Granted Patent B2

US 12,628,554 · App. 18/069,969 · Granted May 12, 2026

Inventors: Hiroki Sugiura (Kanagawa, JP); Yasunori Yonekuta (Kanagawa, JP)

Assignee: FUJIFILM Corporation

H10K85/655H10K10/488H10K30/30H10K39/32H10K71/60H10K85/113H10K2102/101

Abstract

Claims (110)

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),

in Formula (1), A 11 represents a divalent conjugate group having a cyclic structure,

R 11 and R 12 each independently represent a hydrogen atom or a monovalent substituent,

T 11 and T 12 each independently represent a group represented by any of Formulae (T1) to (T3),

in Formula (T1), X 11 and X 12 each independently represent-CN, —S(═O) 2 R 13 , —S(═O) R 13 , —C(═O) R 14 , —C(═O) OR 14 , —C(═S) R 14 , —C(═S) OR 14 , —C(═O) SR 14 , —C(═O) N(R 15 ) 2 , —C(═S) N(R 15 ) 2 , or —S(═O) 2 N(R 15 ) 2 , R 13 and R 14 each independently represent a monovalent substituent, R 15 represents a hydrogen atom or a monovalent substituent,

in Formula (T2) and Formula (T3), Z x1 and Z x2 each independently represent >C═O, >C═S, >C═C(CN) 2 , >S(═O) 2 , >S(═O), >C═C[S(═O) 2 R 15 ] 2 , >C═C[S(═O) R 15 ] 2 , >C═C[C(═O) R 15 ] 2 , >C═C[CN][S(═O) 2 R 15 ], >C═C[CN][S(═O) R 15 ], >C═C[CN][C(═O) R 15 ], >C═C[C(═O) R 15 ] [S(═O) 2 R 15 ], or >C═C[C(═O) R 15 ] [S(═O) R 15 ], R 15 represents a monovalent substituent,

in Formula (T2), Cy x1 represents a ring containing at least one carbon atom and a ring-constituting atom in Z x1 , which may have a substituent,

in Formula (T3), Cy x2 represents a ring containing at least three carbon atoms and a ring-constituting atom in Z x2 , which may have a substituent,

in Formula (T3), R x1 and R x2 each independently represent a hydrogen atom or a monovalent substituent,

in Formulae (T1) to (T3), * represents a bonding position,

Q 11 and Q 12 each independently represent a quinoid-type conjugate linking group represented by Formula (Q),

in Formula (Q), Cy x3 represents a 5- to 10-membered ring containing at least one or more double bonds, * represents a bonding position, s represents an integer of 1 to 10,

where, in a case where s Cy x3 's in Formula (Q) are represented as N 1 to N s from one double bond toward the other double bond, Formula (Q) satisfies conditions (A) to (D) as follows:

(A) in a case where s represents 1, Cy x3 of N 1 forms a quinoid structure together with two double bonds bonded to Cy x3 of N 1 ;

(B) in a case where s represents 2, Cy x3 of N 1 and Cy x3 of N 2 are fused with each other, Cy x3 of N 1 forms a quinoid structure together with a double bond bonded to Cy x3 of N 1 and a double bond contained in Cy x3 of N 2 , and Cy x3 of N 2 forms a quinoid structure together with a double bond contained in Cy x3 of N 1 and contributing to the formation of the quinoid structure by Cy x3 of N 1 , and a double bond bonded to Cy x3 of N 2 ;

(C) in a case where s represents an integer of 3 or more, Cy x3 's of N 1 to N s are fused with each other, Cy x3 of N 1 forms a quinoid structure together with a double bond bonded to Cy x3 of N 1 and a double bond contained in Cy x3 of N 2 , in a case where t is an integer of 2 to (s−1), Cy x3 's of N t each form a quinoid structure together with a double bond contained in Cy x3 of N t−1 and contributing to a formation of a quinoid structure by Cy x3 of N t−1 and a double bond contained in Cy x3 of N t+1 , and Cy x3 of N s forms a quinoid structure together with a double bond contained in Cy x3 of N s-1 and contributing to a formation of a quinoid structure by Cy x3 of N s-1 , and a double bond bonded to Cy x3 of N s ; and

(D) Formula (Q) does not contain the following structures,

in Formulae, R represents an organic group, *1 represents a bonding position with T 11 or T 12 , * represents another bonding position, and

n11 and n12 each independently represent an integer of 1 or more,

where the compound represented by Formula (1) does not contain a carboxy group, a sulfonic acid group, and a phosphoric acid group, and salts thereof.

2 . The photoelectric conversion element according to claim 1 , wherein A 11 is a group represented by any of Formula (A 1 ) to Formula (A 2 ),

*—Ar 11 —*  (A1)

in Formula (A 1 ), Ar 11 represents a divalent monocyclic aromatic ring group, which may have a substituent, a divalent conjugate fused ring group, which may have a substituent, or a divalent conjugate group represented by any of Formulae (a21) to (a24), and * represents a bonding position,

*—(Ar 12 - L 11 ) m11 -Ar 13 —*  (A 2 )

in Formula (A 2 ), Ar 12 and Ar 13 each independently represent a divalent monocyclic aromatic ring group, which may have a substituent, a divalent conjugate fused ring group, which may have a substituent, or a divalent conjugate group represented by any of Formulae (a21) to (a24), L 11 represents a single bond or a divalent conjugate linking group, m11 represents an integer of 1 or more, and * represents a bonding position,

in Formulae (a21) to (a24), W 361 , W 362 , W 371 to W 374 , W 381 to W 384 , and W 391 to W 396 each independently represent a sulfur atom, an oxygen atom, a selenium atom, or >NR U , R U represents a hydrogen atom or a monovalent substituent, P 361 , P 362 , P 371 , P 372 , P 381 to P 384 , and P 391 to P 394 each independently represent an oxygen atom, a sulfur atom, ═C(CN) 2 , ═C[S(═O) 2 R 2U ] 2, ═C[S(═O) R 2U ] 2 , ═C[C(═O) R 2U ] 2 , —C[CN][S(═O) 2 R 2U ], —C[CN][S(═O) R 2U ], ═C[CN][C(═O) R 2U ], —C[C(═O) R 2U ] [S(═O) 2 R 2U ], or —C[C(═O) R 2U ] [S(═O) R 2U ], R 2U represents a monovalent substituent, and * represents a bonding position.

3 . The photoelectric conversion element according to claim 1 , wherein Formula (Q) represents any quinoid-type conjugate linking group selected from the group consisting of Formulae (Q1) to (Q11),

in Formula (Q1), W 91 represents a sulfur atom, a selenium atom, or >NR L , in Formulae (Q2) to (Q4), (Q9), and (Q10), W 101 , W 102 , W 111 , W 112 , W 121 , W 161 , W 171 , and W 172 each independently represent a sulfur atom, an oxygen atom, a selenium atom, or >NR L , R L represents a hydrogen atom or a monovalent substituent,

in Formulae (Q1) to (Q3) and Formulae (Q5) to (Q11), Y 91 , Y 92 , Y 101 , Y 102 , Y 111 , Y 112 , Y 131 to Y 134 , Y 141 to Y 146 , Y 151 to Y 158 , Y 401 , Y 402 , Y 161 to Y 164 , Y 171 to Y 174 , and Y 181 to Y 186 each independently represent ═C(R M )— or a nitrogen atom, R M represents a hydrogen atom or a monovalent substituent,

in Formula (Q4), Cy 121 represents an aromatic ring containing at least two carbon atoms, which may have a substituent,

in Formula (Q8), Cy 401 represents an aromatic ring containing at least two carbon atoms, which may have a substituent,

in Formulae (Q3) and (Q11), V 111 and V 181 each independently represent a sulfur atom, an oxygen atom, a selenium atom, >NR 2L , >C(R 2L ) 2 , >Si(R 2L ) 2 , or >Ge(R 2L ) 2 , R 2L represents a hydrogen atom or a monovalent substituent, and

in Formulae (Q1) to (Q11), * represents a bonding position,

where in Formula (Q1), in a case where W 91 represents a sulfur atom, one of Y 91 or Y 92 represents ═CR M , another one represents a nitrogen atom, R M represents a hydrogen atom.

4 . The photoelectric conversion element according to claim 3 ,

wherein Q 11 and Q 12 each independently represent a quinoid-type conjugate linking group represented by any of Formulae (Q1) to (Q5).

5 . The photoelectric conversion element according to claim 1 ,

wherein R 11 and R 12 each independently represent a hydrogen atom or an alkyl group, an aryl group, or a heteroaryl group, which may have a substituent.

6 . The photoelectric conversion element according to claim 1 ,

wherein T 11 and T 12 each independently represent Formula (T1), and X 11 and X 12 each independently represent-CN.

7 . The photoelectric conversion element according to claim 1 ,

wherein T 11 and T 12 each independently represent a group represented by any of Formula (T21), Formula (T22), and Formula (T25),

in Formula (T21), Formula (T22), and Formula (T25), Z 21 , Z 22 , Z 31 , Z 32 , Z 61 , and Z 62 each independently represent >C═O, >C═S, >C═C(CN) 2 , >S(═O) 2 , >S(═O), >C═C[S(═O) 2 R 15 ] 2 , >C═C[S(═O) R 15 ] 2 , >C═C[C(═O) R 15 ] 2 , >C═C[CN][S(═O) 2 R 15 ], >C═C[CN][S(═O) R 15 ], >C═C[CN][C(═O) R 15 ], >C═C[C(═O) R 15 ] [S(═O) 2 R 15 ], or >C═C[C(═O) R 15 ] [S(═O) R 15 ], R 15 represents a monovalent substituent,

in Formula (T21), 1 represents an integer of 0 to 4, in a case where l represents an integer of 2 to 4, a plurality of Y 21 's in Formula (T21) may be the same or different from each other,

in Formula (T21), in a case where l represents 1, Y 21 represents >C(R 16 ) 2 , >C═O, >C═S, an oxygen atom, a sulfur atom, or >NR 17 , in Formula (T21), in a case where 1 represents an integer of 2 to 4, Y 21 represents >C(R 16 ) 2 , ═C(R 16 )—, =N—, >C—O, >C═S, an oxygen atom, a sulfur atom, or >NR 17 , R 16 and R 17 each independently represent a hydrogen atom or a monovalent substituent,

in Formula (T22), m represents an integer of 0 to 2, in a case where m represents 2, a plurality of Y 31 's in Formula (T22) may be the same or different from each other,

in Formula (T22), in a case where m represents 1, Y 31 represents >C(R 16 ) 2 , >C═O, >C═S, an oxygen atom, a sulfur atom, or >NR 17 , in Formula (T22), in a case where m represents 2, Y 31 represents >C(R 16 ) 2 , —C(R 16 )—, =N—, >C—O, >C═S, an oxygen atom, a sulfur atom, or >NR 17 , R 16 and R 17 each independently represent a hydrogen atom or a monovalent substituent,

in Formula (T22), Cy 31 represents an aromatic ring containing at least two or more carbon atoms, which may have a substituent,

in Formula (T25), W 61 and W 62 each independently represent >C(R 18 ) 2 , an oxygen atom, a sulfur atom, or >NR 19 , and R 18 and R 19 each independently represent a hydrogen atom or a monovalent substituent.

8 . The photoelectric conversion element according to claim 1 ,

wherein the photoelectric conversion film satisfies any of A to C,

A: the photoelectric conversion film has a bulk heterostructure formed in a state in which two or more compounds represented by Formula (1) are mixed with each other;

B: the photoelectric conversion film has a bulk heterostructure formed in a state in which the compound represented by Formula (1) and a p-type organic semiconductor are mixed with each other; and

C: the photoelectric conversion film has a bulk heterostructure formed in a state in which the compound represented by Formula (1) and a n-type semiconductor are mixed with each other.

9 . 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.

10 . An imaging element comprising the photoelectric conversion element according to claim 1 .

11 . An optical sensor comprising the photoelectric conversion element according to claim 1 .

12 . A compound represented by Formula (1),

in Formula (1), A 11 represents a divalent conjugate group having a cyclic structure,

R 11 and R 12 each independently represent a hydrogen atom or a monovalent substituent,

T 11 and T 12 each independently represent a group represented by any of Formulae (T1) to (T3),

in Formula (T1), X 11 and X 12 each independently represent-CN, —S(═O) 2 R 13 , —S(═O) R 13 , —C(═O) R 14 , —C(═O) OR 14 , —C(═S) R 14 , —C(═S) OR 14 , —C(═O) SR 14 , —C(═O) N(R 15 ) 2 , —C(═S) N(R 15 ) 2 , or —S(═O) 2 N(R 15 ) 2 , R 13 and R 14 each independently represent a monovalent substituent, R 15 represents a hydrogen atom or a monovalent substituent,

in Formula (T2) and Formula (T3), Z x1 and Z x2 each independently represent >C═O, >C═S, >C═C(CN) 2 , >S(═O) 2 , >S(═O), >C═C[S(═O) 2 R 15 ] 2 , >C═C[S(═O) R 15 ] 2 , >C═C[C(═O) R 15 ] 2 , >C═C[CN][S(═O) 2 R 15 ], >C═C[CN][S(═O) R 15 ], >C═C[CN][C(═O) R 15 ], >C═C[C(═O) R 15 ] [S(═O) 2 R 15 ], or >C═C[C(═O) R 15 ] [S(═O) R 15 ], R 15 represents a monovalent substituent,

in Formula (T2), Cy x1 represents a ring containing at least one carbon atom and a ring-constituting atom in Z x1 , which may have a substituent,

in Formula (T3), Cy x2 represents a ring containing at least three carbon atoms and a ring-constituting atom in Z x2 , which may have a substituent,

in Formula (T3), R x1 and R x2 each independently represent a hydrogen atom or a monovalent substituent,

in Formulae (T1) to (T3), * represents a bonding position,

Q 11 and Q 12 each independently represent a quinoid-type conjugate linking group represented by Formula (Q),

in Formula (Q), Cy x3 represents a 5- to 10-membered ring containing at least one or more double bonds, * represents a bonding position, s represents an integer of 1 to 10,

where, in a case where s Cy x3 's in Formula (Q) are represented as N 1 to Ns numbers from one double bond toward the other double bond, Formula (Q) satisfies conditions (A) to (D) as follows:

(A) in a case where s represents 1, Cy x3 of N 1 forms a quinoid structure together with two double bonds bonded to Cy x3 of N 1 ;

(B) in a case where s represents 2, Cy x3 of N 1 and Cy x3 of N 2 are fused with each other, Cy x3 of N 1 forms a quinoid structure together with a double bond bonded to Cy x3 of N 1 and a double bond contained in Cy x3 of N 2 , Cy x3 of N 2 forms a quinoid structure together with a double bond contained in Cy x3 of N 1 and contributing to the formation of the quinoid structure by Cy x3 of N 1 , and a double bond bonded to Cy x3 of N 2 ;

(C) in a case where s represents an integer of 3 or more, Cy x3 's of N 1 to N s are fused with each other, Cy x3 of N 1 forms a quinoid structure together with a double bond bonded to Cy x3 of N 1 and a double bond contained in Cy x3 of N 2 , in a case where t is an integer of 2 to (s−1), Cy x3 's of N t each form a quinoid structure together with a double bond contained in Cy x3 of N t−1 and contributing to a formation of a quinoid structure by Cy x3 of N t−1 and a double bond contained in Cy x3 of N t+1 , and Cy x3 of N s forms a quinoid structure together with a double bond contained in Cy x3 of N s-1 and contributing to a formation of a quinoid structure by Cy x3 of N s-1 , and a double bond bonded to Cy x3 of N s ; and

(D) Formula (Q) does not contain the following structures,

in Formulae, R represents an organic group, *1 represents a bonding position with T 11 or T 12 , * Represents another bonding position,

n11 and n12 each independently represent an integer of 1 or more, and

where the compound represented by Formula (1) does not contain a carboxy group, a sulfonic acid group, and a phosphoric acid group, and salts thereof.

13 . The compound according to claim 12 , wherein A 11 is a group represented by any of Formula (A 1 ) to Formula (A 2 ),

*—Ar 11 —*  (A1)

in Formula (A1), Ar 11 represents a divalent monocyclic aromatic ring group, which may have a substituent, a divalent conjugate fused ring group, which may have a substituent, or a divalent conjugate group represented by any of Formulae (a21) to (a24), and * represents a bonding position,

*-(Ar 12 - L 11 ) m11 -Ar 13 —*  (A2)

in Formula (A2), Ar 12 and Ar 13 each independently represent a divalent monocyclic aromatic ring group, which may have a substituent, a divalent conjugate fused ring group, which may have a substituent, or a divalent conjugate group represented by any of Formulae (a21) to (a24), L 11 represents a single bond or a divalent conjugate linking group, m11 represents an integer of 1 or more, and * represents a bonding position,

in Formulae (a21) to (a24), W 361 , W 362 , W 371 to W 374 , W 381 to W 384 , and W 391 to W 396 each independently represent a sulfur atom, an oxygen atom, a selenium atom, or >NR U , R U represents a hydrogen atom or a monovalent substituent, P 361 , P 362 , P 371 , P 372 , P 381 to P 384 , and P 391 to P 394 each independently represent an oxygen atom, a sulfur atom, =C(CN) 2 , ═C[S(═O) 2 R 2U ] 2 , ═C[S(═O) R 2U ] 2 , ═C[C(═O) R 2U ] 2 , ═C[CN][S(═O) 2 R 2U ], ═C[CN][S(═O) R 2U ], ═C[CN][C(═O) R 2U ], ═C[C(═O) R 2U ] [S(═O) 2 R 2U ], or ═C[C(═O) R 2U ] [S(═O) R 2U ], R 2U represents a monovalent substituent, and * represents a bonding position.

14 . The compound according to claim 12 , wherein Formula (Q) represents any quinoid-type conjugate linking group selected from the group consisting of Formulae (Q1) to (Q11),

in Formula (Q 1 ), W 91 represents a sulfur atom, a selenium atom, or >NR L , in Formulae (Q 2 ) to (Q 4 ), (Q 9 ), and (Q 10 ), W 101 , W 102 , W 111 , W 112 , W 121 , W 161 , W 171 , and W 172 each independently represent a sulfur atom, an oxygen atom, a selenium atom, or >NR L , R L represents a hydrogen atom or a monovalent substituent,

in Formulae (Q1) to (Q3) and Formulae (Q5) to (Q11), Y 91 , Y 92 , Y 101 , Y 102 , Y 111 , Y 112 , Y 131 to Y 134 , Y 141 to Y 146 , Y 151 to Y 158 , Y 401 , Y 402 , Y 161 to Y 164 , Y 171 to Y 174 , and Y 181 to Y 186 each independently represent ═C(R M )— or a nitrogen atom, R M represents a hydrogen atom or a monovalent substituent,

in Formula (Q4), Cy 121 represents an aromatic ring containing at least two carbon atoms, which may have a substituent,

in Formula (Q8), Cy 401 represents an aromatic ring containing at least two carbon atoms, which may have a substituent,

in Formulae (Q3) and (Q11), V 111 and V 181 each independently represent a sulfur atom, an oxygen atom, a selenium atom, >NR 2L , >C(R 2L ) 2 , >Si(R 2L ) 2 , or >Ge(R 2L ) 2 , R 2L represents a hydrogen atom or a monovalent substituent, and

in Formulae (Q1) to (Q11), * represents a bonding position,

where in Formula (Q1), in a case where W 91 represents a sulfur atom, one of Y 91 or Y 92 represents ═CR M , another one represents a nitrogen atom, R M represents a hydrogen atom.

15 . The compound according to claim 14 ,

wherein Q 11 and Q 12 each independently represent a quinoid-type conjugate linking group represented by any of Formulae (Q1) to (Q5).

16 . The compound according to claim 12 ,

wherein R 11 and R 12 each independently represent a hydrogen atom or an alkyl group, an aryl group, or a heteroaryl group, which may have a substituent.

17 . The compound according to claim 12 ,

wherein T 11 and T 12 each independently represent Formula (T1), and X 11 and X 12 each independently represent-CN.

18 . The compound according to claim 12 ,

wherein T 11 and T 12 each independently represent a group represented by any of Formula (T21), Formula (T22), and Formula (T25),

in Formula (T21), Formula (T22), and Formula (T25), Z 21 , Z 22 , Z 31 , Z 32 , Z 61 , and Z 62 each independently represent >C—O, >C═S, >C═C(CN) 2 , >S(═O) 2 , >S(═O), >C═C[S(═O) 2 R 15 ] 2 , >C═C[S(═O) R 15 ] 2 , >C═C[C(═O) R 15 ] 2 , >C═C[CN][S(═O) 2 R 15 ], >C═C[CN][S(═O) R 15 ], >C═C[CN][C(═O) R 15 ], >C═C[C(═O) R 15 ] [S(═O) 2 R 15 ], or >C═C[C(═O) R 15 ] [S(═O) R 15 ], R 15 represents a monovalent substituent,

in Formula (T21), 1 represents an integer of 0 to 4, in a case where l represents an integer of 2 to 4, a plurality of Y 21 's in Formula (T21) may be the same or different from each other,

in Formula (T21), in a case where l represents 1, Y 21 represents >C(R 16 ) 2 , >C═O, >C═S, an oxygen atom, a sulfur atom, or >NR 17 , in Formula (T21), in a case where l represents an integer of 2 to 4, Y 21 represents >C(R 16 ) 2 , —C(R 16 )—, ═N—, >C═O, >C═S, an oxygen atom, a sulfur atom, or >NR 17 , R 16 and R 17 each independently represent a hydrogen atom or a monovalent substituent,

in Formula (T22), m represents an integer of 0 to 2, in a case where m represents 2, a plurality of Y 31 's in Formula (T22) may be the same or different from each other,

in Formula (T22), in a case where m represents 1, Y 31 represents >C(R 16 ) 2 , >C═O, >C═S, an oxygen atom, a sulfur atom, or >NR 17 , in Formula (T22), in a case where m represents 2, Y 31 represents >C(R 16 ) 2 , =C(R 16 )—, =N—, >C═O, >C═S, an oxygen atom, a sulfur atom, or >NR 17 , R 16 and R 17 each independently represent a hydrogen atom or a monovalent substituent,

in Formula (T22), Cy 31 represents an aromatic ring containing at least two or more carbon atoms, which may have a substituent,

in Formula (T25), W 61 and W 62 each independently represent >C(R 18 ) 2 , an oxygen atom, a sulfur atom, or >NR 19 , and R 18 and R 19 each independently represent a hydrogen atom or a monovalent substituent.

Assignments (1)

Priority Claims (1)

Continuity (2)

References Cited (19)