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US-12622169-B2 - Photoelectric conversion element, imaging element, optical sensor, and compound

US12622169B2US 12622169 B2US12622169 B2US 12622169B2US-12622169-B2

Abstract

A photoelectric conversion element with an excellent sensitivity, an imaging element, an optical sensor, and a compound are provided. The photoelectric conversion element includes, in the following order, a conductive film, a photoelectric conversion film, and a transparent conductive film, in which the photoelectric conversion film contains a compound represented by Formula (1) and a coloring agent. A-D-A  (1)

Inventors

  • Yukio Tani
  • Hiroki Sugiura
  • Yasunori Yonekuta

Assignees

  • FUJIFILM CORPORATION

Dates

Publication Date
20260505
Application Date
20221028
Priority Date
20200430

Claims (20)

  1. 1 . A photoelectric conversion element comprising, in the following order: a conductive film; a photoelectric conversion film; and a transparent conductive film, wherein the photoelectric conversion film contains a compound represented by Formula (1) and a coloring agent, A-D-A (1) in Formula (1), D is a group represented by any of Formula (1-1) to Formula (1-15), A is a group represented by any of Formula (3-1) to Formula (3-14), in a case where D is a group represented by Formula (1-6), A is a group represented by any one of formula (3-1) to Formula (3-9) and formula (3-11) to Formula (3-14), where, two A's present in Formula (1) are each a group having the same structure, in Formula (1-1) to Formula (1-15), * represents a bonding position, X 1 represents a sulfur atom, an oxygen atom, a selenium atom, or a tellurium atom, one of Y 1 and Y 2 represents a sulfur atom, an oxygen atom, a selenium atom, or a tellurium atom, and another one represents —CH═, one of Y 3 and Y 4 represents a sulfur atom, an oxygen atom, a selenium atom, or a tellurium atom, and another one represents —CH═, one of Y 5 and Y 6 represents a sulfur atom, an oxygen atom, a selenium atom, or a tellurium atom, and another one represents —CH═, one of Y 7 and Y 8 represents a sulfur atom, an oxygen atom, a selenium atom, or a tellurium atom, and another one represents —CH═, n 1 represents an integer of 3 to 5, n 2 represents an integer of 3 to 5, n 3 represents an integer of 0 to 2, where, at least one of two n 3 's present in each of Formula (1-4) to Formula (1-7) represents an integer of 1 or 2, n 4 to n 21 each independently represent an integer of 0 to 2, Ar in Formula (1-1) and Formula (1-2) is a group represented by Formula (2-3), Ar in Formula (1-4) is a group represented by any of Formula (2-1) to Formula (2-3), Ar in Formula (1-5) to Formula (1-9) and Formula (1-11) to Formula (1-15) is a group represented by any of Formula (2-1) to Formula (2-4), in Formula (2-1) to Formula (2-4), * represents a bonding position, X 2 represents a sulfur atom, an oxygen atom, a selenium atom, or a tellurium atom, Z 1 represents —CH═ or —N═, where, at least one of two Z 1 's in Formula (2-3) is —N═, Z 4 represents —CH═ or —N═, one or more of —CH═ included in a ring structure in a group represented by D in Formula (1) may be substituted with —CR 3 ═, R 3 represents a halogen atom, in Formula (3-1) to Formula (3-14), * represents a bonding position, B 1 and B 2 each independently represent a sulfur atom, an oxygen atom, ═C(CN) 2 , or ═C(CN)(CO 2 R 1 ), R 1 represents an alkyl group having 1 or 2 carbon atoms, which may have a halogen atom as a substituent, E represents an aromatic ring, which may have a group selected from the group consisting of a halogen atom, a methyl group, an ethyl group, and a methoxy group, as a substituent, where the methyl group, the ethyl group, and the methoxy group each may further have a halogen atom as a substituent, R represents an alkyl group having 1 or 2 carbon atoms, which may have a halogen atom as a substituent, G represents —CR G ═ or —N═, R G represents a hydrogen atom, a halogen atom, or a cyano group, where, at least one of five G's in Formula (3-8) is —N═, and at least one of seven G's in Formula (3-13) is —N═, m1 represents an integer of 1 to 5, m2 represents an integer of 1 to 5, m3 represents an integer of 0 to 3, m4 represents an integer of 0 to 4, where, in Formula (3-14), m3+m4 is 1 or more, one or more of —CH═ included in a ring structure in a group represented by Formula (3-10) and Formula (3-14) may be substituted with —CR 4 ═, R 4 represents a halogen atom other than a fluorine atom, X 4 represents a sulfur atom, an oxygen atom, a selenium atom, or a tellurium atom, Z 2 to Z 5 each independently represent —CR Z ═ or —N═, R Z represents a hydrogen atom or a halogen atom, where, at least one of Z 2 and Z 3 in Formula (3-11) is —N═, one of four Z 5 's in Formula (3-12) is a substituent including a carbon atom, J represents a hydrogen atom, a halogen atom, an aryl group, a heteroaryl group, or an alkyl group having 1 or 2 carbon atoms, which may have a halogen atom as a substituent, the aryl group and the heteroaryl group that are represented by J may have, as a substituent, one or both of a halogen atom and an alkyl group having 1 or 2 carbon atoms, which has a halogen atom as a further substituent, J and Z 3 may be bonded to each other to form an aromatic ring, which may have a halogen atom as a substituent, in a case where J and Z 3 are bonded to each other to form the aromatic ring, both Z 2 and Z 3 may be other than —N═, ArL is a group represented by any of Formula (Ar1) to Formula (Ar3), in Formula (Ar1) to Formula (Ar3), * D represents a bonding position with respect to a group represented by D, and * A represents a bonding position with respect to a group other than the group represented by D, mx is 1 in a group represented by any of Formula (Ar1) to Formula (Ar3) as ArL in Formula (3-5), and is the same value as m1 in a group represented by any of Formula (Ar1) to Formula (Ar3) as ArL in Formula (3-9), X 3 represents a sulfur atom, an oxygen atom, a selenium atom, or a tellurium atom, Y 9 represents —CH═, —CR 2 ═, or —N═, R 2 represents a halogen atom or an alkyl group having 1 or 2 carbon atoms, which may have a halogen atom as a substituent, Y 10 represents —CH═ or —CR 3 ═, R 3 represents a halogen atom, in a case where A is a group represented by Formula (3-5) and D is a group represented by Formula (1-8) in which n 4 and n 5 are each independently an integer of 1 or 2 and all Ar's are a group represented by Formula (2-1), ArL in Formula (3-5) is a group represented by Formula (Ar1) or Formula (Ar3), in a case where A is a group represented by Formula (3-8), D is a group represented by Formula (1-1) to Formula (1-7), a group represented by Formula (1-8) in which n 4 and n 5 are each independently an integer of 1 or 2 and Ar is a group represented by Formula (2-3), a group represented by Formula (1-9), a group represented by formula (1-11) in which n 8 and n 9 are each independently an integer of 1 or 2 and Ar is a group represented by Formula (2-3), a group represented by Formula (1-12) or Formula (1-13), a group represented by Formula (1-14) in which n 14 and n 15 are each independently an integer of 1 or 2, or a group represented by Formula (1-15), in a case where A is a group represented by Formula (3-9), D is a group represented by Formula (1-1) in which n 18 and n 19 are each independently an integer of 1 or 2, a group represented by Formula (1-2), a group represented by Formula (1-4) in which n 3 is an integer of 1 or 2 and Ar that is directly bonded to A is a group represented by Formula (2-3), a group represented by Formula (1-5) in which n 3 is an integer of 1 or 2, a group represented by Formula (1-6) in which n 3 is an integer of 1 or 2, a group represented by Formula (1-7) in which n 3 is an integer of 1 or 2, a group represented by Formula (1-8) in which n 4 and n 5 are each independently an integer of 1 or 2 and Ar is a group represented by Formula (2-3), a group represented by Formula (1-9) in which n 6 and n 7 are each independently an integer of 1 or 2, a group represented by Formula (1-10), a group represented by Formula (1-11) in which n 8 and n 9 are each independently an integer of 1 or 2, a group represented by Formula (1-12) in which n 10 and n 11 are each independently an integer of 1 or 2, a group represented by Formula (1-13) in which n 12 and n 13 are each independently an integer of 1 or 2, a group represented by Formula (1-14) in which n 14 and n 15 are each independently an integer of 1 or 2, or a group represented by Formula (1-15) in which n 16 and n 17 are each independently an integer of 1 or 2, in a case where A is a group represented by Formula (3-10), D is a group represented by Formula (1-1) in which n 18 and n 19 are each independently an integer of 1 or 2, a group represented by Formula (1-2), a group represented by Formula (1-4) in which n 3 is an integer of 1 or 2 and Ar that is directly bonded to A is a group represented by Formula (2-3), a group represented by Formula (1-5) in which n 3 is an integer of 1 or 2 and Ar is a group represented by Formula (2-3), a group represented by Formula (1-6) in which n 3 is an integer of 1 or 2 and Ar is a group represented by Formula (2-3) or Formula (2-4), a group represented by Formula (1-7) in which n 3 is an integer of 1 or 2, a group represented by Formula (1-8) in which n 4 and n 5 are each independently an integer of 1 or 2 and Ar is a group represented by Formula (2-3), a group represented by Formula (1-9) in which n 6 and n 7 are each independently an integer of 1 or 2, a group represented by Formula (1-11) in which n 8 and n 9 are each independently an integer of 1 or 2 and Ar is a group represented by Formula (2-3), a group represented by Formula (1-12) in which n 10 and n 11 are each independently an integer of 1 or 2, a group represented by Formula (1-13) in which n 12 and n 13 are each independently an integer of 1 or 2, a group represented by Formula (1-14) in which n 14 and n 15 are each independently an integer of 1 or 2, or a group represented by Formula (1-15) in which n 16 and n 17 are each independently an integer of 1 or 2, in a case where A is a group represented by Formula (3-11) and D is a group represented by Formula (1-8), J and Z 3 in Formula (3-11) may not be bonded to each other to form an aromatic ring, in a case where A is a group represented by Formula (3-11) and D is a group represented by Formula (1-11) in which n 8 and n 9 both are 0, J and Z 3 in Formula (3-11) may not be bonded to each other to form an aromatic ring, in a case where A is a group represented by Formula (3-11), and D is a group represented by Formula (1-12) in which n 10 and n 11 both are 1 and all Ar's are a group represented by Formula (2-2), J and Z 3 in Formula (3-11) may not be bonded to each other to form an aromatic ring, in a case where A is a group represented by Formula (3-12), D is a group represented by Formula (1-1) to Formula (1-7), a group represented by Formula (1-8) in which n 4 and n 5 are each independently an integer of 1 or 2, a group represented by Formula (1-9) or Formula (1-10), a group represented by formula (1-11) in which n 8 and n 9 are each independently an integer of 1 or 2 and Ar is a group represented by Formula (2-3) or Formula (2-4), or a group represented by Formula (1-12) to Formula (1-15), when A is a group represented by Formula (3-12) and D is a group represented by Formula (1-12), a case that n 10 and n 11 both are 1, and all Ar's are a group represented by Formula (2-2) is excluded, and in a case where A is a group represented by Formula (3-13), D is a group represented by Formula (1-1) to Formula (1-7), a group represented by Formula (1-8) in which n 4 and n 5 are each independently an integer of 1 or 2 and Ar is a group represented by Formula (2-3) or Formula (2-4), a group represented by Formula (1-9) or Formula (1-10), a group represented by formula (1-11) in which n 8 and n 9 are each independently an integer of 1 or 2 and Ar is a group represented by Formula (2-1), Formula (2-3) or Formula (2-4), or a group represented by Formula (1-12) to Formula (1-15).
  2. 2 . The photoelectric conversion element according to claim 1 , wherein the D is a group represented by any of Formula (1-5) to Formula (1-7), Formula (1-9), and Formula (1-12) to Formula (1-15).
  3. 3 . The photoelectric conversion element according to claim 1 , wherein the D is a group represented by any of Formula (1-9) and Formula (1-12) to Formula (1-15).
  4. 4 . The photoelectric conversion element according to claim 1 , wherein the D is a group represented by any of Formula (1-9), Formula (1-12), Formula (1-13), and Formula (1-15).
  5. 5 . The photoelectric conversion element according to claim 1 , wherein the D is a group represented by any of Formula (1-12), Formula (1-13), and Formula (1-15).
  6. 6 . The photoelectric conversion element according to claim 1 , wherein the D is a group represented by Formula (1-12).
  7. 7 . The photoelectric conversion element according to claim 1 , wherein the A is a group represented by any of Formula (3-1) to Formula (3-3), and Formula (3-5) to Formula (3-14).
  8. 8 . The photoelectric conversion element according to claim 1 , wherein the A is a group represented by any of Formula (3-5) and Formula (3-8) to Formula (3-14).
  9. 9 . The photoelectric conversion element according to claim 1 , wherein the A is a group represented by any of Formula (3-8) and Formula (3-10) to Formula (3-14).
  10. 10 . The photoelectric conversion element according to claim 1 , wherein the A is a group represented by any of Formula (3-10) to Formula (3-12), and Formula (3-14).
  11. 11 . The photoelectric conversion element according to claim 1 , wherein the A is a group represented by any of Formula (3-11) and Formula (3-12).
  12. 12 . The photoelectric conversion element according to claim 1 , wherein the A is a group represented by Formula (3-11).
  13. 13 . The photoelectric conversion element according to claim 1 , wherein the compound represented by Formula (1) has a molecular weight of 400 to 900.
  14. 14 . The photoelectric conversion element according to claim 1 , wherein the photoelectric conversion film is a mixture layer formed in a state where the compound represented by Formula (1) and the coloring agent are mixed.
  15. 15 . A photoelectric conversion element comprising, in the following order: a conductive film; a photoelectric conversion film; and a transparent conductive film, wherein the photoelectric conversion film contains a compound represented by Formula (1A) and a coloring agent, in Formula (1A), X A represents a sulfur atom or an oxygen atom, Ar A represents a group represented by any of Formula (4-1) to Formula (4-8), Formula (5-1) to Formula (5-7), Formula (6-1) and Formula (6-2), Formula (7-1) and Formula (7-2), Formula (8-1) and Formula (8-2), Formula (9-1) to Formula (9-8), Formula (10-1) to Formula (10-3), and Formula (11-1), where, two X A 's present in Formula (1A) are each a group having the same structure, and two Ar A 's present in Formula (1A) are each a group having the same structure, in Formula (4-1) to Formula (4-8), Formula (5-1) to Formula (5-7), Formula (6-1) and Formula (6-2), Formula (7-1) and Formula (7-2), Formula (8-1) and Formula (8-2), Formula (9-1) to Formula (9-8), Formula (10-1) to Formula (10-3), and Formula (11-1), * represents a bonding position, X a1 to X a3 each independently represent a sulfur atom or an oxygen atom, Z a1 to Z a13 each independently represent —CH═, —CF═, or —N═, in Formula (4-1), at least one of Z a1 to Z a7 is —CF═ or —N═, in Formula (4-2), at least one of Z a1 to Z a9 is —CF═ or —N═, in Formula (4-3), at least one of Z a1 to Z a8 is —CF═ or —N═, in Formula (4-4), at least one of Z a1 to Z a7 is —CF═ or —N═, in Formula (4-5), at least one of Z a1 to Z a5 is —CF═ or —N═, in Formula (4-6), at least one of Z a1 to Z a5 is —CF═ or —N═, in Formula (4-7), at least one of Z a1 to Z a9 is —CF═ or —N═, in Formula (4-8), at least one of Z a1 to Z a7 is —CF═ or —N═, in Formula (5-1), at least one of Z a1 to Z a9 is —CF═ or —N═, in Formula (5-2), at least one of Z a1 to Z a11 is —CF═ or —N═, in Formula (5-3), at least one of Z a1 to Z a10 is —CF═ or —N═, in Formula (5-4), at least one of Z a1 to Z a7 is —CF═ or —N═, in Formula (5-5), at least one of Z a1 to Z a7 is —CF═ or —N═, in Formula (5-6), at least one of Z a1 to Z a11 is —CF═ or —N═, in Formula (5-7), at least one of Z a1 to Z a9 is —CF═ or —N═, in Formula (6-1), at least one of Z a1 to Z a5 is —CF═ or —N═, in Formula (6-2), at least one of Z a1 to Z a7 is —CF═ or —N═, in Formula (7-1), at least one of Z a1 to Z a8 is —CF═ or —N═, in Formula (7-2), at least one of Z a1 to Z a10 is —CF═ or —N═, in Formula (8-1), at least one of Z a1 to Z a8 is —CF═ or —N═, in Formula (8-2), at least one of Z a1 to Z a10 is —CF═ or —N═, in Formula (9-1), at least one of Z a1 to Z a7 is —CF═ or —N═, in Formula (9-2), at least one of Z a1 to Z a9 is —CF═ or —N═, in Formula (9-3), at least one of Z a1 to Z a9 is —CF═ or —N═, in Formula (9-4), at least one of Z a1 to Z a11 is —CF═ or —N═, in Formula (9-5), at least one of Z a1 to Z a9 is —CF═ or —N═, in Formula (9-6), at least one of Z a1 to Z a11 is —CF═ or —N═, in Formula (9-7), at least one of Z a1 to Z a11 is —CF═ or —N═, in Formula (9-8), at least one of Z a1 to Z a13 is —CF═ or —N═, in Formula (10-1), at least one of Z a1 to Z a5 is —CF═ or —N═, in Formula (10-2), at least one of Z a1 to Z a7 is —CF═ or —N═, in Formula (10-3), at least one of Z a1 to Z a9 is —CF═ or —N═, in Formula (11-1), at least one of Z a1 to Z a7 is —CF═ or —N═.
  16. 16 . The photoelectric conversion element according to claim 15 , wherein the Ar A is a group represented by any of Formula (4-1) to Formula (4-8), Formula (6-1) and Formula (6-2), Formula (7-1) and Formula (7-2), Formula (8-1) and Formula (8-2), Formula (9-1) to Formula (9-8), Formula (10-1) to Formula (10-3), and Formula (11-1).
  17. 17 . The photoelectric conversion element according to claim 15 , wherein the Ar A is a group represented by any of Formula (4-1) to Formula (4-8), Formula (6-1) and Formula (6-2), and Formula (9-1) to Formula (9-8).
  18. 18 . The photoelectric conversion element according to claim 15 , wherein the compound represented by Formula (1A) has a molecular weight of 400 to 900.
  19. 19 . The photoelectric conversion element according to claim 15 , wherein the photoelectric conversion film is a mixture layer formed in a state where the compound represented by Formula (1A) and the coloring agent are mixed.
  20. 20 . The photoelectric conversion element according to claim 1 , further comprising one or more interlayers between the conductive film and the transparent conductive film, in addition to the photoelectric conversion film.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS This application is a Continuation of PCT International Application No. PCT/JP2021/016995 filed on Apr. 28, 2021, which claims priority under 35 U.S.C. § 119(a) to Japanese Patent Application No. 2020-080089 filed on Apr. 30, 2020, Japanese Patent Application No. 2020-113345 filed on Jun. 30, 2020, Japanese Patent Application No. 2020-141929 filed on Aug. 25, 2020, and Japanese Patent Application No. 2021-002864 filed on Jan. 12, 2021. Each of the above applications is hereby expressly incorporated by reference, in its entirety, into the present application. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoelectric conversion element, an imaging element, an optical sensor, and a compound. 2. Description of the Related Art In recent years, the development of an element (for example, an imaging element) having a photoelectric conversion film has been progressing. For example, a predetermined molecule as an active material of an organic image sensor is disclosed in JP2018-510845A. SUMMARY OF THE INVENTION In recent years, along with the demand for improving the performance of imaging elements, optical sensors, and the like, further improvements are required for various characteristics required for photoelectric conversion elements used therein. For example, further improvements for sensitivity (photoelectric conversion efficiency) in the photoelectric conversion elements are required. The present inventors have examined a photoelectric conversion element obtained by using the material disclosed in JP2018-510845A, and have confirmed that there is a room for improving a sensitivity (for example, sensitivity for blue light such as light having a wavelength of 450 nm or light having a wavelength of 480 nm) in such a photoelectric conversion element. In view of the above circumstances, an object of the present invention is to provide a photoelectric conversion element with an excellent sensitivity. Another object of the present invention is to provide an imaging element, an optical sensor, and a compound related to the above photoelectric conversion element. The present inventors have conducted extensive studies on the above-described problems, and as a result, the inventors have found that it is possible to solve the above-described problems by configurations described below and have completed the present invention. [1] A photoelectric conversion element comprising, in the following order: a conductive film; a photoelectric conversion film; and a transparent conductive film, in which the photoelectric conversion film contains a compound represented by Formula 1) and a coloring agent, A-D-A  (1) in Formula (1), D is a group represented by any of Formula (1-1) to Formula (1-15),A is a group represented by any of Formula (3-1) to Formula (3-14),where, two A's present in Formula (1) are each a group having the same structure, in Formula (1-1) to Formula (1-15), * represents a bonding position,X1 represents a sulfur atom, an oxygen atom, a selenium atom, or a tellurium atom,one of Y1 and Y2 represents a sulfur atom, an oxygen atom, a selenium atom, or a tellurium atom, and another one represents —CH═,one of Y3 and Y4 represents a sulfur atom, an oxygen atom, a selenium atom, or a tellurium atom, and another one represents —CH═,one of Y5 and Y6 represents a sulfur atom, an oxygen atom, a selenium atom, or a tellurium atom, and another one represents —CH═,one of Y7 and Y8 represents a sulfur atom, an oxygen atom, a selenium atom, or a tellurium atom, and another one represents —CH═,n1 represents an integer of 3 to 5,n2 represents an integer of 3 to 5,n3 represents an integer of 0 to 2,where, at least one of two n3's present in each of Formula (1-4) to Formula (1-7) represents an integer of 1 or 2,n4 to n21 each independently represent an integer of 0 to 2,Ar in Formula (1-1) and Formula (1-2) is a group represented by Formula (2-3),Ar in Formula (1-4) is a group represented by any of Formula (2-1) to Formula (2-3),Ar in Formula (1-5) to Formula (1-9) and Formula (1-11) to Formula (1-15) is a group represented by any of Formula (2-1) to Formula (2-4), in Formula (2-1) to Formula (2-4), * represents a bonding position,X2 represents a sulfur atom, an oxygen atom, a selenium atom, or a tellurium atom,Z1 represents —CH═ or —N═, where, at least one of two Z1's in Formula (2-3) is —N═,Z4 represents —CH═ or —N═,one or more of —CH═ included in a ring structure in a group represented by D in Formula (1) may be substituted with —CR3═, R3 represents a halogen atom, in Formula (3-1) to Formula (3-14), * represents a bonding position,B1 and B2 each independently represent a sulfur atom, an oxygen atom, ═C(CN)2, or ═C(CN)(CO2R1), R1 represents an alkyl group having 1 or 2 carbon atoms, which may have a halogen atom as a substituent,E represents an aromatic ring, which may have a group selected from the group consisting of a halogen atom, a methyl grou