# US 10,374,015 B2 · Photoelectric conversion element and solid-state imaging device > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,374,015 B2 - Document ID: US10374015B2 - Status: Granted - Kind: B2 - Application number: 15/575,086 - Filed: 2016-05-19 - Published: 2018-05-31 - Granted: 2019-08-06 - Earliest claimed: 2015-05-29 - Assignees: Sony Semiconductor Solutions Corporation - Applicants: Sony Semiconductor Solutions Corporation - Inventors: Yuta Hasegawa; Nobuyuki Matsuzawa; Yoshiaki Obana; Ichiro Takemura; Norikazu Nakayama; Masami Shimokawa; Tetsuji Yamaguchi; Iwao Yagi; Hideaki Mogi - Web page: https://patentgrep.com/patent/US10374015B2 ## CPC - H10K 39/32: Organic image sensors - H10F 30/20: the devices having potential barriers, e.g. phototransistors - H10F 39/12: Image sensors - H10K 19/20: comprising components having an active region that includes an inorganic semiconductor - H10K 71/164: {using vacuum deposition} - H10K 85/631: {Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine} - H10F 39/014: {of CMOS image sensors} - H10F 39/1825: {Multicolour image sensors having stacked structure, e.g. NPN, NPNPN or multiple quantum well [MQW] structures} - H10K 30/30: comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains - H10K 85/211: {Fullerenes, e.g. C60} - H10K 85/215: {comprising substituents, e.g. PCBM} - H10K 85/322: {comprising boron} - H10K 85/622: {containing four rings, e.g. pyrene} - H10K 85/626: {containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene} - H10K 85/633: {comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom} - H10K 85/6572: {comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole} - H10K 85/6576: {comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene} - Y02E 10/549: Organic PV cells - H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES - H10F: INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION - Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION ## Abstract A photoelectric conversion element according to an embodiment of the present disclosure includes: a first electrode and a second electrode facing each other; and a photoelectric conversion layer provided between the first electrode and the second electrode, and including a first organic semiconductor material, a second organic semiconductor material, and a third organic semiconductor material that have mother skeletons different from one another. The first organic semiconductor material is one of fullerenes and fullerene derivatives. The second organic semiconductor material in a form of a single-layer film has a higher linear absorption coefficient of a maximal light absorption wavelength in a visible light region than a single-layer film of the first organic semiconductor material and a single-layer film of the third organic semiconductor material. The third organic semiconductor material has a value equal to or higher than a HOMO level of the second organic semiconductor material. ## Claims ### Claim 1 A photoelectric conversion element, comprising: a first electrode and a second electrode facing each other; and a photoelectric conversion layer provided between the first electrode and the second electrode, and including a first organic semiconductor material, a second organic semiconductor material, and a third organic semiconductor material that have mother skeletons different from one another, the first organic semiconductor material being one of fullerenes and fullerene derivatives, the second organic semiconductor material in a form of a single-layer film having a higher linear absorption coefficient of a maximal light absorption wavelength in a visible light region than a single-layer film of the first organic semiconductor material and a single-layer film of the third organic semiconductor material, and the third organic semiconductor material having a value equal to or higher than a HOMO level of the second organic semiconductor material. ### Claim 2 (depends on 1) The photoelectric conversion element according to claim 1, wherein the third organic semiconductor material in a form of a single-layer film has higher hole mobility than hole mobility of a single-layer film of the second organic semiconductor material. ### Claim 3 (depends on 1) The photoelectric conversion element according to claim 1, wherein in the photoelectric conversion layer, excitons generated through light absorption by the second organic semiconductor material are separated at an interface between two organic semiconductor materials selected from the first organic semiconductor material, the second organic semiconductor material, and the third organic semiconductor material. ### Claim 4 (depends on 1) The photoelectric conversion element according to claim 1, wherein the photoelectric conversion layer has a maximal absorption wavelength in a range from 450 nm to 650 nm both inclusive. ### Claim 5 (depends on 1) The photoelectric conversion element according to claim 1, wherein the third organic semiconductor material includes a hetero element other than carbon (C) and hydrogen (H) in a molecule of the third organic semiconductor material. ### Claim 6 (depends on 1) The photoelectric conversion element according to claim 1, wherein the photoelectric conversion layer includes the first organic semiconductor material in a range from 10 vol % to 35 vol % both inclusive. ### Claim 7 (depends on 1) The photoelectric conversion element according to claim 1, wherein the photoelectric conversion layer includes the second organic semiconductor material in a range from 30 vol % to 80 vol % both inclusive. ### Claim 8 (depends on 1) The photoelectric conversion element according to claim 1, wherein the photoelectric conversion layer includes the third organic semiconductor material in a range from 10 vol % to 60 vol % both inclusive. ### Claim 9 (depends on 1) The photoelectric conversion element according to claim 1, wherein one of the second organic semiconductor material and the third organic semiconductor material is a quinacridone derivative represented by the following formula where each of R1 and R2 is independently one of a hydrogen atom, an alkyl group, an aryl group, and a heterocyclic group, each of R3 and R4 is independently one of an alkyl chain, an alkenyl group, an alkynyl group, an aryl group, a cyano group, a nitro group, and a silyl group, and two or more of R3 or two or more of R4 optionally form a ring together, and each of n1 and n2 is independently 0 or an integer of 1 or more. ### Claim 10 (depends on 1) The photoelectric conversion element according to claim 1, wherein one of the second organic semiconductor material and the third organic semiconductor material is one of a triallylamine derivative represented by the following formula (3) and a benzothienobenzothiophene derivative represented by the following formula (4): where each of R20 to R23 is independently a substituent represented by a formula (2)′, each of R24 to R28 is independently one of a hydrogen atom, a halogen atom, an aryl group, an aromatic hydrocarbon ring group, an aromatic hydrocarbon ring group having an alkyl chain or a substituent, an aromatic heterocyclic group, and an aromatic heterocyclic group having an alkyl chain or a substituent, adjacent ones of R24 to R28 are optionally saturated or unsaturated divalent groups that are bound to one another to form a ring, and where each of R5 and R6 is independently one of a hydrogen atom and a substituent represented by a formula (3)′, and R7 is one of an aromatic ring group and an aromatic ring group having a substituent. ### Claim 11 (depends on 1) The photoelectric conversion element according to claim 1, wherein one of the second organic semiconductor material and the third organic semiconductor material is a subphthalocyanine derivative represented by the following formula (4): where each of R8 to R19 is independently selected from a group consisting of a hydrogen atom, a halogen atom, a straight-chain, branched, or cyclic alkyl group, a thioalkyl group, a thioaryl group, an arylsulfonyl group, an alkylsulfonyl group, an amino group, an alkylamino group, an arylamino group, a hydroxy group, an alkoxy group, an acylamino group, an acyloxy group, a phenyl group, a carboxy group, a carboxyamide group, a carboalkoxy group, an acyl group, a sulfonyl group, a cyano group, and a nitro group, any adjacent ones of R8 to R19 are optionally part of a condensed aliphatic ring or a condensed aromatic ring, the condensed aliphatic ring or the condensed aromatic ring optionally includes one or more atoms other than carbon, M is one of boron and a divalent or trivalent metal, and X is an anionic group. ### Claim 12 (depends on 1) The photoelectric conversion element according to claim 1, wherein the second organic semiconductor material is a subphthalocyanine derivative, and the third organic semiconductor material is a quinacridone derivative. ### Claim 13 (depends on 1) The photoelectric conversion element according to claim 1, wherein the second organic semiconductor material is a subphthalocyanine derivative and the third organic semiconductor material is a triallylamine derivative or a benzothienobenzothiophene derivative. ### Claim 14 (depends on 1) The photoelectric conversion element according to claim 1, wherein the fullerenes and the fullerene derivatives are represented by one of the following formulas (5) and (6): where each R is independently one of a hydrogen atom, a halogen atom, a straight-chain, branched, or cyclic alkyl group, a phenyl group, a group having a straight-chain or condensed ring aromatic compound, a group having a halide, a partial fluoroalkyl group, a perfluoroalkyl group, a silylalkyl group, a silyl alkoxy group, an arylsilyl group, an arylsulfanyl group, an alkylsulfanyl group, an arylsulfonyl group, an alkylsulfonyl group, an arylsulfide group, an alkylsulfide group, an amino group, an alkylamino group, an arylamino group, a hydroxy group, an alkoxy group, an acylamino group, an acyloxy group, a carbonyl group, a carboxy group, a carboxyamide group, a carboalkoxy group, an acyl group, a sulfonyl group, a cyano group, a nitro group, a group having a chalcogenide, a phosphine group, a phosphone group, and derivatives thereof, and each of “n” and “m” is 0 or an integer of 1 or more. ### Claim 15 (depends on 1) The photoelectric conversion element according to claim 1, wherein the photoelectric conversion layer includes a fourth organic semiconductor material having the same mother skeleton as the mother skeleton of one of the first organic semiconductor material, the second organic semiconductor material, and the third organic semiconductor material, and having a different substituent. ### Claim 16 (depends on 1) The photoelectric conversion element according to claim 1, wherein the visible light region is in a range from 450 nm to 800 nm both inclusive. ### Claim 17 A solid-state imaging device provided with pixels each including one or more organic photoelectric converters, each of the organic photoelectric converters comprising: a first electrode and a second electrode facing each other; and a photoelectric conversion layer provided between the first electrode and the second electrode, and including a first organic semiconductor material, a second organic semiconductor material, and a third organic semiconductor material that have mother skeletons different from one another, the first organic semiconductor material being one of fullerenes and fullerene derivatives, the second organic semiconductor material in a form of a single-layer film having a higher linear absorption coefficient of a maximal light absorption wavelength in a visible light region than a single-layer film of the first organic semiconductor material and a single-layer film of the third organic semiconductor material, and the third organic semiconductor material having a value equal to or higher than a HOMO level of the second organic semiconductor material. ### Claim 18 (depends on 17) The solid-state imaging device according to claim 17, wherein the one or more organic photoelectric converters, and one or more inorganic photoelectric converters that performs photoelectric conversion in a wavelength region different from a wavelength region of the organic photoelectric converters are stacked in each of the pixels. ### Claim 19 (depends on 18) The solid-state imaging device according to claim 18, wherein the one or more inorganic photoelectric converters are formed to be embedded in a semiconductor substrate, and the one or more organic photoelectric converters are formed on first surface side of the semiconductor substrate. ### Claim 20 (depends on 19) The solid-state imaging device according to claim 19, wherein the one or more organic photoelectric converters perform photoelectric conversion on green light, and an inorganic photoelectric converter that performs photoelectric conversion on blue light and an inorganic photoelectric converter that performs photoelectric conversion on red light are stacked in the semiconductor substrate.