JP7804664B2 - Photoelectric conversion elements, imaging elements, optical sensors, compounds - Google Patents

Description

The present invention relates to photoelectric conversion elements, imaging elements, optical sensors, and compounds.

In recent years, development of elements (such as image pickup elements) having photoelectric conversion films has progressed.
For example, Patent Document 1 discloses "an organic thin film transistor characterized by containing a compound represented by the following general formula (1-1) or (1-2) in a semiconductor active layer."

International Publication No. 2014/119713

2. Description of the Related Art In recent years, along with the demand for improved performance of image pickup devices, optical sensors, and the like, further improvements in the performance of the photoelectric conversion elements used therein are also being sought.
For example, there is a demand for high photoelectric conversion efficiency and for the ability to achieve stable photoelectric conversion efficiency even when the voltage applied to the photoelectric conversion element fluctuates.
The present inventors have examined photoelectric conversion elements using the compounds disclosed in Patent Document 1, and have confirmed that such photoelectric conversion elements have low photoelectric conversion efficiency and that it is difficult to suppress the dependency of the photoelectric conversion efficiency on the applied voltage.
Hereinafter, the ability to obtain stable photoelectric conversion efficiency even when the voltage applied to the photoelectric conversion element fluctuates is also referred to as excellent suppression of the dependence of photoelectric conversion efficiency on electric field strength.

In view of the above circumstances, an object of the present invention is to provide a photoelectric conversion element that is excellent in photoelectric conversion efficiency and in suppressing the dependence of the photoelectric conversion efficiency on electric field strength.
Another object of the present invention is to provide an imaging element, an optical sensor, and a compound related to the photoelectric conversion element.

After extensive research into the above-mentioned problems, the inventors discovered that the above-mentioned problems could be solved by the following configuration, and thus completed the present invention.

[1]
A photoelectric conversion element having a conductive film, a photoelectric conversion film, and a transparent conductive film in this order,
The photoelectric conversion element, wherein the photoelectric conversion film contains a compound represented by formula (1) described below.
[2]
The photoelectric conversion element according to [1], wherein Ar ¹¹ to Ar ¹⁴ each independently represent a group represented by any one of formulas (2) to (7) described later.
[3]
The photoelectric conversion element according to [1] or [2], wherein Ar ¹⁵ and Ar ¹⁶ each independently represent a group represented by the formula (8) described later, a group represented by the formula (9) described later, a group represented by the formula (11) described later, a group represented by any one of the formulas (13) to (16) described later, and a group represented by any one of the formulas (19) to (23) described later.
[4]
The photoelectric conversion element according to any one of [1] to [3], wherein n11 and n12 represent 1, and n13 to n16 represent 0.
[5]
The photoelectric conversion element according to any one of [1] to [3], wherein n11 to n14 represent 1, and n15 and n16 represent 0.
[6]
The photoelectric conversion element according to any one of [1] to [3], wherein n11 to n16 represent 0.
[7]
The photoelectric conversion element according to any one of [1] to [3], wherein n11, n12, n15, and n16 each represent 1, and n13 and n14 each represent 0.
[8]
The compound represented by the formula (1) is a compound represented by the formula (24) described later, a compound represented by the formula (25) described later, a compound represented by any one of the formulas (28) to (30) described later, a compound represented by the formula (32) described later, a compound represented by any one of the formulas (34) to (37) described later, a compound represented by the formula (39) described later, a compound represented by the formula (40) described later, a compound represented by any one of the formulas (43) to (52) described later, a compound represented by any one of the formulas (57) to (68) described later, [1] to [3], a photoelectric conversion element according to any one of the following.
[9]
X ¹¹ and X ¹⁴ represent a sulfur atom, and X ¹² and X ¹³ represent a nitrogen atom, or
The photoelectric conversion element according to any one of [1] to [8], wherein X ¹² and X ¹³ represent a sulfur atom, and X ¹¹ and X ¹⁴ represent a nitrogen atom.
[10]
The photoelectric conversion element according to any one of [1] to [9], wherein Ar represents a group represented by any one of the formulas (Ar-1) and (Ar-4) to (Ar-6).
[11]
The photoelectric conversion element according to any one of [1] to [10], wherein Ar represents a group represented by either formula (Ar-1) or formula (Ar-4). [12]
The photoelectric conversion element according to any one of [1] to [11], wherein the photoelectric conversion film further contains an n-type semiconductor material.
[13]
The photoelectric conversion element according to [12], wherein the n-type semiconductor material contains a fullerene selected from the group consisting of fullerenes and derivatives thereof.
[14]
The photoelectric conversion element according to any one of [1] to [13], wherein the photoelectric conversion film further contains a p-type semiconductor material.
[15]
The photoelectric conversion element according to any one of [1] to [14], wherein the photoelectric conversion film further contains a dye.
[16]
The photoelectric conversion element according to any one of [1] to [15], further comprising one or more intermediate layers in addition to the photoelectric conversion film between the conductive film and the transparent conductive film.
[17]
An imaging device having the photoelectric conversion element according to any one of [1] to [16].
[18]
An optical sensor having the photoelectric conversion element according to any one of [1] to [16].
[19]
A compound represented by formula (1) described below.
[20]
The compound according to [19], wherein Ar ¹¹ to Ar ¹⁴ each independently represent a group represented by any one of formulas (2) to (7) described below.
[21]
The compound according to [19] or [20], wherein Ar ¹⁵ and Ar ¹⁶ each independently represent a group represented by formula (8) described later, a group represented by formula (9) described later, a group represented by formula (11) described later, a group represented by formulas (13) to (16) described later, and a group represented by any of formulas (19) to (23) described later.
[22]
The compound according to any one of [19] to [21], wherein n11 and n12 represent 1, and n13 to n16 represent 0.
[23]
The compound according to any one of [19] to [21], wherein n11 to n14 represent 1, and n15 and n16 represent 0.
[24]
The compound according to any one of [19] to [21], wherein n11 to n16 represent 0.
[25]
The compound according to any one of [19] to [21], wherein n11, n12, n15, and n16 represent 1, and n13 and n14 represent 0.
[26]
The compound represented by formula (1) is any one of a compound represented by formula (24) described later, a compound represented by formula (25) described later, a compound represented by any one of formulas (28) to (30) described later, a compound represented by formula (32) described later, a compound represented by any one of formulas (34) to (37) described later, a compound represented by formula (39) described later, a compound represented by formula (40) described later, a compound represented by any one of formulas (43) to (52) described later, and a compound represented by any one of formulas (57) to (68) described later. [19] to [21] The compound according to any one of the above.
[27]
X ¹¹ and X ¹⁴ represent a sulfur atom, and X ¹² and X ¹³ represent a nitrogen atom, or
The compound according to any one of [19] to [26], wherein X ¹² and X ¹³ represent a sulfur atom, and X ¹¹ and X ¹⁴ represent a nitrogen atom.
[28]
The compound according to any one of [19] to [27], wherein Ar represents a group represented by any one of the formulas (Ar-1) and (Ar-4) to (Ar-6).
[29]
The compound according to any one of [19] to [28], wherein Ar represents a group represented by either formula (Ar-1) or formula (Ar-4).

According to the present invention, it is possible to provide a photoelectric conversion element that has excellent photoelectric conversion efficiency and excellent suppression of the dependence of the photoelectric conversion efficiency on electric field strength.
Furthermore, according to the present invention, it is possible to provide an imaging element, an optical sensor, and a compound relating to the photoelectric conversion element.

FIG. 2 is a cross-sectional view showing a configuration example of a photoelectric conversion element. FIG. 2 is a cross-sectional view showing a configuration example of a photoelectric conversion element.

The following describes a preferred embodiment of the photoelectric conversion element of the present invention.

In this specification, examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms and chlorine atoms being preferred, and fluorine atoms being more preferred.

In this specification, a monocyclic aromatic ring group is an aromatic ring group having only one aromatic ring as a ring structure. A bicyclic aromatic ring group is an aromatic ring group having a ring formed by condensing two aromatic rings as a ring structure. A tricyclic aromatic ring group is an aromatic ring group having a ring formed by condensing three aromatic rings as a ring structure. A tetracyclic aromatic ring group is an aromatic ring group having a ring formed by condensing four aromatic rings as a ring structure.
The aromatic ring preferably has 5 to 15 ring atoms.
The aromatic ring group may be either an aromatic hydrocarbon ring group or an aromatic heterocyclic group. An aromatic hydrocarbon ring group is a group constituted of an aromatic hydrocarbon ring. An aromatic heterocyclic group is a group containing an aromatic heterocycle and may contain an aromatic hydrocarbon ring.
The number of heteroatoms contained as ring members in the aromatic heterocycle is preferably 1 to 10. Examples of the heteroatom include a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom.
Examples of the ring constituting the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring.
Examples of the ring constituting the aromatic heterocyclic group include a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a triazine ring (for example, a 1,2,3-triazine ring, a 1,2,4-triazine ring, and a 1,3,5-triazine ring), a tetrazine ring (for example, a 1,2,4,5-tetrazine ring), a quinoxaline ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a benzopyrrole ring, a benzofuran ring, a benzothiophene ring, a benzimidazole ring, a benzoxazole ring, a benzothiazole ring, a naphthopyrrole ring, a naphthofuran ring, a naphthothiophene ring, a naphthoimidazole ring, a naphthoxazole ring, a 3H-pyrrolidine ring, a pyrroloimidazole ring (for example, a 5H-pyrrolo[1,2-a]imidazole ring), an imidazooxazole ring (for example, an imidazo[2,1-b]o thienothiazole ring (for example, thieno[2,3-d]thiazole ring), benzothiadiazole ring, benzodithiophene ring (for example, benzo[1,2-b:4,5-b']dithiophene ring), thienothiophene ring (for example, thieno[3,2-b]thiophene ring), thiazolothiazole ring (for example, thiazolo[5,4-d]thiazole ring), naphthodithiophene ring (for example, naphtho [2,3-b:6,7-b']dithiophene ring, naphtho[2,1-b:6,5-b']dithiophene ring, naphtho[1,2-b:5,6-b']dithiophene ring, 1,8-dithiadicyclopenta[b,g]naphthalene ring, etc.), benzothienobenzothiophene ring, dithieno[3,2-b:2',3'-d]thiophene ring, and 3,4,7,8-tetrathiadicyclopenta[a,e]pentalene ring.
In this specification, the monovalent aromatic ring group includes a group obtained by removing one hydrogen atom from the above-mentioned aromatic ring. Specific examples include an aryl group and a heteroaryl group. More specific examples include a group obtained by removing one hydrogen atom from a monocyclic aromatic ring, and a group obtained by removing one hydrogen atom from a bicyclic aromatic ring (bicyclic fused ring).
The divalent aromatic ring group includes a group obtained by removing two hydrogen atoms from the above-mentioned aromatic ring, and specifically includes an arylene group and a heteroarylene group.

In this specification, when a formula showing a chemical structure contains a plurality of identical symbols indicating the type or number of groups, the meanings of the identical symbols present in the plurality of symbols are independent of each other unless otherwise specified. In addition, the meanings of the identical symbols may be the same or different.
In this specification, when a formula showing a chemical structure contains a plurality of groups of the same type (e.g., aromatic ring groups), the specific details of the plurality of groups of the same type are independent of each other unless otherwise specified. In addition, the specific details of the groups of the same type may be the same or different.

In this specification, a numerical range expressed using "~" means a range that includes the numbers written before and after "~" as the lower and upper limits.

In this specification, a hydrogen atom may be either a proton atom (a normal hydrogen atom) or a deuterium atom (e.g., a deuterium atom, etc.).

[Photoelectric conversion element]
The photoelectric conversion element of the present invention is a photoelectric conversion element having a conductive film, a photoelectric conversion film, and a transparent conductive film in this order, and the photoelectric conversion film contains a compound represented by formula (1) (hereinafter also referred to as a “specific compound”).
The mechanism by which the photoelectric conversion element of the present invention having such a configuration can solve the above problems is not entirely clear, but the present inventors speculate as follows.
The specific compound has, as a mother nucleus (a ring structure containing Ar), a group represented by any one of formulas (Ar-1) to (Ar-6) described below, and a nitrogen-containing five-membered ring having aromaticity at both ends. In the case of the mother nucleus, the specific compound has good crystallinity, resulting in good charge transport properties between the specific compounds in the photoelectric conversion film, and good charge transport properties can be maintained even at low voltages. As a result, it is presumed that the photoelectric conversion element of the present invention, in which the photoelectric conversion film contains the specific compound, has excellent suppression of the dependence of photoelectric conversion efficiency on electric field strength. Furthermore, for the same reasons as above, it is presumed that the photoelectric conversion element of the present invention also has excellent photoelectric conversion efficiency (particularly, photoelectric conversion efficiency for light with a wavelength of 550 nm when combined with a dye).
Hereinafter, superiority in at least one of the effects of photoelectric conversion efficiency and suppression of the dependence of photoelectric conversion efficiency on electric field strength will also be referred to as "superior effect of the present invention."

FIG. 1 is a schematic cross-sectional view of one embodiment of the photoelectric conversion element of the present invention.
The photoelectric conversion element 10a shown in Figure 1 has a configuration in which a conductive film (hereinafter also referred to as the "lower electrode") 11 functioning as a lower electrode, an electron blocking film 16A, a photoelectric conversion film 12 containing a specific compound described later, and a transparent conductive film (hereinafter also referred to as the "upper electrode") 15 functioning as an upper electrode are stacked in this order.
Fig. 2 shows an example of the configuration of another photoelectric conversion element. The photoelectric conversion element 10b shown in Fig. 2 has a configuration in which an electron blocking film 16A, a photoelectric conversion film 12, a hole blocking film 16B, and an upper electrode 15 are stacked in this order on a lower electrode 11. Note that the stacking order of the electron blocking film 16A, the photoelectric conversion film 12, and the hole blocking film 16B in Figs. 1 and 2 may be changed as appropriate depending on the application and characteristics.

In the photoelectric conversion element 10 a (or 10 b ), it is preferable that light be incident on the photoelectric conversion film 12 through the upper electrode 15 .
Furthermore, when the photoelectric conversion element 10a (or 10b) is used, a voltage can be applied. In this case, it is preferable that the lower electrode 11 and the upper electrode 15 form a pair of electrodes, and a voltage is applied between this pair of electrodes.
The voltage is preferably 1.0×10 ⁻⁵ to 1.0×10 ⁷ V/cm, and from the standpoint of performance and power consumption, more preferably 1.0×10 ⁻⁴ to 1.0×10 ⁷ V/cm, and even more preferably 1.0×10 ⁻³ to 5.0×10 ⁶ V/cm.
1 and 2, the voltage is preferably applied so that the electron blocking film 16A side serves as the cathode and the photoelectric conversion film 12 side serves as the anode. When the photoelectric conversion element 10a (or 10b) is used as an optical sensor or incorporated into an imaging element, a voltage can be applied in a similar manner.
As will be described in detail later, the photoelectric conversion element 10a (or 10b) can be suitably used as an imaging element.

The following describes in detail the structure of each layer that constitutes the photoelectric conversion element of the present invention.

[Photoelectric conversion film]
The photoelectric conversion film is a film containing a specific compound.
The specific compounds are described in detail below.

<Compound represented by formula (1) (specific compound)>
The specific compound is a compound represented by formula (1).

In formula (1), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. Ar represents a group represented by any of formulas (Ar-1) to (Ar-6). ^Ar11 to ^Ar14 each independently represent a monocyclic, bicyclic, tricyclic, or tetracyclic divalent aromatic ring group. ^Ar15 to ^Ar16 each independently represent a monocyclic, bicyclic, tricyclic, or tetracyclic monovalent aromatic ring group. The monovalent aromatic ring group and the divalent aromatic ring group may have, as a substituent, one or more groups selected from the group consisting of a halogen atom, a cyano group, and a trifluoromethyl group. ^X15 and ^X16 each independently represent an oxygen atom or a sulfur atom. n11 to n16 each independently represent 0 or 1. However, when n11 to n16 each represent 0, Ar ¹⁵ and Ar ¹⁶ each independently represent a monovalent aromatic ring group having two, three or four rings. * represents a bonding position.

One of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
It is preferable that one of X ¹¹ and X ¹² represents a nitrogen atom and the other represents a sulfur atom.
It is preferable that one of X ¹³ and X ¹⁴ represents a nitrogen atom and the other represents a sulfur atom.
It is also preferred that X ¹¹ and X ¹⁴ represent a sulfur atom and X ¹² and X ¹³ represent a nitrogen atom, or that X ¹² and X ¹³ represent a sulfur atom and X ¹¹ and X ¹⁴ represent a nitrogen atom.

Ar represents a group represented by any one of formulas (Ar-1) to (Ar-6).
Ar is preferably a group represented by any one of formulas (Ar-1) and (Ar-4) to (Ar-6), and more preferably a group represented by formula (Ar-1) and formula (Ar-4).

In formulae (Ar-1) to (Ar-6), * represents a bonding position.
X ¹⁷ and X ¹⁸ each independently represent an oxygen atom, a sulfur atom or a selenium atom.
X ¹⁷ and X ¹⁸ are preferably an oxygen atom or a sulfur atom, more preferably a sulfur atom.

Ar ¹¹ to Ar ¹⁴ each independently represent a monocyclic, bicyclic, tricyclic, or tetracyclic divalent aromatic ring group, and Ar ¹⁵ to Ar ¹⁶ each independently represent a monocyclic, bicyclic, tricyclic, or tetracyclic monovalent aromatic ring group.
Ar ¹¹ to Ar ¹⁴ are divalent aromatic ring groups, and Ar ¹⁵ and Ar ¹⁶ are monovalent aromatic ring groups.
It is also preferable that Ar ¹¹ and Ar ¹² are the same aromatic ring group, it is also preferable that Ar ¹³ and Ar ¹⁴ are the same aromatic ring group, and it is also preferable that Ar ¹⁵ and Ar ¹⁶ are the same aromatic ring group.
The expression "each aromatic ring group is the same" means that each aromatic ring group to be compared is the same group, and the positional relationship of each structure constituting those aromatic ring groups (e.g., heteroatoms and substituents that the aromatic ring groups may have) is also the same with respect to the mother nucleus (ring structure including Ar) of the specific compound.

The divalent aromatic ring groups represented by Ar ¹¹ to Ar ¹⁴ and the monovalent aromatic ring groups represented by Ar ¹⁵ to Ar ¹⁶ may have, as a substituent, one or more groups selected from the group consisting of a halogen atom, a cyano group, and a trifluoromethyl group.
The aromatic ring group does not have any substituents other than those selected from the above group. In other words, if the aromatic ring group has a substituent, the substituent is only one or more groups selected from the group consisting of a halogen atom, a cyano group, and a trifluoromethyl group.
The total number of substituents on the divalent aromatic ring groups represented by Ar ¹¹ to Ar ¹⁴ and the monovalent aromatic ring groups represented by Ar ¹⁵ to Ar ¹⁶ is preferably 0 to 5.

The total number of rings of Ar ¹¹ , Ar ¹³ and Ar ¹⁵ and the total number of rings of Ar ¹² , Ar ¹⁴ and Ar ¹⁶ are preferably 1 to 10, more preferably 1 to 5, and even more preferably 3 to 5.
The total number of rings is the sum of the number of aromatic rings contained in each group excluding the mother nucleus (the ring structure containing Ar). Specifically, the total number of rings of Ar ¹¹ , Ar ¹³ , and Ar ¹⁵ is 2 in the case of a compound represented by formula (1-1), and 4 in the case of a compound represented by formula (1-5). Furthermore, the total number of rings of Ar ¹² , Ar ¹⁴ , and Ar ¹⁶ is 2 in the case of a compound represented by formula (1-1), and 4 in the case of a compound represented by formula (1-5).

Ar ¹¹ to Ar ¹⁴ are preferably groups represented by any one of formulas (2) to (7), and more preferably groups represented by formula (2) and groups represented by any one of formulas (4) to (7).

In formulas (2) to (7), ^Y21 to ^Y24 , ^Y31 to ^Y36 , ^Y41 , ^Y42 , ^Y51 to ^Y54 , ^Y61 , ^Y62 , ^Y71 , and ^Y72 each independently represent -CR= or a nitrogen atom. R represents a hydrogen atom, a halogen atom, a cyano group, or a trifluoromethyl group. ^X41 , ^X51 , ^X61 , ^X62 , and ^X71 each independently represent an oxygen atom, a sulfur atom, or a selenium atom. * represents a bonding position.

Y ²¹ to Y ²⁴ , Y ³¹ to Y ³⁶ , Y ⁴¹ , Y ⁴² , Y ⁵¹ to Y ⁵⁴ , Y ⁶¹ , Y ⁶² , Y ⁷¹ and Y ⁷² each independently represent —CR═ or a nitrogen atom.
Y ²¹ to Y ²⁴ are preferably —CR═. It is also preferable that all of Y ²¹ to Y ²⁴ represent the same group.
Y ³¹ to Y ³⁶ are preferably —CR═. It is also preferable that all of Y ³¹ to Y ³⁶ represent the same group.
It is preferred that one of Y ⁴¹ and Y ⁴² represents —CR= and the other represents a nitrogen atom, or that both represent —CR=.
Y ⁵¹ to Y ⁵⁴ are preferably —CR═. It is also preferable that all of Y ⁵¹ to Y ⁵⁴ represent the same group.
Y ⁶¹ and Y ⁶² are preferably —CR═. It is also preferable that all of Y ⁶¹ and Y ⁶² represent the same group.
Y ⁷¹ and Y ⁷² are preferably —CR═. It is also preferable that all of Y ⁷¹ and Y ⁷² represent the same group.

R represents a hydrogen atom, a halogen atom, a cyano group, or a trifluoromethyl group.
R is preferably a hydrogen atom or a fluorine atom.
When a plurality of R's are present, the R's may be the same or different.

X ⁴¹ , X ⁵¹ , X ⁶¹ , X ⁶² and X ⁷¹ each independently represent an oxygen atom, a sulfur atom or a selenium atom.
X ⁴¹ , X ⁵¹ , X ⁶¹ , X ⁶² and X ⁷¹ are preferably ^{an oxygen atom or a sulfur atom, more preferably a sulfur atom. It is also preferable that all of X 61 and} X ⁶² represent ^the same group.

* indicates the bond position.
In each of the formulas (2) to (7), there are two bonding positions (*), and the left bonding position (*) may be bonded to the mother nucleus, or the right bonding position (*) may be bonded to the mother nucleus.

Ar ¹⁵ and Ar ¹⁶ are preferably a group represented by any one of formulas (8) to (23), more preferably a group represented by formula (8), a group represented by formula (9), a group represented by formula (11), a group represented by any one of formulas (13) to (16), and a group represented by any one of formulas (19) to (23), and even more preferably a group represented by formula (8), a group represented by formula (11), a group represented by any one of formulas (14) to (16), and a group represented by any one of formulas (19) to (22).

In formulas (8) to (23), Y ⁸¹ to Y ⁸⁵ , Y ⁹¹ to Y ⁹⁷ , Y ¹⁰¹ to Y ¹⁰³ , Y ¹¹¹ to Y ¹¹⁵ , Y ¹²¹ to Y ¹²³ , Y ¹³¹ to Y ¹³⁷ , Y ¹⁴¹ to Y ¹⁴⁵ , Y ¹⁵¹ to Y ¹⁵⁷ , Y ¹⁶¹ to Y ¹⁶⁷ , Y ¹⁷¹ to Y ¹⁷⁹ , Y ^{181 to} Y ¹⁸⁵ , Y ¹⁹¹ to Y ¹⁹³ , Y ²⁰¹ to Y ²⁰³ , Y ²¹¹ to Y ²¹⁵ , Y 221 to Y ²²⁵ and Y ²³¹ to Y ²³⁹ each independently represent -CR= or a nitrogen atom. R represents a hydrogen atom, a halogen atom, a cyano group, or a trifluoromethyl group. ^X101 , ^X111 , ^X121 , ^X122 , ^X141 , ^X151 , ^X161 , ^X162 , X171, X181, ^{X182, X191 , X201} , ^X211 , ^{X212 ,} and ^X221 each independently represent ^an oxygen atom, a sulfur atom, or a selenium atom. * represents a bonding position.

Y ⁸¹ ~ Y ⁸⁵ , Y ⁹¹ ~ Y ⁹⁷ , Y ¹⁰¹ ~ Y ¹⁰³ , Y ¹¹¹ ~ Y ¹¹⁵ , Y ¹²¹ ~ Y ¹²³ , Y ¹³¹ ~ Y ¹³⁷ , Y ¹⁴¹ ~ Y ¹⁴⁵ , Y ¹⁵¹ ~ Y ¹⁵⁷ , Y ¹⁶¹ ~ Y ¹⁶⁷ , Y ¹⁷¹ to Y ¹⁷⁹ , Y ¹⁸¹ to Y ¹⁸⁵ , Y ¹⁹¹ to Y ¹⁹³ , Y ²⁰¹ to Y ²⁰³ , Y ²¹¹ to Y ²¹⁵ , Y ²²¹ to Y ²²⁵ and Y ²³¹ to Y ²³⁹ each independently represent -CR= or a nitrogen atom.
It is preferred that all of Y ⁸¹ to Y ⁸⁵ represent -CR=, or ^that one of ^{Y 81 to} Y ⁸⁵ represents a nitrogen atom and the remaining four Y ⁸¹ to Y ⁸⁵ represent -CR=.
Y ⁹¹ to Y ⁹⁷ preferably represent -CR=.
Y ¹⁰¹ to Y ¹⁰³ preferably represent -CR=.
Y ¹¹¹ to Y ¹¹⁵ preferably represent -CR=.
Y ¹²¹ to Y ¹²³ preferably represent -CR=.
Y ¹³¹ to Y ¹³⁷ preferably represent -CR=.
Y ¹⁴¹ to Y ¹⁴⁵ preferably represent -CR=.
Y ¹⁵¹ to Y ¹⁵⁷ preferably represent -CR=.
Y ¹⁶¹ to Y ¹⁶⁷ preferably represent -CR=.
Y ¹⁷¹ to Y ¹⁷⁹ preferably represent -CR=.
Y ¹⁸¹ to Y ¹⁸⁵ preferably represent -CR=.
Y ¹⁹¹ to Y ¹⁹³ preferably represent -CR=.
Y ²⁰¹ to Y ²⁰³ preferably represent -CR=.
Y ²¹¹ to Y ²¹⁵ preferably represent -CR=.
Y ²²¹ to Y ²²⁵ preferably represent -CR=.
Y ²³¹ to Y ²³⁹ preferably represent -CR=.

R represents a hydrogen atom, a halogen atom, a cyano group, or a trifluoromethyl group.
R is preferably a hydrogen atom, a fluorine atom or a cyano group, more preferably a hydrogen atom or a fluorine atom.
When a plurality of R's are present, the R's may be the same or different.

X ¹⁰¹ , X ¹¹¹ , X ¹²¹ , X ¹²² , X ¹⁴¹ , X ¹⁵¹ , X ¹⁶¹ , X ¹⁶² , X ¹⁷¹ , X ¹⁸¹ , X ¹⁸² , X ¹⁹¹ and X ²⁰¹ each independently represent an oxygen atom, a sulfur atom or a selenium atom.
^X101 , ^X111 , ^X121 , ^X122 , ^X141 , ^X151 , ^X161 , ^X162 , ^X171 , X181, ^X182 , ^X191 , ^X201 , ^X211 , ^{X212 and X221} are preferably an oxygen atom or a sulfur atom, more preferably a sulfur atom.

X ¹⁵ and X ¹⁶ each independently represent an oxygen atom or a sulfur atom.
X ¹⁵ and X ¹⁶ are preferably oxygen atoms. It is also preferable that all of X ¹⁵ and X ¹⁶ represent the same group.

n11 to n16 each independently represent 0 or 1. However, when n11 to n16 each represent 0, Ar ¹⁵ and Ar ¹⁶ each independently represent a monovalent aromatic ring group having two, three or four rings, and are preferably monovalent aromatic ring groups having three or four rings.
It is preferable that n11 and n12 have the same value, it is preferable that n13 and n14 have the same value, and it is preferable that n15 and n16 have the same value.
When n11 to n16 are 0, the specific compound does not have a group enclosed in parentheses and accompanied by n11 to n16. For example, when n11, n13, and n15 are 0, the ring structure containing Ar in formula (1) is bonded to Ar ¹⁵ via a single bond.

In addition, when a specific compound is applied to formula (1), if there is a specific compound that can be interpreted both as n11 being 1 and n13 being 0 and as n11 being 0 and n13 being 1, the specific compound is interpreted as a compound in formula (1) in which n11 is 1 and n13 is 0.
Similarly, when a specific compound is applied to formula (1), if there is a specific compound that can be interpreted both as n12 being 1 and n14 being 0 and as n12 being 0 and n14 being 1, then that specific compound is interpreted as a compound in formula (1) in which n12 is 1 and n14 is 0.

As the combinations of n11 to n16, the following combinations A to D are preferred.
A: n11 and n12 represent 1, and n13 to n16 represent 0.
B: n11 to n14 represent 1, and n15 and n16 represent 0.
C: n11 to n16 represent 0.
D: n11, n12, n15 and n16 represent 1, and n13 and n14 represent 0.

It is also preferable that Ar ¹¹ to Ar ¹⁶ contain no nitrogen atoms or fluorine atoms.
The phrase "free of nitrogen atoms and fluorine atoms" means that Ar ¹¹ to Ar ¹⁶ do not have nitrogen atoms as ring atoms or as substituents, and do not have fluorine atoms as substituents.

As the specific compound, a compound represented by any one of formulas (24) to (68) is preferred, and a compound represented by formula (24), a compound represented by formula (25), a compound represented by any one of formulas (28) to (30), a compound represented by formula (32), a compound represented by any one of formulas (34) to (37), a compound represented by formula (39), a compound represented by formula (40), a compound represented by any one of formulas (43) to (52), or a compound represented by any one of formulas (57) to (68) is more preferred.

In formulas (24) to (68), Ar represents a group represented by any one of formulas (Ar-1) to (Ar-6). Y ²¹ to Y ²⁴ , Y ³¹ to Y ³⁶ , Y ⁴¹ , Y ⁴² , Y ⁵¹ to Y ⁵⁴ , Y ⁶¹ , Y ⁶² , Y ⁷¹ , Y ⁷² , Y ⁸¹ to Y ⁸⁵ , Y ⁹¹ to Y ⁹⁷ , Y ¹⁰¹ to Y ¹⁰³ , Y ¹¹¹ to Y ¹¹⁵ , Y ¹²¹ to Y ¹²³ , Y ¹³¹ to Y ¹³⁷ , Y ¹⁴¹ to Y ¹⁴⁵ , Y ¹⁵¹ to Y ¹⁵⁷ , Y ¹⁶¹ to Y ¹⁶⁷ , Y ¹⁷¹ to Y ¹⁷⁹ , Y ¹⁸¹ to Y ¹⁸⁵ , Y ¹⁹¹ to Y ¹⁹³ , Y ²⁰¹ to Y ²⁰³ , Y ²¹¹ ~Y X ²¹⁵ and Y ²²¹ to Y ²²⁵ each independently represent -CR= or a nitrogen atom. R represents a hydrogen atom, a halogen atom, a cyano group or a trifluoromethyl group. ^{X 41} , X ⁵¹ , X ⁶¹ , X 62 , X ⁷¹ , X ¹⁰¹ , X ¹¹¹ , X ¹²¹ , X ¹²² , X ¹⁴¹ , X ¹⁵¹ , X ¹⁶¹ , ^{X 162 ,} X ¹⁷¹ , X ¹⁸¹ , X ¹⁸² , X ¹⁹¹ X ²⁰¹ , X ²¹¹ , X ²¹² and X ²²¹ each independently represent an oxygen atom, a sulfur atom or a selenium atom.
The above-mentioned symbols have the same meanings as the symbols that the specific compounds may have, and the preferred embodiments are also the same.
In formula (24), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (25), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (26), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (27), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (28), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (29), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (30), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (31), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (32), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (33), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (34), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (35), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (36), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (37), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (38), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (39), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (40), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (41), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (42), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (43), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (44), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (45), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (46), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (47), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (48), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (49), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (50), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (51), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (52), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (53), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (54), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (55), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (56), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (57), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (58), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (59), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (60), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (61), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (62), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (63), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (64), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (65), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (66), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (67), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (68), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.

Specific compounds include, for example, the following compounds:

In the above formula, R represents one of the following groups. * represents the bonding position.

The molecular weight of the specific compound is preferably 550 or more, more preferably 600 or more, and the upper limit is preferably 1,200 or less, more preferably 1,000 or less.
If the molecular weight is 1200 or less, the deposition temperature does not become high and decomposition of the compound does not occur easily. If the molecular weight is 550 or more, the glass transition point of the deposited film does not become low and the heat resistance of the photoelectric conversion element is improved.

The specific compounds are particularly useful as materials for photoelectric conversion films used in imaging devices, optical sensors, or photovoltaic cells. The specific compounds can also be used as coloring materials, liquid crystal materials, organic semiconductor materials, charge transport materials, pharmaceutical materials, and fluorescent diagnostic materials.

The maximum absorption wavelength of the specific compound is, for example, preferably in the range of 300 to 550 nm, and more preferably in the range of 400 to 550 nm.
The maximum absorption wavelength is a value measured in a solution state (solvent: chloroform) after adjusting the absorption spectrum of the specific compound to a concentration such that the absorbance is 0.5 to 1. However, if the specific compound is not soluble in chloroform, the specific compound is vapor-deposited and the value measured using the specific compound in a film state is regarded as the maximum absorption wavelength of the specific compound.

The maximum absorption wavelength of the photoelectric conversion film is preferably in the range of 300 to 700 nm, and more preferably in the range of 400 to 700 nm.

Specific compounds can be used as p-type semiconductor materials (materials with excellent hole transport properties) and n-type semiconductor materials (materials with excellent electron transport properties).

When the specific compound is used as an n-type semiconductor material, it is preferable that the specific compound satisfy one or more of the following requirements.
Requirement 1: The specific compound has three or more (e.g., 4 to 16) fluorine atoms in the molecule (preferably fluorine atoms present as substituents of groups represented by Ar ¹¹ to Ar ¹⁶ in formula (1)).
Requirement 2: One or more (preferably 2 to 4) of Ar ¹¹ to Ar ¹⁴ is a nitrogen-containing aromatic ring group containing a nitrogen atom as a ring member atom, and the molecule has a total of one or more (e.g., 2 to 16) fluorine atoms or cyano groups (preferably fluorine atoms).
The nitrogen-containing aromatic ring group may be either a monocyclic group or a polycyclic group (for example, a bicyclic, tricyclic, or tetracyclic group).
When a specific compound is used as a p-type semiconductor material, the specific compound is preferably a compound that does not satisfy any of the above requirements.

When a specific compound is used as a p-type semiconductor material, the ionization potential of the specific compound is preferably 5.0 to 6.0 eV.

When the specific compound is used as an n-type semiconductor material, the electron affinity of the specific compound is preferably 3.0 to 4.5 eV.
In this specification, the electron affinity value is the reciprocal (multiplied by minus 1) of the LUMO value obtained by calculation of B3LYP/6-31G(d) using Gaussian '09 (software, manufactured by Gaussian).

The specific compound contained in the photoelectric conversion film may be only the specific compound used as a substantially p-type semiconductor material, or only the specific compound used as a substantially n-type semiconductor material, or it may be both the specific compound used as a p-type semiconductor material and the specific compound used as an n-type semiconductor material.

The phrase "the specific compound contained in the photoelectric conversion film is essentially only the specific compound used as a p-type semiconductor material" means that the content of the specific compound used as a p-type semiconductor material (= film thickness in monolayer equivalent of the specific compound used as a p-type semiconductor material / total film thickness in monolayer equivalent of all specific compounds x 100) relative to all specific compounds contained in the photoelectric conversion film is more than 90% by volume and 100% by volume or less, with 95 to 100% by volume being preferred, and 99 to 100% by volume being more preferred.

The phrase "the specific compound contained in the photoelectric conversion film is essentially only the specific compound used as an n-type semiconductor material" means that the content of the specific compound used as an n-type semiconductor material (= film thickness in monolayer equivalent of the specific compound used as an n-type semiconductor material / total film thickness in monolayer equivalent of all specific compounds x 100) relative to all specific compounds contained in the photoelectric conversion film is more than 90% by volume and 100% by volume or less, with 95 to 100% by volume being preferred, and 99 to 100% by volume being more preferred.

When the specific compound contained in the photoelectric conversion film is both a specific compound used as a p-type semiconductor material and a specific compound used as an n-type semiconductor material, the content ratio of the specific compound used as a p-type semiconductor material to the specific compound used as an n-type semiconductor material in the photoelectric conversion film (= film thickness in monolayer equivalent of the specific compound used as a p-type semiconductor material / film thickness in monolayer equivalent of the specific compound used as an n-type semiconductor material) is preferably 10/90 to 90/10, more preferably 40/60 to 60/40, and even more preferably 47/53 to 53/47.

The photoelectric conversion film may contain only one type of specific compound, or may contain two types, or may contain three or more types.
The photoelectric conversion film containing only one specific compound means that the photoelectric conversion film contains substantially only one specific compound.
The photoelectric conversion film contains substantially only one type of specific compound, which means that the content of the specific compound contained in the largest amount relative to all the specific compounds contained in the photoelectric conversion film (=film thickness of the specific compound contained in the largest amount, in terms of a single layer/total film thickness of the film thicknesses of all the specific compounds, in terms of a single layer × 100) is more than 90 vol% and 100 vol% or less, preferably 95 to 100 vol%, and more preferably 99 to 100 vol%.
In the case where only one type of specific compound is contained, the one type of specific compound may be a specific compound used as a p-type semiconductor material or a specific compound used as an n-type semiconductor material.

The photoelectric conversion film containing two specific compounds means that the photoelectric conversion film contains substantially only two specific compounds.
The photoelectric conversion film contains substantially only two types of specific compounds means that the total content of the two most abundant specific compounds relative to all specific compounds contained in the photoelectric conversion film (=total film thickness of the two most abundant specific compounds in terms of single layer thickness/total film thickness of all specific compounds in terms of single layer thickness × 100) is more than 90 vol% and 100 vol% or less, preferably 95 to 100 vol%, and more preferably 99 to 100 vol%.
When the two types of specific compounds contained in the largest amounts are specific compound A and specific compound B, respectively, the content ratio of specific compound A to specific compound B in the photoelectric conversion film (=film thickness of specific compound A in terms of a single layer/film thickness of specific compound B in terms of a single layer) is preferably 10/90 to 90/10, more preferably 40/60 to 60/40, and still more preferably 47/53 to 53/47.
In the case where only two types of specific compounds are contained, the two specific compounds may both be specific compounds used as p-type semiconductor materials, or both may be specific compounds used as n-type semiconductor materials, or it is also preferable that one is a specific compound used as a p-type semiconductor material and the other is a specific compound used as an n-type semiconductor material.

In terms of the responsiveness of the photoelectric conversion element, the content of the specific compound in the photoelectric conversion film (=film thickness of the specific compound in terms of a single layer/film thickness of the photoelectric conversion film×100) is preferably 15 to 85% by volume.
When the photoelectric conversion element contains only one specific compound, the content of the specific compound in the photoelectric conversion film is more preferably 20 to 60% by volume, and even more preferably 25 to 40% by volume.
When the photoelectric conversion element contains two types of specific compounds, the content of the specific compounds in the photoelectric conversion film is more preferably 40 to 80% by volume, and even more preferably 60 to 75% by volume.

<Pigment>
The photoelectric conversion film preferably contains a dye in addition to the specific compound.
The dye is preferably an organic dye.
Examples of the dyes include cyanine dyes, styryl dyes, hemicyanine dyes, merocyanine dyes (including zeromethine merocyanine (simple merocyanine)), rhodacyanine dyes, allopolar dyes, oxonol dyes, hemioxonol dyes, squarium dyes, croconium dyes, azamethine dyes, coumarin dyes, arylidene dyes, anthraquinone dyes, triphenylmethane dyes, azo dyes, azomethine dyes, metallocene dyes, fluorenone dyes, and fulgide dyes. dyes, perylene dyes, phenazine dyes, phenothiazine dyes, quinone dyes, diphenylmethane dyes, polyene dyes, acridine dyes, acridinone dyes, quinoxaline dyes, diphenylamine dyes, quinophthalone dyes, phenoxazine dyes, phthaloperylene dyes, dioxane dyes, porphyrin dyes, chlorophyll dyes, phthalocyanine dyes, subphthalocyanine dyes, metal complex dyes, and those described in paragraphs [0083] to [0089] of JP-A-2014-082483 the compounds described in paragraphs [0029] to [0033] of JP-A-2009-167348; the compounds described in paragraphs [0197] to [0227] of JP-A-2012-077064; the compounds described in paragraphs [0035] to [0038] of WO-2018-105269; the compounds described in paragraphs [0041] to [0043] of WO-2018-186389; the compounds described in paragraphs [0059] to [0062] of WO-2018-186397; Compounds described in paragraphs [0078] to [0083] of WO2019-009249, compounds described in paragraphs [0054] to [0056] of WO2019-049946, compounds described in paragraphs [0059] to [0063] of WO2019-054327, compounds described in paragraphs [0086] to [0087] of WO2019-098161, and compounds described in paragraphs [0085] to [0114] of WO2020-013246.

The content of the dye in the photoelectric conversion film (=film thickness of the dye in terms of a single layer/film thickness of the photoelectric conversion film×100) is preferably 15 to 85% by volume, more preferably 20 to 60% by volume, and even more preferably 25 to 40% by volume.
The content of the dye relative to the total content of the specific compound and the dye in the photoelectric conversion film (=(film thickness of the dye in terms of a single layer/(film thickness of the specific compound in terms of a single layer+film thickness of the dye in terms of a single layer)×100) is preferably 15 to 75 vol%, more preferably 20 to 65 vol%, and still more preferably 25 to 60 vol%.
The dyes may be used alone or in combination of two or more.

<n-type semiconductor material>
The photoelectric conversion film preferably contains an n-type semiconductor material in addition to the specific compound and the dye.
When the photoelectric conversion film contains a specific compound used as a p-type semiconductor material, it preferably contains an n-type semiconductor material; when the specific compounds contained in the photoelectric conversion film are only the specific compounds used as p-type semiconductor materials, it is more preferable that the photoelectric conversion film contains an n-type semiconductor material; and when the photoelectric conversion film contains only one specific compound and the one specific compound is the specific compound used as a p-type semiconductor material, it is even more preferable that the photoelectric conversion film contains an n-type semiconductor material.
An n-type semiconductor material is an acceptor organic semiconductor material (compound), which refers to an organic compound that has the property of readily accepting electrons.
More specifically, the n-type semiconductor material is preferably an organic compound that has a larger electron affinity than the specific compound when used in contact with the specific compound.
Furthermore, the n-type semiconductor material is preferably an organic compound that has a larger electron affinity than the dye when used in contact with the dye.
The electron affinity of the n-type semiconductor material is preferably 3.0 to 5.0 eV.

N-type semiconductor materials include, for example, fullerenes selected from the group consisting of fullerenes and their derivatives, fused aromatic carbocyclic compounds (e.g., naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, and fluoranthene derivatives), and 5- to 7-membered heterocyclic compounds having one or more atoms selected from the group consisting of nitrogen atoms, oxygen atoms, and sulfur atoms (e.g., pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, pteridine, acridine, phenazine, phenanthroline, tetrazole, and pyrazole). , imidazole, and thiazole); polyarylene compounds; fluorene compounds; cyclopentadiene compounds; silyl compounds; 1,4,5,8-naphthalenetetracarboxylic anhydride; 1,4,5,8-naphthalenetetracarboxylic anhydride imide derivatives, oxadiazole derivatives; anthraquinodimethane derivatives; diphenylquinone derivatives; bathocuproine, bathophenanthroline, and derivatives thereof; triazole compounds; distyrylarylene derivatives; metal complexes having a nitrogen-containing heterocyclic compound as a ligand; silole compounds; and the compounds described in paragraphs [0056] to [0057] of JP-A No. 2006-100767.

Preferably, the n-type semiconductor material comprises fullerenes selected from the group consisting of fullerenes and derivatives thereof.
Examples of fullerenes include fullerene C60, fullerene C70, fullerene C76, fullerene C78, fullerene C80, fullerene C82, fullerene C84, fullerene C90, fullerene C96, fullerene C240, fullerene C540, and mixed fullerenes.
Examples of fullerene derivatives include compounds in which a substituent is added to the above-mentioned fullerene. The substituent is preferably an alkyl group, an aryl group, or a heterocyclic group. Preferred fullerene derivatives are the compounds described in JP-A-2007-123707.

When the photoelectric conversion film contains an n-type semiconductor material, the content of the n-type semiconductor material in the photoelectric conversion film (=film thickness of n-type semiconductor material in terms of a single layer/film thickness of photoelectric conversion film × 100) is preferably 15 to 75 vol%, more preferably 20 to 60 vol%, and still more preferably 25 to 50 vol%.
The n-type semiconductor material may be used alone or in combination of two or more.

Furthermore, when the n-type semiconductor material contains fullerenes, the content of the fullerenes relative to the total content of the n-type semiconductor material (= (film thickness of fullerenes in monolayer equivalent/total film thickness of each n-type semiconductor material in monolayer equivalent) × 100) is preferably 50 to 100 vol %, more preferably 80 to 100 vol %.
The fullerenes may be used alone or in combination of two or more.

The molecular weight of the n-type semiconductor material is preferably 200 to 1200, more preferably 200 to 1000.

It is also preferable that the photoelectric conversion film is substantially composed only of a specific compound, a dye, and an n-type semiconductor material. "The photoelectric conversion film is substantially composed only of a specific compound, a dye, and an n-type semiconductor material" means that the total content of the specific compound, the dye, and the n-type semiconductor material is 95 to 100% by mass of the total mass of the photoelectric conversion film.

<p-type semiconductor material>
The photoelectric conversion film preferably contains a p-type semiconductor material in addition to the specific compound and the dye.
When the photoelectric conversion film contains a specific compound used as an n-type semiconductor material, it preferably contains a p-type semiconductor material; when the specific compounds contained in the photoelectric conversion film are only the specific compounds used as n-type semiconductor materials, it is more preferable that the photoelectric conversion film contains a p-type semiconductor material; and when the photoelectric conversion film contains only one specific compound and the one specific compound is the specific compound used as an n-type semiconductor material, it is even more preferable that the photoelectric conversion film contains a p-type semiconductor material.
The p-type semiconductor material is a donor organic semiconductor material (compound) and refers to an organic compound that has the property of easily donating electrons. Specifically, the p-type semiconductor material is preferably an organic compound that has a better hole transport property than the specific compound in the photoelectric conversion film, and more preferably an organic compound that has a better hole transport property than both the specific compound and the dye.
In this specification, the hole transport property (hole carrier mobility) of a compound can be evaluated, for example, by a time-of-flight method (for example, a time-of-flight method and a TOF method) or by using a field-effect transistor device.
The hole carrier mobility of the p-type semiconductor material is preferably 10 ⁻⁴ cm ² /V·s or more, more preferably 10 ⁻³ cm ² /V·s or more, and even more preferably 10 ⁻² cm ² /V·s or more. The upper limit is preferably 10 cm ² /V·s or less in order to prevent a small amount of current from flowing in the absence of light irradiation.
The p-type semiconductor material preferably has a smaller ionization potential than the specific compound in the photoelectric conversion film, and more preferably has a smaller ionization potential than both the specific compound and the dye.

Examples of p-type semiconductor materials include triarylamine compounds (e.g., N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TPD), 4,4'-bis[N-(naphthyl)-N-phenyl-amino]biphenyl (α-NPD), the compounds described in paragraphs [0128] to [0148] of JP 2011-228614 A, the compounds described in paragraphs [0052] to [0063] of JP 2011-176259 A, the compounds described in paragraphs [0119] to [0158] of JP 2011-225544 A, the compounds described in paragraphs [0044] to [0051] of JP 2015-153910 A, and the compounds described in paragraphs [0086] to [009] of JP 2012-094660 A). 0], etc.), pyrazoline compounds, styrylamine compounds, hydrazone compounds, polysilane compounds, thiophene compounds (for example, thienothiophene derivatives, dibenzothiophene derivatives, benzodithiophene derivatives, dithienothiophene derivatives, [1]benzothieno[3,2-b]thiophene (BTBT) derivatives, thieno[3,2-f:4,5-f']bis[1]benzothiophene (TBBT) derivatives, compounds described in paragraphs [0031] to [0036] of JP 2018-14474 A, compounds described in paragraphs [0043] to [0045] of WO 2016-194630 A, compounds described in paragraphs [0025] to [0037] and [0099] to [0109] of WO 2017-159684 A, the compounds described in paragraphs [0029] to [0034] of JP-A-2017-076766; the compounds described in paragraphs [0015] to [0025] of WO2018-207722; the compounds described in paragraphs [0045] to [0053] of JP-A-2019-54228; and the compounds described in paragraphs [0045] to [0055] of WO2019-058995. compounds described in paragraphs [0063] to [0089] of WO2019-081416, compounds described in paragraphs [0033] to [0036] of JP2019-80052, compounds described in paragraphs [0044] to [0054] of WO2019-054125, and compounds described in paragraphs [0041] to [0046] of WO2019-093188, etc.), cia Examples of the metal complexes having a nitrogen-containing heterocyclic compound as a ligand include amine compounds, oxonol compounds, polyamine compounds, indole compounds, pyrrole compounds, pyrazole compounds, polyarylene compounds, fused aromatic carbocyclic compounds (e.g., naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pentacene derivatives, pyrene derivatives, perylene derivatives, and fluoranthene derivatives), porphyrin compounds, phthalocyanine compounds, triazole compounds, oxadiazole compounds, imidazole compounds, polyarylalkane compounds, pyrazolone compounds, amino-substituted chalcone compounds, oxazole compounds, fluorenone compounds, silazane compounds, and metal complexes having a nitrogen-containing heterocyclic compound as a ligand.

Furthermore, the p-type semiconductor material is preferably a compound represented by any of formulas (p1) to (p6), and more preferably a compound represented by formula (p1).

In formulae (p1) to (p6), two Rs each independently represent a hydrogen atom or a substituent.
Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkylthio group, a (hetero)arylthio group, an alkylamino group, a (hetero)arylamino group, and a (hetero)aryl group. The substituent may further have a substituent. Specifically, the (hetero)aryl group may be an arylaryl group (biaryl group) which may further have a substituent. At least one of the two aryl groups constituting the biaryl group may be a heteroaryl group.
The term "(hetero)aryl group" is a concept that includes both an aryl group and a heteroaryl group. Specifically, a "(hetero)arylthio group" may be either an arylthio group or a heteroarylthio group.
As R, a group represented by R in formula (IX) described in WO 2019-081416 is also preferred.

X and Y each independently represent —CR ² ₂ —, a sulfur atom (—S—), an oxygen atom (—O—), —NR ² — or —SiR ² ₂ —.
^R2 represents a hydrogen atom, an optionally substituted alkyl group (preferably a methyl group or a trifluoromethyl group), an optionally substituted aryl group, or an optionally substituted heteroaryl group. Two or more ^R2s may be the same or different.
Ar represents an aromatic ring group, and is preferably a benzene ring group.
The aromatic ring group may be either a monocyclic group or a polycyclic group (for example, a bicyclic group, a tricyclic group, a tetracyclic group, etc.).

When the photoelectric conversion film contains a p-type semiconductor material, the content of the p-type semiconductor material in the photoelectric conversion film (=film thickness of the p-type semiconductor material in terms of a single layer/film thickness of the photoelectric conversion film × 100) is preferably 15 to 75 vol%, more preferably 20 to 60 vol%, and still more preferably 25 to 50 vol%.
The n-type semiconductor material may be used alone or in combination of two or more.

It is also preferable that the photoelectric conversion film is substantially composed only of a specific compound, a dye, and a p-type semiconductor material. "The photoelectric conversion film is substantially composed only of a specific compound, a dye, and a p-type semiconductor material" means that the total content of the specific compound, the dye, and the p-type semiconductor material is 95 to 100% by mass of the total mass of the photoelectric conversion film.

It is also preferable that the photoelectric conversion film is substantially composed only of a specific compound, a dye, an n-type semiconductor material, and a p-type semiconductor material. "The photoelectric conversion film is substantially composed only of a specific compound, a dye, an n-type semiconductor material, and a p-type semiconductor material" means that the total content of the specific compound, the dye, the n-type semiconductor material, and the p-type semiconductor material is 95 to 100% by mass of the total mass of the photoelectric conversion film.

When the photoelectric conversion film contains a dye, the photoelectric conversion film is preferably a mixed layer formed in a state in which a specific compound and the dye are mixed.
Furthermore, when the photoelectric conversion film contains an n-type semiconductor material and/or a p-type semiconductor material, the photoelectric conversion film is preferably a mixed layer formed in a state in which the specific compound and the n-type semiconductor material and/or the p-type semiconductor material are mixed.
When the photoelectric conversion film contains a dye and an n-type semiconductor material and/or a p-type semiconductor material, the photoelectric conversion film is preferably a mixed layer formed in a state in which the specific compound, the dye, and the n-type semiconductor material and/or the p-type semiconductor material are mixed.
A mixed layer is a layer in which two or more materials are mixed within a single layer.

Photoelectric conversion films containing specific compounds are non-luminescent films and have properties different from those of organic electroluminescent devices (OLEDs: organic light-emitting diodes). A non-luminescent film refers to a film with a luminescent quantum efficiency of 1% or less, preferably 0.5% or less, and more preferably 0.1% or less.

<Film formation method>
As a method for forming the photoelectric conversion film, for example, a dry film formation method can be mentioned.
Examples of dry film formation methods include vapor deposition (e.g., vacuum deposition), sputtering, physical vapor deposition such as ion plating and molecular beam epitaxy (MBE), and chemical vapor deposition (CVD) such as plasma polymerization, with vacuum deposition being preferred. When forming the photoelectric conversion film by vacuum deposition, the manufacturing conditions, such as the degree of vacuum and the deposition temperature, can be set according to conventional methods.

The thickness of the photoelectric conversion film is preferably 10 to 1000 nm, more preferably 50 to 800 nm, even more preferably 50 to 500 nm, and particularly preferably 50 to 400 nm.

[Electrode (conductive film)]
The electrodes (upper electrode (transparent conductive film) 15 and lower electrode (conductive film) 11) are made of a conductive material. Examples of the conductive material include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof.
Since light is incident from the upper electrode 15, the upper electrode 15 is preferably transparent to the light to be detected. Examples of materials constituting the upper electrode 15 include conductive metal oxides such as antimony- or fluorine-doped tin oxide (ATO: Antimony Tin Oxide, or FTO: Fluorine-doped Tin Oxide), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO: Indium Tin Oxide), and indium zinc oxide (IZO); metal thin films such as gold, silver, chromium, and nickel; mixtures or laminates of these metals and conductive metal oxides; organic conductive materials such as polyaniline, polythiophene, and polypyrrole; and carbon materials such as graphene and carbon nanotubes. From the viewpoint of high conductivity and transparency, conductive metal oxides are preferred.

While typically, reducing the thickness of a conductive film below a certain range results in a rapid increase in resistance, in a solid-state imaging device incorporating a photoelectric conversion element according to this embodiment, the sheet resistance can be, for example, 100 to 10,000 Ω/□, allowing for a wide range of film thicknesses. Furthermore, the thinner the upper electrode (transparent conductive film) 15, the less light it absorbs, and generally the higher its light transmittance. Increased light transmittance is desirable because it increases light absorption in the photoelectric conversion film and enhances photoelectric conversion performance. Considering the suppression of leakage current, the increase in the resistance of the thin film, and the increase in transmittance that accompany thinning, the film thickness of the upper electrode 15 is preferably 5 to 100 nm, and more preferably 5 to 20 nm.

Depending on the application, the bottom electrode 11 may be transparent or non-transparent and reflective. Examples of materials that can be used to form the bottom electrode 11 include conductive metal oxides such as antimony- or fluorine-doped tin oxide (ATO or FTO), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); metals such as gold, silver, chromium, nickel, titanium, tungsten, and aluminum, as well as conductive compounds such as oxides or nitrides of these metals (e.g., titanium nitride (TiN)); mixtures or laminates of these metals and conductive metal oxides; organic conductive materials such as polyaniline, polythiophene, and polypyrrole; and carbon materials such as graphene and carbon nanotubes.

The method for forming the electrodes can be appropriately selected depending on the electrode material, and specific examples include wet methods such as printing and coating, physical methods such as vacuum deposition, sputtering and ion plating, and chemical methods such as CVD and plasma CVD.
When the electrode material is ITO, examples of methods include an electron beam method, a sputtering method, a resistance heating vapor deposition method, a chemical reaction method (for example, a sol-gel method), and a method of applying a dispersion of indium tin oxide.

[Charge-blocking film: electron-blocking film, hole-blocking film]
The photoelectric conversion element of the present invention preferably has one or more intermediate layers between the conductive film and the transparent conductive film in addition to the photoelectric conversion film.
The intermediate layer may be, for example, a charge-blocking film. The photoelectric conversion element may have such a film, which improves the properties of the resulting photoelectric conversion element (e.g., photoelectric conversion efficiency, responsiveness, etc.). Examples of the charge-blocking film include an electron-blocking film and a hole-blocking film. Each of these films will be described in detail below.

<Electron blocking film>
The electron blocking film is a donor organic semiconductor material (compound).
The donor organic semiconductor material may also be the p-type organic semiconductor. The p-type organic semiconductor may be used alone or in combination of two or more.

In addition, p-type organic semiconductors used in electron blocking films include, for example, compounds with a lower ionization potential than n-type semiconductor materials, and if this condition is met, the above-mentioned dyes can also be used.

Furthermore, polymeric materials can also be used as the electron blocking film.
Examples of polymeric materials include polymers of phenylene vinylene, fluorene, carbazole, indole, pyrene, pyrrole, picoline, thiophene, acetylene, and diacetylene, and derivatives thereof.

The electron blocking film may be composed of multiple films.
The electron blocking film may be composed of an inorganic material. Generally, inorganic materials have a higher dielectric constant than organic materials, so when an inorganic material is used for the electron blocking film, a higher voltage is applied to the photoelectric conversion film, resulting in higher photoelectric conversion efficiency. Examples of inorganic materials that can be used for the electron blocking film include calcium oxide, chromium oxide, chromium copper oxide, manganese oxide, cobalt oxide, nickel oxide, copper oxide, gallium copper oxide, strontium copper oxide, niobium oxide, molybdenum oxide, indium copper oxide, indium silver oxide, and iridium oxide.

<Hole-blocking film>
The hole-blocking film is an acceptor organic semiconductor material (compound).
As the acceptor organic semiconductor material, the above-mentioned n-type semiconductor material can also be used.

The charge blocking film can be produced by, for example, a dry film-forming method or a wet film-forming method.
Examples of dry film formation methods include vapor deposition and sputtering. Vapor deposition may be either physical vapor deposition (PVD) or chemical vapor deposition (CVD), with physical vapor deposition such as vacuum deposition being preferred. Wet film formation methods include inkjet printing, spray printing, nozzle printing, spin coating, dip coating, casting, die coating, roll coating, bar coating, and gravure coating, with the inkjet printing being preferred from the viewpoint of high-precision patterning.

The thickness of the charge blocking film (electron blocking film and hole blocking film) is preferably 3 to 200 nm, more preferably 5 to 100 nm, and even more preferably 5 to 30 nm.

〔substrate〕
The photoelectric conversion element may further include a substrate.
Examples of the substrate include a semiconductor substrate, a glass substrate, and a plastic substrate.
In the photoelectric conversion element, the position of the substrate is not particularly limited, and typically, a conductive film, a photoelectric conversion film, and a transparent conductive film are laminated in this order on the substrate.

[Sealing layer]
The photoelectric conversion element may further include a sealing layer.
The performance of photoelectric conversion materials can be significantly degraded in the presence of degrading factors such as water molecules, etc. Therefore, the degradation can be prevented by covering and sealing the entire photoelectric conversion film with a sealing layer made of ceramics such as dense metal oxide, metal nitride, or metal nitride oxide, which does not allow water molecules to penetrate, or diamond-like carbon (DLC).
The sealing layer may be made of a material selected and produced in accordance with the description in paragraphs [0210] to [0215] of JP-A-2011-082508.

[Image sensor, optical sensor]
Photoelectric conversion elements are used, for example, as imaging elements.
An imaging element is an element that converts the optical information of an image into an electrical signal, and typically has multiple photoelectric conversion elements arranged in a matrix on the same plane, with each photoelectric conversion element (pixel) converting the optical signal into an electrical signal and outputting the electrical signal pixel by pixel from the imaging element. To this end, each pixel is composed of one or more photoelectric conversion elements and one or more transistors.
The imaging device is mounted on an imaging device of a digital camera, a digital video camera, an electronic endoscope, an imaging module of a mobile phone, or the like.

The photoelectric conversion element of the present invention is also preferably used in an optical sensor having the photoelectric conversion element of the present invention.
The optical sensor may be the photoelectric conversion element alone, or may be a line sensor in which the photoelectric conversion elements are arranged in a straight line, or a two-dimensional sensor in which the photoelectric conversion elements are arranged in a plane.

[Compound]
The present invention also relates to compounds.
The compound of the present invention has the same meaning as the specific compound described above, and the preferred embodiments are also the same.

The present invention will be described in more detail below based on the following examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples.

[Compound]
<Synthesis of Compound (1-3)>
The specific compound (1-3) was synthesized according to the following scheme.

(Synthesis of compound (1-3-3))
Compound (1-3-1) (2.3 mmol), compound (1-3-2) (7.2 mmol), tetrahydrofuran (96 mL), and triethylamine (14.4 mmol) were added to a glass reaction vessel to obtain a mixed solution. After the atmosphere inside the reaction vessel was replaced with nitrogen, the mixed solution was reacted at 80°C for 6 hours. Methanol (96 mL) was added to the mixed solution, and the mixture was reacted under reflux for 1 hour. The precipitate was then collected by filtration and washed with methanol. The obtained solid (filtered residue) was dried under reduced pressure to obtain compound (1-3-3) (2.1 mmol).
The results of the analysis of compound (1-3-3) by ¹ H-NMR (nuclear magnetic resonance) are shown below.
Compound (1-3-3): ¹ H-NMR (DMSO-d ₆ ) δ (ppm) 7.38-7.47 (4H, m), 7.83-8.07 (12H, m), 8.09 (2H, s), 8.18 (2H, s) 8.20 (2H, s), 10.5 (2H, s).

(Synthesis of compound (1-3-4))
Compound (1-3-3) (0.72 mmol), Lawesson's reagent (8.6 mmol), and o-dichlorobenzene (40 mL) were added to a glass reaction vessel to obtain a mixed solution. After the atmosphere inside the reaction vessel was replaced with nitrogen, the mixed solution was reacted at 150°C for 3 hours. The solid in the mixed solution was collected by filtration and washed with methanol. The obtained solid (filtered residue) was dried under reduced pressure to obtain compound (1-3-4) (0.60 mmol).
The results of ¹ H-NMR analysis of compound (1-3-4) are shown below.
Compound (1-3-4): ¹ H-NMR (DMSO-d ₆ ) δ (ppm) 7.36-7.48 (4H, m), 7.83-8.21 (18H, m), 12.1 (2H, s).

(Synthesis of Compound (1-3))
Compound (1-3-4) (0.47 mmol), cesium carbonate (1.9 mmol), and N,N,N-dimethylacetamide (14 mL) were added to a glass reaction vessel to obtain a mixed solution. After the atmosphere inside the reaction vessel was replaced with nitrogen, the mixed solution was reacted at 130°C for 1 hour and then at 140°C for 2 hours. The precipitate deposited in the mixed solution was collected by filtration and washed with methanol. The obtained solid (filtered residue) was suspended in methanol (14 mL), heated under reflux for 30 minutes, and then collected by filtration. The obtained solid (filtered residue) was dried under reduced pressure and purified by sublimation to obtain compound (1-3) (0.27 mmol).
Since compound (1-3) was poorly soluble, its structure was identified by LDI-MS (soft laser desorption ionization mass spectrometry). The results of the identification are shown below.
Compound (1-3): LDI-MS: 657.9 (M ⁺ ).

Other specific compounds and comparative compounds were synthesized by referring to the synthesis method for the above compounds (1-3). Hereinafter, the specific compounds and comparative compounds will be collectively referred to as the evaluation compounds.

[Dye (evaluation dye)]
The dyes shown below were used to prepare photoelectric conversion elements, which will be described later.

[n-type semiconductor material]
A photoelectric conversion element, which will be described later, was fabricated using fullerene C60 as the n-type semiconductor material.

[p-type semiconductor material]
The photoelectric conversion element described below was fabricated using the p-type semiconductor material shown below.

[test]
Tests X, Y, and Z were carried out using the above materials.

[Test X]
<Examples and Comparative Examples: Fabrication of Photoelectric Conversion Element>
Using the obtained compounds, photoelectric conversion elements of each of the examples and comparative examples having the configuration shown in FIG. 2 were fabricated.
The photoelectric conversion element is composed of a lower electrode 11 , an electron blocking film 16 A, a photoelectric conversion film 12 , a hole blocking film 16 B, and an upper electrode 15 .
Specifically, amorphous ITO was formed on a glass substrate by sputtering to form a lower electrode 11 (thickness: 30 nm). Compound (B-1) below was then formed on the lower electrode 11 by vacuum heating deposition to form an electron blocking film 16A (thickness: 30 nm). Furthermore, a p-type semiconductor material, an n-type semiconductor material, and a dye shown in Tables 1 and 2 were vapor-deposited on the electron blocking film 16A in the component ratios shown in Table 1 to form a photoelectric conversion film 12 (thickness: 350 nm) having a bulk heterostructure. Compound (B-2) below was then vapor-deposited on the photoelectric conversion film 12 to form a hole blocking film 16B (thickness: 10 nm). Amorphous ITO was then formed on the hole blocking film 16B by sputtering to form an upper electrode 15 (transparent conductive film) (thickness: 10 nm). An SiO film was formed as a sealing layer on the upper electrode 15 by vacuum deposition, and then an aluminum oxide (Al ₂ O ₃ ) layer was formed thereon by atomic layer chemical vapor deposition (ALCVD), thereby producing a photoelectric conversion element.
The evaluation compound contained in the photoelectric conversion film of the example in Test X exhibits properties as a p-type semiconductor.

<Evaluation of dark current>
The dark current of each of the obtained photoelectric conversion elements was evaluated by the following method.
A voltage was applied to the lower electrode and upper electrode of each photoelectric conversion element to achieve an electric field strength of 2.5 x ¹⁰⁵ V/cm, and the current value in a dark place (dark current) was measured. Next, a voltage was applied to achieve an electric field strength of 5.0 x ¹⁰⁵ V/cm, and the current value in a dark place (dark current) was measured. The relative ratio of the dark currents was calculated using the following formula and evaluated according to the following criteria.
Relative ratio of dark current=(dark current of 5.0×10 ⁵ V/cm)/(dark current of 2.5×10 ⁵ V/cm)
A: The relative ratio of dark current is less than 2.0. B: The relative ratio of dark current is 2.0 or more but less than 2.5. C: The relative ratio of dark current is 2.5 or more but less than 3.0. D: The relative ratio of dark current is 3.0 or more but less than 3.5. E: The relative ratio of dark current is 3.5 or more.

<Evaluation of photoelectric conversion efficiency (quantum efficiency)>
The photoelectric conversion efficiency of each of the obtained photoelectric conversion elements was evaluated by the following method.
A voltage was applied to each photoelectric conversion element to achieve an electric field strength of 2.0 × 10 ⁵ V/cm. Thereafter, light was irradiated from the upper electrode (transparent conductive film) side to evaluate the photoelectric conversion efficiency (external quantum efficiency) at a wavelength of 550 nm. The relative ratio of the integrated values of the photoelectric conversion efficiency was calculated using formula (S) and evaluated according to the following criteria.
Formula (S): Relative ratio of integral value of photoelectric conversion efficiency=(integral value of photoelectric conversion efficiency at a wavelength of 550 nm of the photoelectric conversion element to be evaluated)/(integral value of photoelectric conversion efficiency at a wavelength of 550 nm of the photoelectric conversion element of Example 1-1)
A: The relative ratio of the integral value of the photoelectric conversion efficiency is 1.4 or more. B: The relative ratio of the integral value of the photoelectric conversion efficiency is 1.2 or more and less than 1.4. C: The relative ratio of the integral value of the photoelectric conversion efficiency is 1.0 or more and less than 1.2. D: The relative ratio of the integral value of the photoelectric conversion efficiency is 0.8 or more and less than 1.0. E: The relative ratio of the integral value of the photoelectric conversion efficiency is less than 0.8.

<Evaluation of the dependence of photoelectric conversion efficiency on electric field strength>
The electric field strength dependency of quantum efficiency of each of the obtained photoelectric conversion elements was evaluated by the following method.
A voltage was applied to each photoelectric conversion element to achieve an electric field strength of 1.5×10 ⁵ V/cm, and then light was irradiated from the upper electrode (transparent conductive film) side to evaluate the photoelectric conversion efficiency (external quantum efficiency) at a wavelength of 550 nm.
Furthermore, a voltage was applied to each photoelectric conversion element so as to achieve an electric field strength of 2.0 × 10 ⁵ V/cm, and then light was irradiated from the upper electrode (transparent conductive film) side to evaluate the photoelectric conversion efficiency (external quantum efficiency) at a wavelength of 550 nm.
The photoelectric conversion efficiency ratio was calculated using the integrated value of the photoelectric conversion efficiency at a wavelength of 550 nm measured at each electric field strength according to the following formula, and evaluated according to the following criteria: The higher the photoelectric conversion efficiency ratio, the better the suppression of the electric field strength dependence of the photoelectric conversion efficiency.
Photoelectric conversion efficiency ratio = (integral value of each photoelectric conversion efficiency at a wavelength of 550 nm when a voltage is applied to give an electric field strength of 1.5 × 10 ⁵ V/cm) / (integral value of each photoelectric conversion efficiency at a wavelength of 550 nm when a voltage is applied to give an electric field strength of 2.0 × 10 ⁵ V/cm)
A: Photoelectric conversion efficiency ratio is 0.9 or more B: Photoelectric conversion efficiency ratio is 0.8 or more but less than 0.9 C: Photoelectric conversion efficiency ratio is 0.7 or more but less than 0.8 D: Photoelectric conversion efficiency ratio is less than 0.7

<Results of Test X>
The characteristics of the photoelectric conversion elements of each Example and Comparative Example in Test X, and the results of the tests carried out using the photoelectric conversion elements of each Example or Comparative Example are shown in Tables 1 and 2 below.
In Tables 1 and 2, the symbols indicate the following:
The column "Ar" indicates the formula (any of formulas (Ar-1) to (Ar-6)) to which Ar in each specific compound corresponds.
The column "Ar ¹¹ and Ar ¹³ , or Ar ¹² and Ar ¹⁴ " indicates the formula to which Ar ¹¹ and Ar ¹³ , or Ar ¹² and Ar ¹⁴ , of each specific compound correspond. Note that "2/4" indicates that the compound corresponds to both formula (2) and formula (4).
The column "Ar ¹⁵ and Ar ¹⁶ " indicates the formula (any of formulas (8) to (23)) to which Ar ¹⁵ and Ar ¹⁶ in each specific compound correspond.
The column "Number of rings of Ar ^x " indicates either the total number of rings of Ar ¹¹ , Ar ¹³ and Ar ¹⁵ or the total number of rings of Ar ¹² , Ar ¹⁴ and Ar ¹⁶ .
In the column "Nitrogen atom or fluorine atom in Ar ^X ", when any of the groups represented by Ar ¹¹ to Ar ¹⁶ does not have a nitrogen atom or a fluorine atom, it is marked as "A", and when it has a nitrogen atom or a fluorine atom, it is marked as "B".

From the results shown in Tables 1 and 2, it was confirmed that the photoelectric conversion element of the present invention using the photoelectric conversion film containing the specific compound exhibits excellent effects of the present invention.
It was confirmed that the effects of the present invention are more excellent when the total number of rings of Ar ¹¹ , Ar ¹³ and Ar ¹⁵ and the total number of rings of Ar ¹² , Ar ¹⁴ and Ar ¹⁶ is 3 to 5 (e.g., comparison between Examples 1-1 to 1-9 and Examples 1-14 and 1-15).
When Ar ¹⁵ and Ar ¹⁶ represent any of a group represented by formula (8), a group represented by formula (11), a group represented by formulas (14) to (16), and a group represented by formulas (19) to (22), it has been confirmed that the effects of the present invention are more excellent (e.g., comparison of Example 1-10 with Examples 1-18, 1-19, and 1-64).
It was confirmed that the effects of the present invention are more excellent when Ar ¹¹ to Ar ¹⁴ are a group represented by formula (2) or a group represented by any one of formulas (4) to (7) (e.g., comparison between Examples 1-10, 1-11, and 1-15 and Examples 1-22 to 1-25).
It was confirmed that the effects of the present invention are more excellent when Ar ¹¹ to Ar ¹⁶ do not contain nitrogen atoms or fluorine atoms (comparison between Examples 1-10 to 1-13 and Examples 1-16 and 1-17, etc.).
It was confirmed that when Ar is a group represented by any one of formula (Ar-1) and formula (Ar-4) to formula (Ar-6), the effects of the present invention are more excellent, and when Ar is a group represented by any one of formula (Ar-1) and formula (Ar-4), the effects of the present invention are even more excellent (e.g., comparison of Examples 1-10, 1-11, 1-14, 1-15, 1-56, and 1-57 with Examples 1-68 to 1-79).

[Test Y]
<Examples and Comparative Examples: Fabrication of Photoelectric Conversion Element>
Photoelectric conversion elements of each example and comparative example were produced in the same manner as in Test X, except that fullerene C60 was replaced with the evaluation compounds shown in Table 3 below.
The photoelectric conversion film of the example in Test Y contains two types of evaluation compounds. Each evaluation compound exhibits properties as an n-type semiconductor or a p-type semiconductor.

<Evaluation of dark current>
The dark current of each of the obtained photoelectric conversion elements was evaluated by the following method.
A voltage was applied to the lower and upper electrodes of each photoelectric conversion element to achieve an electric field strength of 2.5 × 10 ⁵ V/cm, and the current value (dark current) in a dark place was measured. As a result, it was confirmed that the dark current in all photoelectric conversion elements was 50 nA/cm ² or less, which is a sufficiently low dark current.

<Evaluation of photoelectric conversion efficiency (quantum efficiency)>
The photoelectric conversion efficiency (quantum efficiency) of each of the obtained photoelectric conversion elements was evaluated in the same manner as in Test X.
However, in Test Y, the following formula was used as formula (S):
Formula (S): Relative ratio of integral value of photoelectric conversion efficiency=(integral value of photoelectric conversion efficiency at a wavelength of 550 nm of the photoelectric conversion element to be evaluated)/(integral value of photoelectric conversion efficiency at a wavelength of 550 nm of the photoelectric conversion element of Example 2-1)

<Evaluation of the dependence of photoelectric conversion efficiency on electric field strength>
In the same manner as in Test X, the electric field strength dependency of the photoelectric conversion efficiency of each of the obtained photoelectric conversion elements was evaluated.

<Results of Test Y>
Table 3 below shows the characteristics of the photoelectric conversion elements of each example and comparative example in Test Y, as well as the results of the tests carried out using the photoelectric conversion elements of each example and comparative example.

From the results shown in Table 3, it was confirmed that the photoelectric conversion element of the present invention has excellent effects of the present invention.
When a specific compound is used as an n-type semiconductor material, it has been confirmed that the effects of the present invention are more excellent when the specific compound satisfies one or more of the following requirements (e.g., comparison between Example 2-2 and Example 2-1):
Requirement 1: The specific compound has three or more fluorine atoms in the molecule.
Requirement 2: At least one of Ar ¹¹ to Ar ¹⁴ is a nitrogen-containing aromatic ring group containing a nitrogen atom as a ring member atom, and has a total of one or more fluorine atoms in the molecule.
When a specific compound is used as an n-type semiconductor material, it has been confirmed that the effects of the present invention are more excellent when Ar represents a group represented by any one of Formula (Ar-1) and Formulas (Ar-4) to (Ar-6) (e.g., comparison between Example 2-2 and Examples 2-24 and 2-25).

[Test Z]
<Examples and Comparative Examples: Fabrication of Photoelectric Conversion Element>
In the same manner as in Test X, photoelectric conversion elements of each of the examples and comparative examples were prepared.
The evaluation compound contained in the photoelectric conversion film of the example in Test Z exhibits properties as an n-type semiconductor.

<Evaluation of dark current>
In the same manner as in Test Y, the dark current of each of the obtained photoelectric conversion elements was evaluated.
As a result, it was confirmed that the dark current was 50 nA/cm ² or less in all photoelectric conversion elements, and that the dark current was sufficiently low.

<Evaluation of photoelectric conversion efficiency (quantum efficiency)>
The photoelectric conversion efficiency (quantum efficiency) of each of the obtained photoelectric conversion elements was evaluated in the same manner as in Test X.
However, in Test Z, the following formula was used as formula (S):
Formula (S): Relative ratio of integral value of photoelectric conversion efficiency=(integral value of photoelectric conversion efficiency at a wavelength of 550 nm of the photoelectric conversion element to be evaluated)/(integral value of photoelectric conversion efficiency at a wavelength of 550 nm of the photoelectric conversion element of Example 3-1)

<Evaluation of the dependence of photoelectric conversion efficiency on electric field strength>
For each of the obtained photoelectric conversion elements, the dependence of the photoelectric conversion efficiency on the electric field strength was evaluated in the same manner as in Test Y.

<Test Z Results>
Table 4 below shows the characteristics of the photoelectric conversion elements of each example and comparative example in Test Z, as well as the results of the tests carried out using the photoelectric conversion elements of each example and comparative example.

From the results shown in Table 4, it was confirmed that the photoelectric conversion element of the present invention has excellent effects of the present invention.
When a specific compound is used as an n-type semiconductor material, it has been confirmed that the effects of the present invention are more excellent when the specific compound satisfies one or more of the following requirements (e.g., comparison between Example 3-2 and Example 3-1):
Requirement 1: The specific compound has three or more fluorine atoms in the molecule.
Requirement 2: At least one of Ar ¹¹ to Ar ¹⁴ is a nitrogen-containing aromatic ring group containing a nitrogen atom as a ring member atom, and has a total of one or more fluorine atoms in the molecule.
When a specific compound is used as an n-type semiconductor material, it has been confirmed that the effects of the present invention are more excellent when Ar represents a group represented by any one of Formula (Ar-1) and Formulas (Ar-4) to (Ar-6) (e.g., comparison between Example 3-2 and Examples 3-24 and 3-25).

10a, 10b Photoelectric conversion element 11 Conductive film (lower electrode)
12 Photoelectric conversion film 15 Transparent conductive film (upper electrode)
16A: Electron blocking film 16B: Hole blocking film

Claims (29)

A photoelectric conversion element having a conductive film, a photoelectric conversion film, and a transparent conductive film in this order,
The photoelectric conversion element, wherein the photoelectric conversion film contains a compound represented by formula (1):
In formula (1), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. Ar represents a group represented by any of formulas (Ar-1) to (Ar-6). ^Ar11 to ^Ar14 each independently represent a monocyclic, bicyclic, tricyclic, or tetracyclic divalent aromatic ring group. ^Ar15 to ^Ar16 each independently represent a monocyclic, bicyclic, tricyclic, or tetracyclic monovalent aromatic ring group. The monovalent aromatic ring group and the divalent aromatic ring group may have, as a substituent, one or more groups selected from the group consisting of a halogen atom, a cyano group, and a trifluoromethyl group. ^X15 and ^X16 each independently represent an oxygen atom or a sulfur atom. n11 to n16 each independently represent 0 or 1. However, when n11 to n16 each represent 0, Ar ¹⁵ and Ar ¹⁶ each independently represent a monovalent aromatic ring group having two, three or four rings. * represents a bonding position.
In formulae (Ar-1) to (Ar-6), * represents a bonding position, and ^{X 17} and X ¹⁸ each independently represent an oxygen atom, a sulfur atom, or a selenium atom. 2. The photoelectric conversion element according to claim 1, wherein Ar ¹¹ to Ar ¹⁴ each independently represent a group represented by any one of formulas (2) to (7).
In formulas (2) to (7), ^Y21 to ^Y24 , ^Y31 to ^Y36 , ^Y41 , ^Y42 , ^Y51 to ^Y54 , ^Y61 , ^Y62 , ^Y71 , and ^Y72 each independently represent -CR= or a nitrogen atom. R represents a hydrogen atom, a halogen atom, a cyano group, or a trifluoromethyl group. ^X41 , ^X51 , ^X61 , ^X62 , and ^X71 each independently represent an oxygen atom, a sulfur atom, or a selenium atom. * represents a bonding position. The Ar ¹⁵ and the Ar ¹⁶ each independently represent a group represented by formula (8), a group represented by formula (9), a group represented by formula (11), a group represented by any one of formulas (13) to (16), and a group represented by any one of formulas (19) to (23). The photoelectric conversion element according to claim 1.
In formulas (8), (9), (11), (13) to (16), and (19) to (23), Y ⁸¹ to Y ⁸⁵ , Y ⁹¹ to Y ⁹⁷ , Y ¹¹¹ to Y ¹¹⁵ , Y ¹³¹ to Y ¹³⁷ , Y ¹⁴¹ to Y ¹⁴⁵ , Y ¹⁵¹ to Y ¹⁵⁷ , Y ¹⁶¹ to Y ¹⁶⁷ , Y ¹⁹¹ to Y ¹⁹³ , Y ²⁰¹ to Y ²⁰³ , Y ²¹¹ to Y ²¹⁵ , Y ²²¹ to Y ²²⁵ , and Y ²³¹ to Y ²³⁹ each independently represent -CR= or a nitrogen atom. R represents a hydrogen atom, a halogen atom, a cyano group, or a trifluoromethyl group. X ¹¹¹ , X ¹⁴¹ , X ¹⁵¹ , X ¹⁶¹ , X ¹⁶² , X ¹⁹¹ , X ²⁰¹ , X ²¹¹ , X ²¹² and X ²²¹ each independently represent an oxygen atom, a sulfur atom or a selenium atom. * represents a bonding position. A photoelectric conversion element as described in claim 1, wherein n11 and n12 represent 1 and n13 to n16 represent 0. A photoelectric conversion element as described in claim 1, wherein n11 to n14 represent 1 and n15 and n16 represent 0. A photoelectric conversion element as described in claim 1, wherein n11 to n16 represent 0. A photoelectric conversion element as described in claim 1, wherein n11, n12, n15 and n16 represent 1, and n13 and n14 represent 0. The compound represented by the formula (1) is a compound represented by the formula (24), a compound represented by the formula (25), a compound represented by any one of the formulas (28) to (30), a compound represented by the formula (32), a compound represented by any one of the formulas (34) to (37), a compound represented by the formula (39), a compound represented by the formula (40), a compound represented by any one of the formulas (43) to (52), or a compound represented by any one of the formulas (57) to (68). The photoelectric conversion element according to claim 1.
In formulas (24), (25), (28) to (30), (32), (34) to (37), (39), (40), (43) to (52), and (57) to (68), * represents a bonding position. Ar represents a group represented by any one of formulas (Ar-1) to (Ar-6). ^Y21 to ^Y24 , ^Y31 to Y36, ^Y41 , ^Y42 , ^{Y51 to Y54} , ^{Y61, Y62 , Y71} , ^Y72 , ^Y81 to Y85, Y91 to ^Y97 , ^Y111 to ^Y115 , ^Y131 to ^Y137 , ^Y141 to ^Y145 , ^Y151 to ^Y157 , ^Y161 to ^Y167 , ^Y191 to ^Y193 , ^{Y201 to Y203 , Y211} to ^Y215 and ^{Y221 to Y225} each independently represent -CR= or a nitrogen atom. ^R represents a hydrogen atom, a halogen atom, ^a cyano group or a trifluoromethyl group. ^X41 , ^X51 , ^X61 , ^X62 , ^X71 , ^X111 , ^X141 , ^X151 , ^X161 , ^X162 , ^X191 , ^X201 , ^X211 , ^X212 and ^X221 each independently represent an oxygen atom, a sulfur atom or a selenium atom.
In formula (24), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (25), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (28), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (29), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (30), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (32), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (34), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (35), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (36), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (37), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (39), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (40), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (43), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (44), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (45), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (46), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (47), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (48), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (49), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (50), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (51), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (52), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (57), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (58), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (59), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (60), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (61), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (62), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (63), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (64), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (65), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (66), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (67), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (68), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. X ¹¹ and X ¹⁴ represent a sulfur atom, and X ¹² and X ¹³ represent a nitrogen atom, or
The photoelectric conversion element according to claim 1 , wherein X ¹² and X ¹³ represent sulfur atoms, and X ¹¹ and X ¹⁴ represent nitrogen atoms. A photoelectric conversion element as described in claim 1, wherein Ar represents a group represented by any one of formulas (Ar-1) and (Ar-4) to (Ar-6). A photoelectric conversion element as described in claim 1, wherein Ar represents a group represented by either formula (Ar-1) or formula (Ar-4). A photoelectric conversion element as described in claim 1, wherein the photoelectric conversion film further contains an n-type semiconductor material. The photoelectric conversion element described in claim 12, wherein the n-type semiconductor material comprises a fullerene selected from the group consisting of fullerenes and derivatives thereof. A photoelectric conversion element as described in claim 1, wherein the photoelectric conversion film further contains a p-type semiconductor material. A photoelectric conversion element as described in claim 1, wherein the photoelectric conversion film further contains a dye. A photoelectric conversion element as described in claim 1, which has one or more intermediate layers in addition to the photoelectric conversion film between the conductive film and the transparent conductive film. An imaging element having a photoelectric conversion element according to any one of claims 1 to 16. An optical sensor having a photoelectric conversion element according to any one of claims 1 to 16. A compound represented by formula (1):
In formula (1), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. Ar represents a group represented by any of formulas (Ar-1) to (Ar-6). ^Ar11 to ^Ar14 each independently represent a monocyclic, bicyclic, tricyclic, or tetracyclic divalent aromatic ring group. ^Ar15 to ^Ar16 each independently represent a monocyclic, bicyclic, tricyclic, or tetracyclic monovalent aromatic ring group. The monovalent aromatic ring group and the divalent aromatic ring group may have, as a substituent, one or more groups selected from the group consisting of a halogen atom, a cyano group, and a trifluoromethyl group. ^X15 and ^X16 each independently represent an oxygen atom or a sulfur atom. n11 to n16 each independently represent 0 or 1. However, when n11 to n16 each represent 0, Ar ¹⁵ and Ar ¹⁶ each independently represent a monovalent aromatic ring group having two, three or four rings. * represents a bonding position.
In formulae (Ar-1) to (Ar-6), * represents a bonding position, and ^{X 17} and X ¹⁸ each independently represent an oxygen atom, a sulfur atom, or a selenium atom. The compound according to claim 19, wherein Ar ¹¹ to Ar ¹⁴ each independently represent a group represented by any one of formulas (2) to (7).
In formulas (2) to (7), ^Y21 to ^Y24 , ^Y31 to ^Y36 , ^Y41 , ^Y42 , ^Y51 to ^Y54 , ^Y61 , ^Y62 , ^Y71 , and ^Y72 each independently represent -CR= or a nitrogen atom. R represents a hydrogen atom, a halogen atom, a cyano group, or a trifluoromethyl group. ^X41 , ^X51 , ^X61 , ^X62 , and ^X71 each independently represent an oxygen atom, a sulfur atom, or a selenium atom. * represents a bonding position. The compound according to claim 19 or 20, wherein Ar ¹⁵ and Ar ¹⁶ each independently represent a group represented by formula (8), a group represented by formula (9), a group represented by formula (11), a group represented by formulas (13) to (16), or a group represented by any of formulas (19) to (23).
In formulas (8), (9), (11), (13) to (16), and (19) to (23), Y ⁸¹ to Y ⁸⁵ , Y ⁹¹ to Y ⁹⁷ , Y ¹¹¹ to Y ¹¹⁵ , Y ¹³¹ to Y ¹³⁷ , Y ¹⁴¹ to Y ¹⁴⁵ , Y ¹⁵¹ to Y ¹⁵⁷ , Y ¹⁶¹ to Y ¹⁶⁷ , Y ¹⁹¹ to Y ¹⁹³ , Y ²⁰¹ to Y ²⁰³ , Y ²¹¹ to Y ²¹⁵ , Y ²²¹ to Y ²²⁵ , and Y ²³¹ to Y ²³⁹ each independently represent -CR= or a nitrogen atom. R represents a hydrogen atom, a halogen atom, a cyano group, or a trifluoromethyl group. X ¹¹¹ , X ¹⁴¹ , X ¹⁵¹ , X ¹⁶¹ , X ¹⁶² , X ¹⁹¹ , X ²⁰¹ , X ²¹¹ , X ²¹² and X ²²¹ each independently represent an oxygen atom, a sulfur atom or a selenium atom. * represents a bonding position. A compound described in claim 19 or 20, wherein n11 and n12 represent 1, and n13 to n16 represent 0. A compound described in claim 19 or 20, wherein n11 to n14 represent 1, and n15 and n16 represent 0. A compound described in claim 19 or 20, wherein n11 to n16 represent 0. A compound described in claim 19 or 20, wherein n11, n12, n15 and n16 represent 1, and n13 and n14 represent 0. The compound according to claim 19 or 20, wherein the compound represented by formula (1) is any one of a compound represented by formula (24), a compound represented by formula (25), a compound represented by any one of formulas (28) to (30), a compound represented by formula (32), a compound represented by any one of formulas (34) to (37), a compound represented by formula (39), a compound represented by formula (40), a compound represented by any one of formulas (43) to (52), and a compound represented by any one of formulas (57) to (68).
In formulas (24), (25), (28) to (30), (32), (34) to (37), (39), (40), (43) to (52), and (57) to (68), * represents a bonding position. Ar represents a group represented by any one of formulas (Ar-1) to (Ar-6). ^Y21 to ^Y24 , ^Y31 to Y36, ^Y41 , ^Y42 , ^{Y51 to Y54} , ^{Y61, Y62 , Y71} , ^Y72 , ^Y81 to Y85, Y91 to ^Y97 , ^Y111 to ^Y115 , ^Y131 to ^Y137 , ^Y141 to ^Y145 , ^Y151 to ^Y157 , ^Y161 to ^Y167 , ^Y191 to ^Y193 , ^{Y201 to Y203 , Y211} to ^Y215 and ^{Y221 to Y225} each independently represent -CR= or a nitrogen atom. ^R represents a hydrogen atom, a halogen atom, ^a cyano group or a trifluoromethyl group. ^X41 , ^X51 , ^X61 , ^X62 , ^X71 , ^X111 , ^X141 , ^X151 , ^X161 , ^X162 , ^X191 , ^X201 , ^X211 , ^X212 and ^X221 each independently represent an oxygen atom, a sulfur atom or a selenium atom.
In formula (24), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (25), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (28), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (29), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (30), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (32), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (34), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (35), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (36), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (37), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (39), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (40), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (43), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (44), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (45), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (46), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (47), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (48), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (49), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (50), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (51), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (52), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (57), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (58), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (59), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (60), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (61), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (62), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (63), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (64), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (65), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (66), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (67), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom.
In formula (68), one of ^X11 and ^X12 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. One of ^X13 and ^X14 represents a nitrogen atom, and the other represents a sulfur atom or a selenium atom. X ¹¹ and X ¹⁴ represent a sulfur atom, and X ¹² and X ¹³ represent a nitrogen atom, or
The compound according to claim 19 or 20, wherein X ¹² and X ¹³ represent a sulfur atom, and X ¹¹ and X ¹⁴ represent a nitrogen atom. A compound described in claim 19 or 20, wherein Ar represents a group represented by any one of formulas (Ar-1) and (Ar-4) to (Ar-6). A compound described in claim 19 or 20, wherein Ar represents a group represented by either formula (Ar-1) or formula (Ar-4).