Photoelectric conversion element

Patent metadata

Field	Value
Publication number	US-11128791-B2
Application number	US-201916523115-A
Country	US
Kind code	B2
Filing date	Jul 26, 2019
Priority date	Feb 7, 2017
Publication date	Sep 21, 2021
Grant date	Sep 21, 2021

Abstract

Provided is a photoelectric conversion element including an anode, a photoelectric conversion layer that contains a first organic semiconductor, a second organic semiconductor, and a third organic semiconductor, and a cathode. As each of the first organic semiconductor, the second organic semiconductor, and the third organic semiconductor, a low-molecular weight organic semiconductor is used. The first organic semiconductor, the second organic semiconductor, and the third organic semiconductor have mass ratios that satisfy the following relationship: the first organic semiconductor≥the second organic semiconductor≥the third organic semiconductor. Further, when a total amount of the first organic semiconductor, the second organic semiconductor, and the third organic semiconductor is 100 mass %, a content of the second organic semiconductor is 6 mass % or more, and a content of the third organic semiconductor is 3 mass % or more.

First claim

What is claimed is:

1. A photoelectric conversion element comprising in this order:
an anode;
a photoelectric conversion layer; and
a cathode,
the photoelectric conversion layer containing a first organic semiconductor, a second organic semiconductor, and a third organic semiconductor,
wherein the first organic semiconductor, the second organic semiconductor, and the third organic semiconductor each comprise a low-molecular weight organic semiconductor,
wherein one of the first organic semiconductor and the second organic semiconductor is a p-type semiconductor, and another is a n-type semiconductor,
wherein the first organic semiconductor, the second organic semiconductor, and the third organic semiconductor have mass ratios that satisfy the following relationship:
the first organic semiconductor≥the second organic semiconductor≥the third organic semiconductor, and
wherein, when a total amount of the first organic semiconductor, the second organic semiconductor, and the third organic semiconductor is 100 mass %, a content of the second organic semiconductor is 6 mass % or more, and a content of the third organic semiconductor is 3 mass % or more, and
wherein, when a solubility parameter of the first organic semiconductor is represented by SP1, a solubility parameter of the second organic semiconductor is represented by SP2, and a solubility parameter of the third organic semiconductor is represented by SP3, the SP1, the SP2, and the SP3 satisfy the following expression (2) and expression (3)
| SP 1− SP 2|>| SP 2− SP 3|  (2)

| SP 1− SP 3|>| SP 2− SP 3|  (3).

2. The photoelectric conversion element according to claim 1 , wherein a ratio of a mass ratio of the third organic semiconductor with respect to a mass ratio of the second organic semiconductor is 0.12 or more.

3. The photoelectric conversion element according to claim 1 , wherein, when the total amount of the first organic semiconductor, the second organic semiconductor, and the third organic semiconductor is 100 mass %, the content of the second organic semiconductor is 10 mass % or more.

4. The photoelectric conversion element according to claim 1 , wherein the first organic semiconductor comprises the n-type semiconductor, and the second organic semiconductor comprises the p-type semiconductor.

5. The photoelectric conversion element according to claim 4 , wherein the third organic semiconductor comprises the p-type semiconductor.

6. The photoelectric conversion element according to claim 1 , wherein the SP1, the SP2, and the SP3 satisfy the following expression (4) to expression (6)
| SP 1− SP 2|≥2.5  (4)

| SP 1− SP 3|≥2.5  (5)

| SP 2− SP 3|≤2.5  (6).

7. The photoelectric conversion element according to claim 1 , wherein the SP2 and the SP3 satisfy the following expression (7)
| SP 2− SP 3|≤1.0  (7).

8. The photoelectric conversion element according to claim 4 , wherein, when an oxidation potential of the second organic semiconductor is represented by Eox2, an oxidation potential of the third organic semiconductor is represented by Eox3, a reduction potential of the first organic semiconductor is represented by Ered1, and a reduction potential of the third organic semiconductor is represented by Ered3, a relationship of each of the potentials satisfies the following expression (11) and expression (12)
Eox 2≤ Eox 3  (11)

Ered 1 ≥Ered 3  (12).

9. The photoelectric conversion element according to claim 1 , wherein, among the first organic semiconductor, the second organic semiconductor, and the third organic semiconductor, the organic semiconductor comprising the p-type semiconductor comprises any one of compounds represented by the following general formulae [1] to [5], a quinacridone derivative, and a 3H-phenoxazin-3-one derivative:

in the general formula [1]:
R 1 represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted amino group, or a cyano group;
“n 1 ”, “n 2 ”, and “n 3 ” each independently represent an integer of from 0 to 4;
X 1 to X 3 each represent any one of a nitrogen atom, a sulfur atom, an oxygen atom, and a carbon atom that may have a substituent;
Ar 1 and Ar 2 are each independently selected from a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, when Ar 1 and Ar 2 are present in a plural number, each of Ar 1 and Ar 2 may be identical or different, and when X 2 or X 3 represents a carbon atom, Ar 1 and Ar 2 may be bonded to each other to form a ring; and
Z 1 represents any one of a halogen atom, a cyano group, a vinyl group substituted with a cyano group, a substituted or unsubstituted heteroaryl group, or substituents represented by the following general formulae [1-1] to [1-9]:

in the general formulae [1-1] to [1-9], R 521 to R 588 are each independently selected from a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted amino group, and a cyano group, and a symbol “*” represents a bonding position with respect to a carbon atom;

in the general formula [2], R 20 to R 29 are each independently selected from a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted amino group, and a cyano group, and among R 20 to R 29 , two adjacent groups may be bonded to each other to form a ring;

in the general formulae [3] to [5]:
M represents a metal atom, and the metal atom may have an oxygen atom or a halogen atom as a substituent; and
L 1 to L 9 each represent a ligand that is coordinated with the metal M, and are each formed of a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, and among L 1 to L 9 , two adjacent ligands may be bonded to each other to form a ring.

10. The photoelectric conversion element according to claim 1 , wherein, of the first organic semiconductor and the second organic semiconductor, the organic semiconductor comprising the n-type semiconductor comprises a fullerene or a fullerene derivative.

11. The photoelectric conversion element according to claim 10 , wherein the fullerene derivative comprises fullerene C60.

12. The photoelectric conversion element according to claim 1 , wherein the first organic semiconductor, the second organic semiconductor, and the third organic semiconductor satisfy the following condition:
when two different photoelectric conversion layers are formed through use of only the first organic semiconductor, the sec

Assignees

• Canon Kk

Inventors

• Takahashi Tetsuo
• Shiobara Satoru
• Kamatani Jun
• Yamada Naoki
• Yamaguchi Tomona
• Ohrui Hiroki
• Iwawaki Hironobu
• Itabashi Masumi
• Nishide Yosuke
• Miyashita Hirokazu
• Kajimoto Norifumi
• Takahira MOE
• Kawata Isao
• Ito Yuto

Classifications

• H04N23/55

  Optical parts specially adapted for electronic image sensors; Mounting thereof · CPC title

• H10K85/322

  comprising boron · CPC title

• H10K30/50

  Photovoltaic [PV] devices · CPC title

• H04N23/66

  Remote control of cameras or camera parts, e.g. by remote control devices · CPC title

• H04N25/76 Primary

  Addressed sensors, e.g. MOS or CMOS sensors · CPC title