight of the composition. ### Claim 15 (depends on 1) A quantum dot-polymer composite pattern, which is a product of a method comprising: coating the composition of claim 1 on a substrate to form a film; selectively exposing the film; and developing the selectively exposed film with an alkali aqueous solution. ### Claim 16 (depends on 15) An electronic device comprising the quantum dot-polymer composite pattern of claim 15. ### Claim 17 A quantum dot complex comprising: an organic ligand compound bonded to the surface of the quantum dot, and a polymeric outer layer comprising a copolymer, which comprises; a first repeating unit comprising a moiety capable of intermolecularly interacting with the organic ligand compound, the quantum dot surface, or a combination thereof, and a second repeating unit comprising a reactive moiety selected from the group consisting of a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, an epoxy group, a thiol group, an anhydride group represented by Chemical Formula 4, an imide group represented by Chemical Formula 5, a group represented by any of Chemical Formula 6 to Chemical Formula 12, and a combination thereof: wherein, in the chemical formulae, R is H, a C1 to C10 alkyl group, or a C6 to C20 aryl group, and * is a linking portion to an adjacent atom present in a backbone of the copolymer. ### Claim 18 (depends on 17) The quantum dot complex of claim 17, wherein the polymeric outer layer further comprises an intermolecular or intramolecular crosslinking moiety that links the reactive moieties of the copolymer. ### Claim 19 (depends on 18) The quantum dot complex of claim 18, wherein the crosslinking moiety is represented by Chemical Formula 1 or Chemical Formula 2: wherein, each A is the same or different and is independently an amide group, an ester group, a thioester group, an ether group, a thioether group, a C1 to C20alkylene group, a C3 to C20 alkenylene group, or a combination thereof, L is a C1 to C20 aliphatic hydrocarbon group, a C3 to C40 alicyclic hydrocarbon group, or C6 to C40 aromatic hydrocarbon group, * is a linking portion to the reactive moiety of the copolymer, and n is an integer ranging from 2 to 7 wherein n is less than or equal to valence of L, wherein, each A is the same or different and is independently an amide group, an ester group, a thioester group, an ether group, a thioether group, a C1 to C20 alkylene group, a C3 to C20 alkenylene group, or a combination thereof, each L is the same or different and is independently a C1 to C20 aliphatic hydrocarbon group or a C6 to C40 aromatic hydrocarbon group, * is a linking portion to the reactive moiety of the copolymer, and m is an integer ranging from 1 to 10. ### Claim 20 (depends on 17) The quantum dot complex of claim 17, wherein the first repeating unit comprises a moiety in a backbone or as a pendant group of the copolymer, which is capable of interacting with the surface of the quantum dot, the organic ligand compound bonded to the surface of the quantum dot, or a combination thereof. ### Claim 21 (depends on 17) The quantum dot complex of claim 17, wherein the moiety capable of interacting with the organic ligand compound bonded to the surface of the quantum dot is a monovalent or divalent aliphatic hydrocarbon group, a monovalent or divalent aromatic hydrocarbon group, or a monovalent or divalent fluorinated aliphatic hydrocarbon group. ### Claim 22 (depends on 17) The quantum dot complex of claim 17, wherein the first repeating unit is represented by Chemical Formula 3: wherein, R1, R2, R3, and R4are independently hydrogen, C1 to C20 alkyl group, a C1 to C20 alkyl group substituted with a functional group capable of bonding to the surface of the quantum dot, a C6 to C40 aryl group, a C6 to C40 aryl group substituted with a functional group capable of bonding to the surface of the quantum dot, a C7 to C40 arylalkyl group, a C7 to C40 arylalkyl group substituted with a functional group capable of bonding to the surface of the quantum dot, a C1 to C30 fluoroalkyl group, a C1 to C30 fluoroalkyl group substituted with a functional group capable of bonding to the surface of the quantum dot, a C1 to C30 perfluoroalkyl group, or a C1 to C30perfluoroalkyl group substituted with a functional group capable of bonding to the surface of the quantum dot, provided that R1, R2, R3and R4are not simultaneously hydrogen. ### Claim 23 (depends on 17) The quantum dot complex of claim 17, wherein the reactive moiety of the second repeating unit is present in a backbone or as a pendant group of the copolymer. ### Claim 24 (depends on 17) The quantum dot complex of claim 17, wherein the copolymer is a random copolymer. ### Claim 25 (depends on 17) The quantum dot complex of claim 17, wherein the copolymer is a styrene-maleic anhydride copolymer, a styrene-maleimide copolymer, or a combination thereof.