TW202041645A - Photoelectric conversion element, imaging element, optical sensor, material for photoelectric conversion element for imaging element, and material for photoelectric conversion element for optical sensor - Google Patents

Abstract

The present invention provides a photoelectric conversion element having excellent photoelectric conversion efficiency and having stable performance even when a photoelectric conversion film is manufactured by vapor deposition using a vapor deposition material continuously supplied to vapor deposition for a long time. In addition, an image sensor, an optical sensor, a photoelectric conversion element material for an image sensor, and a photoelectric conversion element material for an optical sensor are provided. This photoelectric conversion element has a conductive film, a photoelectric conversion film, and a transparent conductive film in this order, wherein the photoelectric conversion film includes a compound represented by formula (1) and an n-type semiconductor material.

Description

Photoelectric conversion element, imaging element, photo sensor, material for photoelectric conversion element for imaging element, material for photoelectric conversion element for photo sensor

The present invention relates to a photoelectric conversion element, an imaging element, a photo sensor, a material for a photoelectric conversion element for an imaging element, and a material for a photoelectric conversion element for a photo sensor.

In recent years, the development of devices with photoelectric conversion films (for example, imaging devices) has been ongoing. For example, Patent Document 1 discloses an organic photoelectric conversion element having a layer containing a predetermined compound.

[Patent Document 1] Japanese Patent No. 543758

In recent years, with the demand for improved performance of imaging elements, light sensors, etc., further improvements have been required for various characteristics required for photoelectric conversion elements used in these. For example, the photoelectric conversion element is required to further improve the photoelectric conversion efficiency. In addition, from the manufacturing requirements, even if the vapor deposition material continuously supplied for the vapor deposition is used for a long time (for example, 5 hours), the photoelectric conversion element requires stable performance (especially, dark current characteristics) to manufacture the photoelectric conversion film. ).

In view of the foregoing facts, the subject of the present invention is to provide a photoelectric conversion element with excellent photoelectric conversion efficiency and stable performance even when a photoelectric conversion film is produced by vapor deposition using a vapor deposition material continuously supplied for vapor deposition for a long time. In addition, the subject of the present invention is to provide an imaging element, a photo sensor, a material for a photoelectric conversion element for an imaging element, and a material for a photoelectric conversion element for a photo sensor.

As a result of intensive research on the above-mentioned problems, the inventors have found that the above-mentioned problems can be solved by the following structure, and 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, wherein the photoelectric conversion film includes a compound represented by the following formula (1) and an n-type semiconductor material. [2] The photoelectric conversion element according to [1], wherein the molecular weight of the compound represented by the formula (1) described later is 500 to 900. [3] The photoelectric conversion element according to [1] or [2], wherein in the formula (1) described later, Y ¹ and Y ² represent CR ^a9 . [4] The photoelectric conversion element according to any one of [1] to [3], wherein in the formula (1) described later, X ¹ represents a sulfur atom or an oxygen atom. [5] The photoelectric conversion element according to any one of [1] to [4], wherein in formula (1) described later, X ¹ represents a sulfur atom. [6] The photoelectric conversion element according to any one of [1] to [5], wherein the compound represented by formula (1) described later is a compound represented by formula (2) described later. [7] The photoelectric conversion element according to any one of [1] to [6], wherein the photoelectric conversion film has a compound in a state where the compound represented by the formula (1) described later is mixed with the n-type semiconductor material Formed body heterogeneous structure. [8] The photoelectric conversion element according to any one of [1] to [7], wherein between the conductive film and the transparent conductive film, in addition to the photoelectric conversion film, there is one or more types of middle layer. [9] The photoelectric conversion element according to any one of [1] to [8], wherein the n-type semiconductor material includes fullerenes selected from the group consisting of fullerenes and derivatives thereof. [10] An imaging element having the photoelectric conversion element described in any one of [1] to [9]. [11] A photo sensor having the photoelectric conversion element described in any one of [1] to [9]. [12] A material for a photoelectric conversion element for an imaging element, which contains a compound represented by formula (1) described later. [13] The material for a photoelectric conversion element for an imaging element as described in [12], wherein the compound represented by the formula (1) described later is a compound represented by the formula (2) described later. [14] A material for a photoelectric conversion element for a light sensor, which contains a compound represented by the formula (1) described later. [15] The material for a photoelectric conversion element for a photo sensor according to [14], wherein the compound represented by the formula (1) described later is a compound represented by the formula (2) described later. [Invention Effect]

According to the present invention, it is possible to provide a photoelectric conversion element with excellent photoelectric conversion efficiency and stable performance even when a photoelectric conversion film is produced by vapor deposition using a vapor deposition material continuously supplied for vapor deposition for a long time. Furthermore, according to the present invention, it is possible to provide an imaging element, a photo sensor, a material for a photoelectric conversion element for an imaging element, and a material for a photoelectric conversion element for a photo sensor.

Hereinafter, preferred embodiments of the photoelectric conversion element of the present invention will be described. In addition, in the present specification, unless otherwise specified, the "substituent" includes groups exemplified by the substituent W described later.

(Substituent W) The substituent W in this specification is described. The substituent W includes, for example, halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), alkyl (including cycloalkyl, bicycloalkyl, and tricyclic alkyl), alkenyl (including cycloalkenyl and Bicycloalkenyl), alkynyl, aryl, heteroaryl (also called heterocyclic group.), cyano, hydroxyl, carboxy, nitro, alkoxy, aryloxy, siloxy, heteroepoxy Group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amine group (including anilino group.), ammonium group, amide group, aminocarbonylamino group, alkoxy Carbonylamino group, aryloxycarbonylamino group, sulfamsulfonylamino group, alkyl or arylsulfonylamino group, mercapto, alkylthio, arylthio, heterocyclic thio, sulfasulfonyl, Alkyl or arylsulfinyl group, alkyl or arylsulfinyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, aminomethanyl group, aryl group or heterocyclic azo group, imidinyl group, Phosphine group, phosphinyl group, phosphinyloxy group, phosphinyl amine group, phosphinyl group, silyl group, hydrazine group, ureido group and boronic acid group (-B(OH) ₂ ). In addition, where possible, each of the aforementioned groups may further have a substituent (for example, one or more groups of the aforementioned groups). For example, an alkyl group which may have a substituent is also included in one form of the substituent W. In addition, when the substituent W has carbon atoms, the number of carbons the substituent W has is, for example, 1-20. The number of atoms other than the hydrogen atom possessed by the substituent W is, for example, 1-30.

In addition, in this specification, unless otherwise specified, the carbon number of the alkyl group is preferably 1-20, more preferably 1-10, and still more preferably 1-6. The alkyl group may be any of linear, branched and cyclic. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-hexyl, and cyclopentyl. In addition, the alkyl group may be, for example, a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group, and may have these cyclic structures as a partial structure. Among the alkyl groups that may have substituents, the substituents that the alkyl groups may have are not particularly limited. Examples include substituent W, aryl (preferably carbon number 6 to 18, more preferably carbon number 6), hetero An aryl group (preferably a carbon number of 5 to 18, more preferably a carbon number of 5 to 6) or a halogen atom (preferably a fluorine atom or a chlorine atom) is preferred.

In addition, in this specification, unless otherwise specified, the alkyl part of the alkoxy group is preferably the above-mentioned alkyl group. The alkyl part of the alkylthio group is preferably the above-mentioned alkyl group. In the alkoxy group which may have a substituent, the substituent which the alkoxy group may have is the same as the substituent in the alkyl group which may have a substituent. In the alkylthio group which may have a substituent, the substituent which the alkylthio group may have may be the same as the substituent in the alkyl group which may have a substituent.

In addition, in this specification, unless otherwise specified, the aryl group preferably has 6 to 18 ring members. The aryl group may be monocyclic or polycyclic. The aryl group is preferably phenyl, naphthyl, anthryl or phenanthryl, and more preferably phenyl. Among the aryl groups that may have substituents, the substituents that the aryl group may have are not particularly limited. For example, substituent W may be mentioned. An alkyl group that may have substituents (preferably carbon number 1-10) is preferred. Methyl is more preferred.

In addition, in this specification, unless otherwise specified, a heteroaryl group is a monocyclic or multiple heteroatoms containing nitrogen atoms, sulfur atoms, oxygen atoms, selenium atoms, tellurium atoms, phosphorus atoms, silicon atoms, and/or boron atoms. The heteroaryl group of the ring structure of the ring is preferred. The number of carbons in the ring member atoms of the heteroaryl group is not particularly limited, and 3-18 is preferred, and 3-5 is more preferred. The number of heteroatoms in the ring member atoms of the heteroaryl group is not particularly limited, and 1-10 is preferable, 1-4 is more preferable, and 1-2 is still more preferable. The number of ring members of the heteroaryl group is not particularly limited, and 5 to 8 are preferred, 5 to 7 are more preferred, and 5 to 6 are further preferred. The above heteroaryl groups include furyl, pyridyl, quinolinyl, isoquinolinyl, acridinyl, phenanthridinyl, pteridinyl group, pyrazinyl group, and quinolinyl group. , Pyrimidinyl, quinazolinyl, pyridazinyl, cinnolinyl, phthalazinyl group, phthalazinyl group, triazolyl, oxazolyl, benzoxazolyl, thiazolyl, benzothiazolyl, imidazolyl, Benzimidazolyl, pyrazolyl, indazolyl, isoazolyl, benzisothiazolyl, isothiazolyl, benzisothiazolyl, ethadiazolyl, thiadiazolyl, triazolyl, tetrazolium Azolyl, benzofuranyl, thienyl, benzothienyl, dibenzofuranyl, dibenzothienyl, pyrrolyl, indolyl, imidazopyridyl, carbazolyl, etc. Among the heteroaryl groups that may have a substituent, the substituents that the heteroaryl group may have are not particularly limited. For example, the substituent W may be mentioned.

In addition, in this specification, the numerical range represented by "-" means the range which includes the numerical value described before and after "-" as the lower limit and the upper limit.

In this specification, the hydrogen atom may be a light hydrogen atom (usual hydrogen atom) or a heavy hydrogen atom (dihydrogen atom, etc.).

The photoelectric conversion element of the present invention has a conductive film, a photoelectric conversion film, and a transparent conductive film in this order. The photoelectric conversion film includes a compound represented by formula (1) (hereinafter, also referred to as "specific compound") and an n-type semiconductor material. Although the mechanism by which the photoelectric conversion element of the present invention can solve the above-mentioned problems by having these structures is not necessarily clear, the inventors of the present invention speculate as follows. That is, it is presumed that the specific compound bonds a plurality of aromatic rings of a predetermined structure on both sides of the heterocyclic ring as the central ring, and therefore can effectively separate charges and improve the photoelectric conversion efficiency. In addition, it is believed that even when the molecular structure is rigid and heated for a long time, it is difficult to generate a reaction between molecules and is difficult to decompose. Therefore, even if the vapor deposition material that is continuously supplied for vapor deposition for a long time is used for vapor deposition to produce photoelectric conversion In the case of the film, the performance of the photoelectric conversion element can also be stabilized (hereinafter also referred to as "the photoelectric conversion film has excellent suitability for continuous vapor deposition"). Hereinafter, the excellent photoelectric conversion efficiency and/or the excellent continuous vapor deposition suitability of the photoelectric conversion film are also simply referred to as "the effect of the present invention is excellent".

Fig. 1 shows a schematic cross-sectional view of an embodiment of the photoelectric conversion element of the present invention. The photoelectric conversion element 10a shown in FIG. 1 has a structure in which the following layers are sequentially stacked: a conductive film that functions as a lower electrode (hereinafter also referred to as a lower electrode) 11; an electron blocking film 16A; including the following The photoelectric conversion film 12 of a specific compound; and a transparent conductive film (hereinafter, also referred to as the upper electrode) 15 that functions as an upper electrode. FIG. 2 shows another configuration example of the 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 sequentially laminated on the lower electrode 11. In addition, 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 can also be appropriately changed according to the use and characteristics.

In the photoelectric conversion element 10a (or 10b), light is preferably incident on the photoelectric conversion film 12 via the upper electrode 15. Furthermore, when the photoelectric conversion element 10a (or 10b) is used, a voltage can be applied. In this case, the lower electrode 11 and the upper electrode 15 constitute a pair of electrodes, and a voltage of 1×10 ^-5 to 1×10 ⁷ V/cm is preferably applied between the pair of electrodes. From the viewpoint of performance and power consumption, the applied voltage is more preferably 1×10 ^-4 to 1×10 ⁷ V/cm, and more preferably 1×10 ^-3 to 5×10 ⁶ V/cm. Regarding the voltage application method, in FIGS. 1 and 2, it is preferable to apply such that the electron blocking film 16A side becomes the cathode and the photoelectric conversion film 12 side becomes the anode. When the photoelectric conversion element 10a (or 10b) is used as a light sensor, when it is assembled in an imaging element, voltage can be applied by the same method. As described in detail in the latter paragraph, the photoelectric conversion element 10a (or 10b) can be preferably used in imaging element applications.

Hereinafter, the form of each layer constituting the photoelectric conversion element of the present invention will be described in detail.

＜Photoelectric conversion film＞ The photoelectric conversion film is a film containing a specific compound. Hereinafter, the specific compound is described in detail.

(Compound (specific compound) represented by formula 1) The specific compound is a compound represented by the following formula (1).

[Chemical formula 1]

In formula (1), Ar ¹ and Ar ⁴ are each independently selected from the group consisting of an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, and a methyl group which may have a substituent. Silyl group, optionally substituted aryl group, optionally substituted heteroaryl group, and halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc. The same applies to the halogen atom described below) One or more aromatic rings which may have substituents. The above-mentioned aromatic ring may be monocyclic or polycyclic. The polycyclic aromatic ring is preferably a condensed ring containing at least any one of a 5-membered ring and a 6-membered ring. The number of rings forming the above fused ring is preferably 2 to 4, more preferably 2 to 3. The above-mentioned aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. Examples of the heteroatom of the aromatic heterocyclic ring 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. The number of heteroatoms in the ring member atoms of the aromatic heterocyclic ring is preferably 1 to 5, and more preferably 1 to 2. The number of ring members of the above aromatic ring is preferably 5-20, more preferably 6-10. Examples of the above-mentioned aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a quinoline ring, a pyridine ring, a pyridine ring, a pyrrole ring, a furan ring, a thiazole ring, a benzothiazole ring, a thiophene ring, and a benzothiazole ring. Thiophene ring, imidazole ring and azole ring. Among them, the above-mentioned aromatic ring is preferably a benzene ring, a naphthalene ring or a benzothiophene ring.

The substituents that the aromatic ring represented by Ar ¹ and Ar ⁴ may have are selected from the group consisting of an alkyl group that may have a substituent, an alkoxy group that may have a substituent, an alkylthio group that may have a substituent, and a substituent that may have a substituent. One or more substituents in the group of silyl group, optionally substituted aryl group, optionally substituted heteroaryl group and halogen atom. Examples of the above-mentioned silyl group include groups represented by -Si(R ^S1 )(R ^S2 )(R ^S3 ). R ^S1 , R ^S2 and R ^S3 each independently represent an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, an optionally substituted aryl group, or an optionally substituted group The heteroaryl.

In formula (1), Ar ² and Ar ³ are each independently selected from the group consisting of an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, and a methyl group which may have a substituent. One or more of the group of a silyl group, an optionally substituted aryl group, and an optionally substituted heteroaryl group is a monocyclic aromatic ring that may have a substituent. The above-mentioned monocyclic aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. Examples of the heteroatom of the aromatic heterocyclic ring 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. The number of heteroatoms in the ring member atoms of the aromatic heterocyclic ring is preferably 1 to 3, and more preferably 1 to 2. The number of ring members of the above-mentioned monocyclic aromatic ring is preferably 5-10, more preferably 5-6. Examples of the monocyclic aromatic ring include a benzene ring, a pyridine ring, a pyrrole ring, a furan ring, a thiazole ring, a thiophene ring, an imidazole ring, and an azole ring. Among them, the above-mentioned monocyclic aromatic ring is preferably a benzene ring or a thiophene ring.

The substituents that the monocyclic aromatic ring represented by Ar ² and Ar ³ may have are selected from the group consisting of an alkyl group that may have a substituent, an alkoxy group that may have a substituent, an alkylthio group that may have a substituent, and Substituent silyl group, optionally substituted aryl group, optionally substituted heteroaryl group, and one or more substituents in the group of halogen atoms. The substituents that the monocyclic aromatic ring represented by Ar ² and Ar ³ may have are, for example, the same as the substituents that the aromatic ring represented by Ar ¹ and Ar ⁴ may have.

In the formula (1), X ¹ represents a sulfur atom, an oxygen atom, a selenium atom, SiR ^a1 R ^a2 or NR ^a3 . R ^a1 to R ^a3 each independently represent a hydrogen atom or a substituent. Among them, from the viewpoint that the effect of the present invention is more excellent, it is preferable that X ¹ is a sulfur atom or an oxygen atom, and a sulfur atom is more preferable.

In formula (1), m1 and m2 each independently represent 0 or 1. From the viewpoint that the effect of the present invention is more excellent, it is preferable that m1 and m2 are 0.

In formula (1), n1 to n4 each independently represent 0 or 1. In addition, the "n2" described along the brackets surrounding L ^{2 and the two} "n2" of "1-n2" described along the brackets surrounding R ^{11 have} the same value. The "n3" described along the brackets surrounding L ³ and the two "n3" of "1-n3" described along the brackets surrounding R ^{12 have} the same value. Among them, it is preferable that n1 and n4 independently represent 0 or 1 respectively. From the viewpoint that the effect of the present invention is more excellent, it is preferable that n2 and n3 are 0.

In formula (1), R ¹ to R ¹² each independently represent an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, an optionally substituted silyl group, An aryl group which may have a substituent, a heteroaryl group which may have a substituent, a halogen atom or a hydrogen atom. Examples of the above-mentioned silyl group include groups represented by -Si(R ^S1 )(R ^S2 )(R ^S3 ). R ^S1 , R ^S2 and R ^S3 each independently represent an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, an optionally substituted aryl group, or an optionally substituted group The heteroaryl. Among them, R ¹ to R ¹² are preferably hydrogen atoms. However, when n2 is 1, R ¹¹ does not exist (in other words, when n2 is 1, "-(R ¹¹ ) _1-n2 "does not exist). When n3 is 1, R ¹² does not exist (in other words, when n3 is 1, "-(R ¹² ) _1-n3 "does not exist).

In formula (1), L ¹ to L ⁴ each independently represent a sulfur atom, an oxygen atom, a selenium atom, SiR ^a4 R ^a5 , NR ^a6 or CR ^a7 R ^a8 , and CR ^a7 R ^a8 is preferred. R ^a4 to R ^a8 each independently represent a hydrogen atom or a substituent. The above-mentioned substituent is preferably an alkyl group, and more preferably a methyl group. However, when n1 represents 0, L ¹ does not exist, and Ar ¹ and Ar ² are only connected by the single bond clearly shown in formula (1). (In other words, when n1 is 0, the "-(L ¹ ) _n1 -" bond does not exist). When n2 represents 0, L ² does not exist, and the monocyclic or polycyclic aromatic ring bonded to R ² and Ar ² are only connected by the single bond shown in formula (1) (in other words, when n2 is 0 Next, the "-(L ² ) _n2 -" bond does not exist). When n3 represents 0, L ³ does not exist, and the monocyclic or polycyclic aromatic ring bonded to R ³ and Ar ³ are only connected by the single bond shown in formula (1) (in other words, when n3 is 0 Next, the "-(L ³ ) _n3 -" bond does not exist). When n4 represents 0, L ⁴ does not exist, and Ar ⁴ and Ar ³ are only connected by the single bond shown in formula (1) (in other words, when n4 is 0, "-(L ⁴ ) _n4 -" key The knot does not exist).

For example, when n1 to n4 all represent 1, the specific compound is a compound represented by the following formula (1a). When n1 and n4 represent 1, and n2 and n3 represent 0, the specific compound is a compound represented by the following formula (1b). When n1 and n4 represent 0 and n2 and n3 represent 1, the specific compound is a compound represented by the following formula (1c). When n1 to n4 all represent 0, the specific compound is a compound represented by the following formula (1d).

[Chemical formula 2]

In formula (1), Y ¹ and Y ² each independently represent a nitrogen atom or CR ^a9 . R ^a9 represents a hydrogen atom or a substituent, and a hydrogen atom is preferred. The above-mentioned substituents are alkyl groups which may have substituents, alkoxy groups which may have substituents, alkylthio groups which may have substituents, silyl groups which may have substituents, aryl groups which may have substituents, and which may have substituents. The heteroaryl group or halogen atom of the group is preferred. Examples of the above-mentioned silyl group include groups represented by -Si(R ^S1 )(R ^S2 )(R ^S3 ). R ^S1 , R ^S2 and R ^S3 each independently represent an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, an optionally substituted aryl group, or an optionally substituted group The heteroaryl. Among them, R ^a9 as a substituent is preferably the above-mentioned alkyl group, and an alkyl group having 1 to 8 carbon atoms is more preferable. When both Y ¹ and Y ² represent CR ^a9 , two ^Ra9 may be bonded to each other to form a ring. The group formed by bonding two ^{Ra9 to} each other is preferably an alkylene group. In the above-mentioned alkylene group, at least one methylene group constituting the alkylene group may be substituted with an oxygen atom (wherein, it is preferable that the oxygen atoms are not adjacent to each other). The carbon number of the above-mentioned alkylene group is preferably 1 to 5, and 2 is more preferable. In addition, in the carbon number of the above-mentioned alkylene group, a methylene group substituted with an oxygen atom is not included in the carbon number. The group formed by bonding two ^{Ra9 to} each other is preferably "-O-(CH ₂ ) _w -O- (w is an integer of 1 to 4)".

The compound represented by the formula (1) can be a benzene ring except that "Ar ² and Ar ³ both represent an unsubstituted benzene ring, and Ar ¹ and Ar ⁴ both represent an unsubstituted benzene ring or a benzene ring having only a fluorine atom as a substituent , X ¹ represents a sulfur atom, m1 and m2 both represent 0, Y ¹ and Y ² both represent CH, R ² , R ³ , R ⁶ , R ⁷ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² all represent hydrogen atoms , And n1 to n4 all represent compounds other than the 0 compound.

(Compound represented by formula (2)) It is more preferable that the specific compound is a compound represented by formula (2).

[Chemical formula 3]

In formula (2), Ar ¹ to Ar ⁴ , n1, n4, R ² , R ³ , R ⁶ , R ⁷ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , L ¹ and L ^{4 have} the same meanings as those of the formula (1) The meanings of the groups represented by the same symbols are the same. In formula (2), R ¹³ and R ¹⁴ each independently represent an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, an optionally substituted silyl group, An aryl group which may have a substituent, a heteroaryl group which may have a substituent, a halogen atom or a hydrogen atom. Examples of the above-mentioned silyl group include groups represented by -Si(R ^S1 )(R ^S2 )(R ^S3 ). R ^S1 , R ^S2 and R ^S3 each independently represent an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, an optionally substituted aryl group, or an optionally substituted group The heteroaryl. Among them, R ¹³ and R ¹⁴ are each independently the above-mentioned alkyl group or a hydrogen atom, preferably, a hydrogen atom is more preferable. In addition, R ¹³ and R ¹⁴ may be bonded to each other to form a ring. The group formed by R ¹³ and R ¹⁴ bonded to each other is preferably an alkylene group. In the above-mentioned alkylene group, at least one methylene group constituting the alkylene group may be substituted with an oxygen atom (wherein, it is preferable that the oxygen atoms are not adjacent to each other). The carbon number of the above-mentioned alkylene group is preferably 1 to 5, and 2 is more preferable. In addition, in the carbon number of the above-mentioned alkylene group, a methylene group substituted with an oxygen atom is not included in the carbon number. The group formed by bonding R ¹³ and R ^{14 to} each other is preferably "-O-(CH ₂ ) _w -O- (w is an integer of 1 to 4)".

The compound represented by the formula (2) may be a benzene ring except that "Ar ² and Ar ³ both represent an unsubstituted benzene ring, and Ar ¹ and Ar ⁴ both represent an unsubstituted benzene ring or a benzene ring having only a fluorine atom as a substituent , R ² , R ³ , R ⁶ , R ⁷ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ all represent a hydrogen atom, and n1 and n4 all represent compounds other than 0.

Below, specific compounds are exemplified.

[Chemical formula 4]

[Chemical formula 5]

[Chemical formula 6]

[Chemical formula 7]

The molecular weight of the specific compound is not particularly limited, and 500-1200 is preferred, and 500-900 is more preferred. If the molecular weight is 900 or less, the vapor deposition temperature will not increase, and the compound will not easily decompose. If the molecular weight is 500 or more, the glass transition temperature of the vapor-deposited film does not decrease, and the heat resistance of the photoelectric conversion element is improved. A specific compound may be used individually by 1 type, and may use 2 or more types.

The specific compound is particularly useful as a material of a photoelectric conversion film used in an imaging element or a photo sensor. In addition, specific compounds can also be used as coloring materials, liquid crystal materials, organic semiconductor materials, charge transport materials, medical materials, and fluorescent light diagnostic materials.

From the viewpoint of energy level matching with the n-type semiconductor material described later, the specific compound is preferably a compound having a free potential in a single film of -5.0 to -6.0 eV.

The maximum absorption wavelength of a specific compound is not particularly limited, and for example, it is preferably in the range of 300 to 500 nm. In addition, the above-mentioned absorption maximum wavelength is a value measured in a solution state (solvent: chloroform) after adjusting the absorption spectrum of the specific compound to a concentration where the absorbance becomes about 0.5 to 1.

The maximum absorption wavelength of the photoelectric conversion film is not particularly limited, and for example, it is preferably in the range of 300 to 700 nm.

＜n-type semiconductor material＞ The photoelectric conversion film contains an n-type semiconductor material as a component other than the above-mentioned specific compound. The n-type semiconductor material is an acceptor organic semiconductor material (compound), which refers to an organic compound that can easily accept electrons. More specifically, the n-type semiconductor material refers to an organic compound that has a greater electron affinity than the specific compound when used in contact with the specific compound. In this manual, as the value of electron affinity, use Gaussian'09 (software made by Gaussian) and calculated by B3LYP/6-31G(d), which is the inverse of the value of LUMO (multiplied by negative 1 value). The electron affinity of the n-type semiconductor material is preferably 3.0 to 5.0 eV.

Examples of n-type semiconductor materials include fullerenes selected from the group including fullerenes and their derivatives, condensed aromatic carbocyclic compounds (for example, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, and Tetraphenyl derivatives, pyrene derivatives, perylene derivatives, and 1,2-benzoacenaphthene derivatives); heterocyclic compounds having at least one of a nitrogen atom, an oxygen atom and a sulfur atom and a 5- to 7-membered ring (for example , Pyridine, pyridine, pyrimidine, pyridine, triazole, quinoline, quinoline, quinazoline, phthaloline, quinoline, isoquinoline, pteridine, acridine, phenimidine, phenanthroline, tetrazole, Pyrazole, imidazole, thiazole, etc.); polyarylene compounds; pyrene compounds; cyclopentadiene compounds; silyl compounds; 1,4,5,8-naphthalenetetracarboxylic anhydride; 1,4,5 ,8-Naphthalenetetracarboxylic acid anhydride imine derivatives, oxadiazole derivatives; anthraquinone dimethane derivatives; diphenyl quinone derivatives; bathocuproine, bathophenanthroline And these derivatives; triazole compounds; distyrylarylene; metal complexes having nitrogen-containing heterocyclic compounds as ligands; silicopentadiene compounds; and Japanese Patent Application Publication 2006 The compound described in paragraphs [0056] to [0057] of Bulletin No. 100767.

Among them, the n-type semiconductor material preferably contains fullerenes selected from the group including fullerenes and their derivatives. Fullerenes include, for example, fullerene C60, fullerene C70, fullerene C76, fullerene C78, fullerene C80, fullerene C82, fullerene C84, fullerene C90, fullerene C96, fullerene C240, fullerene C540 and mixed fullerene. The fullerene derivatives include, for example, 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. The fullerene derivative is preferably the compound described in JP 2007-123707 A. When the n-type semiconductor material contains fullerenes, the content of fullerenes relative to the total content of the n-type semiconductor materials in the photoelectric conversion film (=(film thickness of fullerenes converted to a single layer/ The film thickness of the total n-type semiconductor material in terms of a single layer)×100) is preferably 15-100% by volume, more preferably 35-100% by volume.

An organic dye can be used as an n-type semiconductor material in place of the n-type semiconductor material described in the previous paragraph or together with the n-type semiconductor material described in the previous paragraph. By using an organic dye as an n-type semiconductor material, it is easy to control the absorption wavelength (absorption maximum wavelength) of the photoelectric conversion element in any wavelength range. The above-mentioned organic pigments include, for example, cyanine pigments, styrene pigments, hemicyanine pigments, merocyanine pigments (including zero-methine merocyanine (simple merocyanine)), rhodan cyanine pigments, and Aropola Pigments, oxocyanine pigments, semioxocyanine pigments, squaraine pigments, crotonium pigments, azamethine pigments, coumarin pigments, arylene pigments, anthraquinone pigments, triphenylmethane pigments, Azo pigments, methine azo pigments, metallocene pigments, ketone pigments, fulgides pigments, perylene pigments, brown pigments, phenanthrene pigments, quinone pigments, diphenylmethane pigments, polyene pigments, acridine Pyridinic pigments, acridinone pigments, diphenylamine pigments, quinoline yellow pigments, phenanthrene pigments, phthaloperylene pigments, dioxane pigments, porphyrin pigments, chlorophyll pigments, phthalocyanine pigments, subphthalocyanine pigments and metal complexes Dyes, the compounds described in paragraphs [0083] to [0089] of JP 2014-082483, the compounds described in paragraphs [0029] to [0033] of JP 2009-167348, Japan The compounds described in paragraphs [0197] to [0227] of JP 2012-077064. When the n-type semiconductor material contains an organic dye, the content of the organic dye relative to the total content of the n-type semiconductor material in the photoelectric conversion film (= (the film thickness of the organic dye converted to a single layer/the total n-type semiconductor material The film thickness converted to a single layer)×100) is preferably 15-100% by volume, and more preferably 35-100% by volume.

The molecular weight of the n-type semiconductor material is preferably 200-1200, more preferably 200-900.

The photoelectric conversion film preferably has a bulk heterostructure formed in a state where a specific compound and an n-type semiconductor material are mixed. The bulk heterostructure is a layer in which specific compounds and n-type semiconductor materials are mixed and dispersed in the photoelectric conversion film. In addition, the heterogeneous structure of the body is described in detail in paragraphs [0013] to [0014] of JP 2005-303266 A, etc.

From the viewpoint of the responsiveness of the photoelectric conversion element, the content of the specific compound relative to the total content of the specific compound and the n-type semiconductor material (= the film thickness of the specific compound converted to a single layer/(the specific compound converted to a single layer) The film thickness + the film thickness of the n-type semiconductor material in terms of a single layer)×100) is preferably 15 to 75 vol%, and more preferably 35 to 75 vol%. In addition, the photoelectric conversion film is preferably substantially composed of a specific compound and an n-type semiconductor material. It essentially means that the total content of the specific compound and the n-type semiconductor material is 95% by mass or more relative to the total mass of the photoelectric conversion film.

In addition, the n-type semiconductor material contained in the photoelectric conversion film may be used singly or in combination of two or more kinds.

The non-luminescent film of the photoelectric conversion film containing the specific compound has different characteristics from the organic electroluminescence device (OLED: Organic Light Emitting Diode). The non-luminous film refers to a film with a luminous quantum efficiency of 1% or less, preferably a luminous quantum efficiency of 0.5% or less, and more preferably 0.1% or less.

＜Film forming method＞ The photoelectric conversion film is mainly formed by a dry film forming method. Dry film forming methods include, for example, vapor deposition methods (especially vacuum deposition methods), sputtering methods, ion plating methods, and MBE (Molecular Beam Epitaxy) methods such as physical vapor deposition methods and plasma CVD (Chemical Vapor Deposition) methods such as polymerization. Among them, the vacuum evaporation method is preferred. When the photoelectric conversion film is formed into a film by a vacuum evaporation method, manufacturing conditions such as the degree of vacuum and the evaporation temperature can be set in accordance with a conventional method.

The thickness of the photoelectric conversion film is preferably 10 to 1000 nm, more preferably 50 to 800 nm, more preferably 50 to 500 nm, and particularly preferably 50 to 300 nm.

＜Electrode＞ The electrodes (the upper electrode (transparent conductive film) 15 and the lower electrode (conductive film) 11) are made of a conductive material. Examples of conductive materials include metals, alloys, metal oxides, 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. The material constituting the upper electrode 15 includes, for example, tin oxide doped with antimony or fluorine (ATO: Antimony Tin Oxide, FTO: Fluorine doped Tin Oxide), tin oxide, oxide Conductive metal oxides such as zinc, indium oxide, indium tin oxide (ITO: Indium Tin Oxide), and indium zinc oxide (IZO: Indium zinc oxide); metal thin films such as gold, silver, chromium, and nickel; these metals are conductive Mixtures or laminates of metal oxides; and organic conductive materials such as polyaniline, polythiophene, and polypyrrole. Among them, from the viewpoints of high conductivity, transparency, etc., conductive metal oxides are preferred.

Generally, if the conductive film is made thinner than a certain range, the resistance value will increase sharply. However, in the solid-state imaging element incorporating the photoelectric conversion element of this embodiment, the sheet resistance is preferably 100 to 10000Ω /□ is sufficient, and the film thickness range that can be thinned has a large degree of freedom. In addition, the thinner the thickness of the upper electrode (transparent conductive film) 15 is, the smaller the amount of light absorbed, and in general, the light transmittance increases. The increase in light transmittance increases the light absorption in the photoelectric conversion film, thereby increasing the photoelectric conversion energy, which is therefore preferable. Considering the suppression of leakage current, the increase in the resistance value of the film, and the increase in transmittance accompanying 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 lower electrode 11 may have transparency and, conversely, may not have transparency and reflect light. The materials constituting the lower electrode 11 include, for example, tin oxide (ATO, FTO), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO) doped with antimony or fluorine. Metal oxides; metals such as gold, silver, chromium, nickel, titanium, tungsten, and aluminum, and conductive compounds such as oxides or nitrides of these metals (for example, titanium nitride (TiN)); Mixtures or laminates of metals and conductive metal oxides; and organic conductive materials such as polyaniline, polythiophene, and polypyrrole.

The method of forming the electrode is not particularly limited, and can be appropriately selected according to the electrode material. Specifically, wet methods such as printing methods and coating methods; physical methods such as vacuum evaporation methods, sputtering methods, and ion plating methods; chemical methods such as CVD and plasma CVD methods, and the like can be cited. When the electrode material is ITO, methods such as an electron beam method, a sputtering method, a resistance heating vapor deposition method, a chemical reaction method (sol-gel method, etc.), and coating of a dispersion of indium tin oxide can be mentioned.

<Charge blocking film: electron blocking film, hole blocking film> The photoelectric conversion element of the present invention preferably has one or more kinds of intermediate layers in addition to the photoelectric conversion film between the conductive film and the transparent conductive film. The intermediate layer may be a charge blocking film. When the photoelectric conversion element has this film, the characteristics (photoelectric conversion efficiency, responsiveness, etc.) of the obtained photoelectric conversion element are more excellent. The charge blocking film includes an electron blocking film and a hole blocking film. Hereinafter, each film will be described in detail.

(Electron Blocking Film) The electron blocking film is a donor organic semiconductor material (compound), and for example, the following p-type organic semiconductor can be used. A p-type organic semiconductor may be used individually by 1 type, and may use 2 or more types.

Examples of p-type organic semiconductors include triarylamine compounds (for example, N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TPD ), 4,4'-bis[N-(naphthyl)-N-phenyl-amino]biphenyl (α-NPD), in paragraphs [0128] to [0148] of JP 2011-228614 The compound described in Japanese Patent Application Publication No. 2011-176259, the compound described in paragraphs [0052] to [0063], and the compound described in Japanese Patent Application Publication No. 2011-225544, which is described in paragraphs [0119] to [0158] , Japanese Unexamined Patent Publication No. 2015-153910, the compounds described in paragraphs [0044] to [0051], and the compounds described in Japanese Patent Application Publication No. 2012-094660, paragraphs [0086] to [0090], etc.), pyridine Oxazoline compounds, styrylamine compounds, hydrazone compounds, polysilane compounds, thiophene compounds (for example, thienothiophene derivatives, dibenzothiophene derivatives, benzodithiophene derivatives, dithienothiophene derivatives, [1 ]Benzothiophene[3,2-b]thiophene (BTBT) derivatives, thieno[3,2-f:4,5-f´]bis[1]benzothiophene (TBBT) derivatives, Japanese Patent Application The compounds described in paragraphs [0031] to [0036] of No. 2018-014474, the compounds described in paragraphs [0043] to [0045] of WO2016-194630, and [0025] to [0037] of WO2017-159684 , [0099] to [0109] the compounds described in paragraphs [0029] to [0034] of Japanese Patent Application Publication No. 2017-076766, etc.), cyanine compounds, oxacyanine compounds, poly Amine compounds, indole compounds, pyrrole compounds, pyrazole compounds, polyarylene compounds, condensed aromatic carbocyclic compounds (for example, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, naphthacene derivatives, pentacene Derivatives, pyrene derivatives, perylene derivatives and 1,2-benzoacenaphthene derivatives), porphyrin compounds, phthalocyanine compounds, triazole compounds, oxadiazole compounds, imidazole compounds, polyarylalkane compounds, pyrazole Lintong compounds, amine-substituted chalcone compounds, azole compounds, quinone compounds, silazane compounds, and metal complexes with nitrogen-containing heterocyclic compounds as ligands. Examples of p-type organic semiconductors include compounds having a free potential smaller than that of n-type semiconductor materials. As long as this condition is satisfied, organic dyes exemplified by n-type semiconductor materials can also be used.

In addition, as the electron blocking film, a polymer material can also be used. Examples of the polymer material include polymers such as phenylacetylene, pyrene, carbazole, indole, pyrene, pyrrole, picoline, thiophene, acetylene, and diacetylene, and derivatives thereof.

In addition, the electron blocking film may be composed of a plurality of films. The electron blocking film may be composed of an inorganic material. Generally speaking, the dielectric constant of inorganic materials is greater than that of organic materials. Therefore, when inorganic materials are used for electron blocking films, more voltage is applied to the photoelectric conversion film, and the photoelectric conversion efficiency becomes higher. Inorganic materials that can become electron barrier films include, for example, 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, and indium oxide. Copper, indium silver oxide and iridium oxide.

(Hole blocking film) The hole blocking film is an acceptor organic semiconductor material (compound), and the aforementioned n-type semiconductor material can be used.

The manufacturing method of the charge blocking film is not particularly limited, and a dry film forming method and a wet film forming method can be mentioned. Examples of the dry film forming method include a vapor deposition method and a sputtering method. The vapor deposition method may be any of a physical vapor deposition (PVD: Physical Vapor Deposition) method and a chemical vapor deposition (CVD) method, and a physical vapor deposition method such as a vacuum vapor deposition method is preferable. Examples of wet film forming methods include inkjet, spray, nozzle printing, spin coating, dip coating, casting, die coating, roll coating, bar coating, and gravure coating methods. From the viewpoint of precision patterning, the inkjet method is preferable.

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 also have a substrate. The type of substrate used is not particularly limited, and examples include semiconductor substrates, glass substrates, and plastic substrates. In addition, the position of the substrate is not particularly limited. Usually, a conductive film, a photoelectric conversion film, and a transparent conductive film are sequentially laminated on the substrate.

＜Sealing layer＞ The photoelectric conversion element may also have a sealing layer. Sometimes the performance of the photoelectric conversion material is significantly deteriorated due to the presence of deterioration factors such as water molecules. Therefore, the use of dense metal oxides, metal nitrides, or metal nitride oxides that do not allow water molecules to permeate, such as ceramics or diamond-like carbon (DLC: Diamond-like Carbon), is used to seal the photoelectric conversion film. The whole is covered and sealed, thereby preventing the aforementioned deterioration. In addition, the sealing layer can be selected and manufactured in accordance with the description in paragraphs [0210] to [0215] of JP 2011-082508 A.

＜Imaging components＞ As the use of the photoelectric conversion element, for example, an imaging element can be cited. The imaging element is an element that converts the optical information of the image into an electrical signal. It usually refers to a plurality of photoelectric conversion elements arranged in the same plane on a matrix, and each photoelectric conversion element (pixel) can convert the optical signal into an electrical signal And output its electrical signal to those outside the imaging element one by one for each pixel. Therefore, each pixel is composed of one or more photoelectric conversion elements and one or more transistors. Fig. 3 is a schematic cross-sectional view illustrating the basic structure of an imaging element according to an embodiment of the present invention. The imaging element is mounted on imaging elements such as digital cameras and digital video cameras, electronic endoscopes, and camera modules such as mobile phones. The imaging element 20a shown in FIG. 3 includes the photoelectric conversion element 10a (green photoelectric conversion element 10a) of the present invention, the blue photoelectric conversion element 22, and the red photoelectric conversion element 24, which are laminated in the direction in which light enters. The photoelectric conversion element 10a is the photoelectric conversion element of the present invention, and the absorption wavelength is mainly controlled to be a green photoelectric conversion element so that it can receive green light. As a method of controlling the absorption wavelength of the photoelectric conversion element of the present invention, for example, a method of using an appropriate organic dye as an n-type semiconductor material can be cited. The imaging element 20a is a so-called multi-layer type dichroic imaging element. The photoelectric conversion element 10a, the blue photoelectric conversion element 22, and the red photoelectric conversion element 24 respectively detect different wavelength spectra. That is, the blue photoelectric conversion element 22 and the red photoelectric conversion element 24 correspond to photoelectric conversion elements that receive light of a different wavelength from the light received (absorbed) by the photoelectric conversion element 10a. The photoelectric conversion element 10a can mainly receive green light, the blue photoelectric conversion element 22 can mainly receive blue light, and the red photoelectric conversion element can mainly receive red light. In addition, green light refers to light in a wavelength range of 500 to 600 nm, blue light refers to light in a wavelength range of 400 to 500 nm, and red light refers to light in a wavelength range of 600 to 700 nm. When light enters the imaging element 20a from the direction of the arrow, first, although green light is mainly absorbed in the photoelectric conversion element 10a, blue light and red light are transmitted through the photoelectric conversion element 10a. When the light transmitted through the photoelectric conversion element 10a enters the blue photoelectric conversion element 22, it mainly absorbs blue light, but for red light, it transmits the blue photoelectric conversion element 22. Then, the light transmitted through the blue photoelectric conversion element 22 is absorbed by the red photoelectric conversion element 24. In this way, in the imaging element 20a which is a multi-layered dichroic imaging element, one pixel can be constituted by three light receiving parts of green, blue, and red, and a large light receiving part area can be adopted.

The structures of the blue photoelectric conversion element 22 and the red photoelectric conversion element 24 are not particularly limited. For example, it may be a photoelectric conversion element that uses silicon and separates colors by the difference in light absorption length. More specifically, for example, both the blue photoelectric conversion element 22 and the red photoelectric conversion element 24 may be made of silicon. In this case, the light including blue light, green light, and red light incident on the imaging element 20a in the direction of the arrow is mainly received by the photoelectric conversion element 10a, and the remaining blue light And red light becomes easy to separate. Blue light and red light have a difference in the light absorption length of silicon (the wavelength dependence of the absorption coefficient of silicon). Blue light is easily absorbed near the silicon surface, and red light can invade the deeper parts of silicon. Based on this difference in light absorption length, blue light is mainly received by the blue photoelectric conversion element 22 existing in a shallower position, and red light is mainly received by the red photoelectric conversion element 24 existing in a deeper position. In addition, the blue photoelectric conversion element 22 and the red photoelectric conversion element 24 may be photoelectric conversion elements having a conductive film, an organic photoelectric conversion film that absorbs blue light or red light, and a transparent conductive film (blue Photoelectric conversion element 22 or red photoelectric conversion element 24). For example, the blue photoelectric conversion element 22 may be the photoelectric conversion element of the present invention whose absorption wavelength is controlled so as to have a maximum absorption in blue light. Similarly, the red photoelectric conversion element 24 may be the photoelectric conversion element of the present invention in which the absorption wavelength is controlled so as to have a maximum absorption in red light.

In FIG. 3, the photoelectric conversion element, the blue photoelectric conversion element, and the red photoelectric conversion element of the present invention are arranged in order from the light incident side, but it is not limited to this aspect, and another arrangement order may be used. For example, the blue photoelectric conversion element, the photoelectric conversion element of the present invention, and the red photoelectric conversion element may be arranged in order from the side where light enters. In addition, a green photoelectric conversion element is used as a photoelectric conversion element other than the photoelectric conversion element of the present invention, and a blue photoelectric conversion element and/or a red photoelectric conversion element may be used as the photoelectric conversion element of the present invention.

As the imaging element, as described above, the structure of the photoelectric conversion element in which the three primary colors of blue, green, and red are laminated has been described, but it may be two layers (two colors) or four layers (four colors) or more. For example, the photoelectric conversion element 10a of the present invention may be arranged on the blue photoelectric conversion element 22 and the red photoelectric conversion element 24 arranged. In addition, a color filter that absorbs light of a predetermined wavelength can be further arranged on the incident side of the light as required.

The form of the imaging element is not limited to FIG. 3 and the above-mentioned form, and other forms may be used. For example, it may be an aspect in which the photoelectric conversion element, the blue photoelectric conversion element, and the red photoelectric conversion element of the present invention are arranged in the same plane.

In addition, it may be a structure in which a photoelectric conversion element is used in a single layer. For example, it may be a structure in which colors are separated by disposing blue, red, and green color filters on the photoelectric conversion element 10a of the present invention.

The photoelectric conversion element of the present invention is also preferably used as a light sensor. The photo sensor can use the photoelectric conversion element alone, or can be used as a line sensor in which the photoelectric conversion element is arranged in a linear shape or a two-dimensional sensor in which the photoelectric conversion element is arranged in a planar shape.

<Materials for photoelectric conversion elements for imaging elements, materials for photoelectric conversion elements for light sensors> The present invention also includes the invention of materials for photoelectric conversion elements for imaging elements and the invention of materials for photoelectric conversion elements for photo sensors. The material for a photoelectric conversion element for an imaging element of the present invention is a material for producing a photoelectric conversion element for an imaging element containing a compound (specific compound) represented by formula (1). The material for a photoelectric conversion element for a photosensor of the present invention is a material for manufacturing a photoelectric conversion element for a photosensor containing a compound (specific compound) represented by formula (1). The compound represented by formula (1) in the material for photoelectric conversion element for imaging element and the material for photoelectric conversion element for light sensor is the same as the compound represented by formula (1) above. It is preferable that the compound represented by formula (1) in the material for photoelectric conversion elements for imaging elements and the material for photoelectric conversion elements for light sensors is the compound represented by formula (2) above. The specific compound contained in the material for photoelectric conversion element for imaging element and the material for photoelectric conversion element for light sensor is used to produce the photoelectric conversion film contained in the photoelectric conversion element for imaging element and the photoelectric conversion element for light sensor, respectively The photoelectric conversion film is preferred. The content of the specific compound contained in the material for the photoelectric conversion element for the imaging element and the material for the photoelectric conversion element for the photo sensor is the total mass of the material for the photoelectric conversion element for the imaging element and the material for the photoelectric conversion element for the photo sensor, respectively It is preferably 30-100% by mass of the total mass, more preferably 70-100% by mass, and still more preferably 99-100% by mass. The specific compound contained in the material for photoelectric conversion elements for imaging elements and the material for photoelectric conversion elements for light sensors may be one type alone or two or more types. [Example]

Hereinafter, the present invention will be described in further detail based on examples. The materials, usage amounts, ratios, processing contents, and processing steps shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the embodiments shown below.

<Synthesis of Compound (D-1)> The compound (D-1) was synthesized according to the following scheme.

[Chemical formula 8]

Add 2,5-dibromothiophene (1.20g, 5.0mmol) and 4-p-terphenylboronic acid (3.67g, 13.4mmol) to tetrahydrofuran (100mL) in the flask, and add 2M sodium carbonate aqueous solution (60mL) to it . A series of operations of vacuuming and nitrogen replacement in the flask were repeated three times in sequence, tetrakis(triphenylphosphine)palladium(0) (115mg, 0.10mmol) was added to the obtained reaction liquid, and the obtained reaction liquid was refluxed and reacted It took 4 hours. After cooling the reaction liquid, filtration was performed, and the obtained solid was washed with water and methanol to obtain a crude product. Chloroform was added to the obtained crude product, and dispersed and washed under reflux for 1 hour. The liquid after cooling, dispersion and washing was returned to room temperature, and then filtered, and the obtained solid was washed with chloroform and methanol to obtain compound (D-1) (1.95 g, 3.61 mmol, 73% yield). The obtained compound (D-1) was confirmed by MS (Mass Spectrometry). ¹ MS (ESI ⁺ ) m/z: 541.2 ([M+H] ⁺ )

Referring to the synthesis method of compound (D-1), compounds (D-2) to (D-8) were synthesized. Below, compounds (D-1) to (D-8) and comparative compounds (R-1) to (R-3) are shown.

[Chemical formula 9]

The values of HOMO and LUMO of each compound are shown below. In addition, the value of HOMO and the value of LUMO were calculated by B3LYP/6-31G(d) using Gaussian'09 (software manufactured by Gaussian), respectively. The value of the inverse of the obtained LUMO value is adopted as the value of the electron affinity of the compound. ============================== HOMO (eV) LUMO (eV) ------------ --------------------------------------- D-1 -5.23 -1.66 D-2- 5.15 -1.61 D-3 -5.06 -1.86 D-4 -5.16 -1.81 D-5 -5.24 -1.65 D-6 -5.25 -1.82 D-7 -5.06 -1.61 D-8 -5.06 -1.58 R-1 -5.27 -1.57 R-2 -5.06 -1.79 R-3 -5.42 -2.18 C ₆₀ -5.99 -3.23 ======================

<Examples and Comparative Examples: Production of Photoelectric Conversion Element> The obtained compound was used to produce a photoelectric conversion element of the form of FIG. 2. Among them, the photoelectric conversion element is composed of a lower electrode 11, an electron blocking film 16A, a photoelectric conversion film 12, a positive hole blocking film 16B, and an upper electrode 15. Specifically, the lower electrode 11 (thickness: 30 nm) was formed by forming amorphous ITO on a glass substrate by a sputtering method, and the following compound was further deposited on the lower electrode 11 by a vacuum heating vapor deposition method ( B-1) The electron blocking film 16A (thickness: 10 nm) was formed by film formation. Furthermore, while the temperature of the substrate was controlled at 25°C, the electron blocking film 16A was deposited on the electron blocking film 16A by vacuum deposition at a deposition rate of 2.0 Å/sec and converted to a single layer of 100 nm and 100 nm, respectively. The compound (D-1) and the fullerene (C ₆₀ ) were co-evaporated by the method to form a film, thereby forming a photoelectric conversion film 12 having a bulk heterostructure of 200 nm (photoelectric conversion film formation step). In addition, the following compound (B-2) was formed on the photoelectric conversion film 12 to form a positive hole barrier film 16B (thickness: 10 nm). In addition, an amorphous ITO film was formed on the positive hole barrier film 16B by a sputtering method to form the upper electrode 15 (transparent conductive film) (thickness: 10 nm). After forming a SiO film as a sealing layer on the upper electrode 15 by a vacuum evaporation method, aluminum oxide (Al ₂ O ₃ ) is formed thereon by an ALCVD (Atomic Layer Chemical Vapor Deposition) method. ) Layer to produce a photoelectric conversion element.

[Chemical formula 10]

Instead of the compound (D-1), the respective compounds (D-2) to (D-8) or (R-1) to (R-3) were used to produce a photoelectric conversion element in the same manner.

<Evaluation of quantum efficiency (photoelectric conversion efficiency)> The drive of each photoelectric conversion element obtained was confirmed. A voltage was applied to each photoelectric conversion element to have an electrical boundary strength of 1.0×10 ⁵ V/cm. After that, light was irradiated from the upper electrode (transparent conductive film) side, and the photoelectric conversion efficiency (external quantum efficiency) at 400 nm was evaluated. The external quantum efficiency was measured using the energy quantum efficiency measuring device developed by NIHON OPTEL CORPORATION. The amount of light irradiated is 50 μW/cm ² . Set the quantum efficiency of 50% or more as A, 30% or more and less than 50% as B, 10% or more and less than 30% as C, and less than 10% as D, and evaluated using each compound. The photoelectric conversion efficiency of the photoelectric conversion element. In practice, B or more is preferable, and A is more preferable. The results are shown in Table 1.

<Confirmation of Drive (Evaluation of Dark Current)> The dark current of the obtained device was measured. A voltage was applied to the lower electrode and the upper electrode of the photoelectric conversion element to have an electrical boundary strength of 2.0×10 ⁵ V/cm, and the current value in a dark place was measured. As a result, it was confirmed that in any photoelectric conversion element, the dark place is 1 nA/cm ² or less, showing a sufficiently low dark current.

<Evaluation of suitability for continuous vapor deposition> The suitability for continuous vapor deposition of the photoelectric conversion film was evaluated. The vapor deposition rate was set to 2.0 Å/sec, and the compound (D-1) and fullerene (C ₆₀ ) were vapor-deposited continuously for 5 hours. The above-mentioned photoelectric conversion film formation step was performed at the time when the vapor deposition was started and at the time when 5 hours had passed, and two types of photoelectric conversion elements were produced. The dark currents of the two types of photoelectric conversion elements produced were evaluated by the above-mentioned method, and the relative values were evaluated. The value of the dark continuous flow of the electrical conversion element produced by performing the photoelectric conversion film forming step after 5 hours/the dark continuous flow of the photoelectric conversion element produced by performing the photoelectric conversion film forming step at the start of vapor deposition Value) The relative value was calculated, and the suitability of the photoelectric conversion film for continuous vapor deposition was evaluated. In place of the compound (D-1), the compounds (D-2) to (D-8) and (R-1) to (R-3) were used, and the suitability of the photoelectric conversion film for continuous vapor deposition was evaluated in the same manner. Regarding the suitability for continuous vapor deposition of the photoelectric conversion film using each compound, the evaluation was performed as follows: if the relative value is 1.5 or less, it is set as A, if it is greater than 1.5 and 3 or less, it is set as B, and if it is greater than 3 and 10 or less, it is set It is C, if it is greater than 10, it is set to D. In practice, B or more is preferable, and A is more preferable. The results are shown in Table 1. In addition, the photoelectric conversion element used in the test of <Quantum Efficiency (Evaluation of Photoelectric Conversion Efficiency)> and <Drive Confirmation (Evaluation of Dark Current)> is a photoelectric conversion film produced by performing a photoelectric conversion film formation step when starting vapor deposition Conversion components.

The results of the test performed with the photoelectric conversion element produced using each compound are shown in Table 1 below. In Table 1, the column "m1, m2" shows the values of m1 and m2 when the specific compound used is applied to the formula (1). The column of "n2, n3" shows the values of n2 and n3 when the specific compound used is applied to formula (1). The column "X ¹ "shows the atom of X ¹ when the specific compound used is applied to the formula (1). S is a sulfur atom, and O is an oxygen atom. The column "Formula (2)" shows whether the specific compound used corresponds to the compound represented by the formula (2). It is set to "A" if it matches, and it is set to "B" if it does not.

[Table 1] Compound characteristics Photoelectric conversion efficiency Suitability for continuous vapor deposition species m1,m2 n2,n3 X ¹ Formula (2) Example 1 D-1 0 0 S A A A Example 2 D-2 0 0 S A A A Example 3 D-3 0 0 S A A A Example 4 D-4 1 0 S B A B Example 5 D-5 0 0 S A A A Example 6 D-6 0 0 S A A A Example 7 D-7 0 1 S B B A Example 8 D-8 0 0 O B A B Comparative example 1 R-1 - - - - D B Comparative example 2 R-2 - - - - D B Comparative example 3 R-3 - - - - B D

From the results shown in Table 1, it was confirmed that the photoelectric conversion element of the present invention was excellent in photoelectric conversion efficiency. Furthermore, it was confirmed that the photoelectric conversion element of the present invention has a small increase in the value of dark current and stable performance even when a photoelectric conversion film is produced by vapor deposition using a vapor deposition material continuously supplied for vapor deposition for a long time. On the other hand, when a compound (R-1) that does not have groups corresponding to Ar ¹ and Ar ⁴ in formula (1) is used, the photoelectric conversion efficiency of the resulting photoelectric conversion film is insufficient. Similarly, in the case of using a compound (R-2) that does not have groups equivalent to Ar ¹ and Ar ⁴ in formula (1) and the central structure of the compound is a bithiophene structure, the resulting photoelectric conversion film The photoelectric conversion efficiency is not sufficient. When the compound (R-2) in which the ring existing adjacent to the center structure of the compound is an aromatic heterocyclic ring is used, the suitability for continuous vapor deposition is insufficient.

In formula (1), when m1 and m2 are 0, it is confirmed that the photoelectric conversion film has more excellent suitability for continuous vapor deposition. (Results of Example 4, etc.)

In formula (1), when n2 and n3 are 0, it is confirmed that the photoelectric conversion efficiency of the photoelectric conversion element is more excellent. (Results of Example 7, etc.)

In the formula (1), when X ¹ is a sulfur atom, it is confirmed that the photoelectric conversion film has more excellent suitability for continuous vapor deposition. (Results of Example 8, etc.)

When the specific compound is a compound represented by formula (2), it was confirmed that the effect of the present invention is more excellent. (Results of Examples 4, 7, 8, etc.)

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 20a: Image sensor 22: Blue photoelectric conversion element 24: Red photoelectric conversion element

Fig. 1 is a schematic cross-sectional view showing a configuration example of a photoelectric conversion element. Fig. 2 is a schematic cross-sectional view showing a configuration example of a photoelectric conversion element. Fig. 3 is a schematic cross-sectional view of an embodiment of the imaging element.

10a: photoelectric conversion element

11: Conductive film (lower electrode)

12: Photoelectric conversion film

15: Transparent conductive film (upper electrode)

16A: Electron blocking film

Claims (15)

A photoelectric conversion element having a conductive film, a photoelectric conversion film, and a transparent conductive film in this order, wherein the photoelectric conversion film includes a compound represented by formula (1) and an n-type semiconductor material,

In formula (1), Ar ¹ and Ar ⁴ are each independently selected from the group consisting of an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, and a methyl group which may have a substituent. One or more of the silyl group, the optionally substituted aryl group, the optionally substituted heteroaryl group and the halogen atom group of the optionally substituted aromatic ring, Ar ² and Ar ³ are each independently selected from Including alkyl groups which may have substituents, alkoxy groups which may have substituents, alkylthio groups which may have substituents, silyl groups which may have substituents, aryl groups which may have substituents, heterocyclic groups which may have substituents One or more monocyclic aromatic rings that may have substituents in the group of aryl and halogen atoms, X ¹ represents a sulfur atom, an oxygen atom, a selenium atom, SiR ^a1 R ^a2 or NR ^a3 , R ^a1 to R ^a3 Each independently represents a hydrogen atom or a substituent, m1 and m2 each independently represent 0 or 1, n1 to n4 each independently represent 0 or 1, and R ¹ to R ¹² each independently represent an optionally substituted alkyl group, Substituent alkoxy group, optionally substituted alkylthio group, optionally substituted silyl group, optionally substituted aryl group, optionally substituted heteroaryl group, halogen atom or hydrogen atom, L ¹ to L ⁴ each independently represent a sulfur atom, an oxygen atom, a selenium atom, SiR ^a4 R ^a5 , NR ^a6 or CR ^a7 R ^a8 , R ^a4 to R ^a8 each independently represent a hydrogen atom or a substituent, Y ¹ and Y ² Each independently represents a nitrogen atom or CR ^a9 , R ^a9 represents a hydrogen atom or a substituent, wherein when n2 is 1, R ¹¹ does not exist, when n3 is 1, R ¹² does not exist, and n1 represents 0 In the case, L ¹ does not exist, Ar ¹ and Ar ² are only connected by the single bond shown in the aforementioned formula (1), and when n2 represents 0, L ² does not exist, and the single ring bonded to R ^{2 is} either The polycyclic aromatic ring and Ar ² are only connected by the single bond shown in the aforementioned formula (1). When n3 represents 0, L ³ does not exist, and the monocyclic or polycyclic aromatic ring bonded to R ^{3 is} connected with Ar ³ is connected only by the single bond explicitly shown in the aforementioned formula (1), and when n4 represents 0, L ⁴ does not exist, and Ar ⁴ and Ar ³ are only connected by the single bond explicitly shown in the aforementioned formula (1). The photoelectric conversion element according to claim 1, wherein The molecular weight of the compound represented by the aforementioned formula (1) is 500-900. The photoelectric conversion element according to claim 1 or 2, wherein Y ¹ and Y ² represent CR ^a9 . The photoelectric conversion element according to claim 1 or 2, wherein X ¹ represents a sulfur atom or an oxygen atom. The photoelectric conversion element according to claim 1 or 2, wherein X ¹ represents a sulfur atom. The photoelectric conversion element according to claim 1 or claim 2, wherein the compound represented by the aforementioned formula (1) is a compound represented by the formula (2),

In formula (2), Ar ¹ and Ar ⁴ are each independently selected from the group consisting of an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, and a methyl group which may have a substituent. One or more of the silyl group, the optionally substituted aryl group, the optionally substituted heteroaryl group and the halogen atom group of the optionally substituted aromatic ring, Ar ² and Ar ³ are each independently selected from Including alkyl groups which may have substituents, alkoxy groups which may have substituents, alkylthio groups which may have substituents, silyl groups which may have substituents, aryl groups which may have substituents, heterocyclic groups which may have substituents One or more monocyclic aromatic rings that may have substituents in the group of aryl and halogen atoms, n1 and n4 each independently represent 0 or 1, R ² , R ³ , R ⁶ , R ⁷ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, and an optionally substituted alkyl group A silyl group, an aryl group that may have a substituent, a heteroaryl group that may have a substituent, a halogen atom or a hydrogen atom, L ¹ and L ⁴ each independently represent a sulfur atom, an oxygen atom, a selenium atom, SiR ^a4 R ^a5 , NR ^a6 or CR ^a7 R ^a8 , and R ^a4 to R ^a8 each independently represent a hydrogen atom or a substituent. When n1 represents 0, L ¹ does not exist, and Ar ¹ and Ar ² are only represented by the aforementioned formula (2) In the single-bond connection indicated, when n4 represents 0, L ⁴ does not exist, and Ar ⁴ and Ar ³ are only connected by the single-bond indicated in the aforementioned formula (2). The photoelectric conversion element according to claim 1 or 2, wherein The photoelectric conversion film has a bulk heterostructure formed in a state where the compound represented by the formula (1) and the n-type semiconductor material are mixed. The photoelectric conversion element according to claim 1 or 2, wherein Between the conductive film and the transparent conductive film, in addition to the photoelectric conversion film, there is one or more intermediate layers. The photoelectric conversion element according to claim 1 or 2, wherein The aforementioned n-type semiconductor material includes fullerenes selected from the group including fullerenes and derivatives thereof. An imaging element having the photoelectric conversion element described in any one of claim 1 to claim 9. A photo sensor having the photoelectric conversion element described in any one of claim 1 to claim 9. A material for photoelectric conversion elements for imaging elements, which contains a compound represented by formula (1), wherein

In formula (1), Ar ¹ and Ar ⁴ are each independently selected from the group consisting of an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, and a methyl group which may have a substituent. One or more of the silyl group, the optionally substituted aryl group, the optionally substituted heteroaryl group and the halogen atom group of the optionally substituted aromatic ring, Ar ² and Ar ³ are each independently selected from Including alkyl groups which may have substituents, alkoxy groups which may have substituents, alkylthio groups which may have substituents, silyl groups which may have substituents, aryl groups which may have substituents, heterocyclic groups which may have substituents One or more monocyclic aromatic rings that may have substituents in the group of aryl and halogen atoms, X ¹ represents a sulfur atom, an oxygen atom, a selenium atom, SiR ^a1 R ^a2 or NR ^a3 , R ^a1 to R ^a3 Each independently represents a hydrogen atom or a substituent, m1 and m2 each independently represent 0 or 1, n1 to n4 each independently represent 0 or 1, and R ¹ to R ¹² each independently represent an optionally substituted alkyl group, Substituent alkoxy group, optionally substituted alkylthio group, optionally substituted silyl group, optionally substituted aryl group, optionally substituted heteroaryl group, halogen atom or hydrogen atom, L ¹ to L ⁴ each independently represent a sulfur atom, an oxygen atom, a selenium atom, SiR ^a4 R ^a5 , NR ^a6 or CR ^a7 R ^a8 , R ^a4 to R ^a8 each independently represent a hydrogen atom or a substituent, Y ¹ and Y ² Each independently represents a nitrogen atom or CR ^a9 , R ^a9 represents a hydrogen atom or a substituent, wherein when n2 is 1, R ¹¹ does not exist, when n3 is 1, R ¹² does not exist, and n1 represents 0 In the case, L ¹ does not exist, Ar ¹ and Ar ² are only connected by the single bond shown in the aforementioned formula (1), and when n2 represents 0, L ² does not exist, and the single ring bonded to R ^{2 is} either The polycyclic aromatic ring and Ar ² are only connected by the single bond shown in the aforementioned formula (1). When n3 represents 0, L ³ does not exist, and the monocyclic or polycyclic aromatic ring bonded to R ^{3 is} connected with Ar ³ is connected only by the single bond explicitly shown in the aforementioned formula (1), and when n4 represents 0, L ⁴ does not exist, and Ar ⁴ and Ar ³ are only connected by the single bond explicitly shown in the aforementioned formula (1). The material for photoelectric conversion elements for imaging elements according to claim 12, wherein the compound represented by the aforementioned formula (1) is a compound represented by the formula (2),

In formula (2), Ar ¹ and Ar ⁴ are each independently selected from the group consisting of an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, and a methyl group which may have a substituent. One or more of the silyl group, the optionally substituted aryl group, the optionally substituted heteroaryl group and the halogen atom group of the optionally substituted aromatic ring, Ar ² and Ar ³ are each independently selected from Including alkyl groups which may have substituents, alkoxy groups which may have substituents, alkylthio groups which may have substituents, silyl groups which may have substituents, aryl groups which may have substituents, heterocyclic groups which may have substituents One or more monocyclic aromatic rings that may have substituents in the group of aryl and halogen atoms, n1 and n4 each independently represent 0 or 1, R ² , R ³ , R ⁶ , R ⁷ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, and an optionally substituted alkyl group A silyl group, an aryl group that may have a substituent, a heteroaryl group that may have a substituent, a halogen atom or a hydrogen atom, L ¹ and L ⁴ each independently represent a sulfur atom, an oxygen atom, a selenium atom, SiR ^a4 R ^a5 , NR ^a6 or CR ^a7 R ^a8 , and R ^a4 to R ^a8 each independently represent a hydrogen atom or a substituent. When n1 represents 0, L ¹ does not exist, and Ar ¹ and Ar ² are only represented by the aforementioned formula (2) In the single-bond connection indicated, when n4 represents 0, L ⁴ does not exist, and Ar ⁴ and Ar ³ are only connected by the single-bond indicated in the aforementioned formula (2). A material for a photoelectric conversion element for a light sensor, which contains a compound represented by formula (1), wherein

In formula (1), Ar ¹ and Ar ⁴ are each independently selected from the group consisting of an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, and a methyl group which may have a substituent. One or more of the silyl group, the optionally substituted aryl group, the optionally substituted heteroaryl group and the halogen atom group of the optionally substituted aromatic ring, Ar ² and Ar ³ are each independently selected from Including alkyl groups which may have substituents, alkoxy groups which may have substituents, alkylthio groups which may have substituents, silyl groups which may have substituents, aryl groups which may have substituents, heterocyclic groups which may have substituents One or more monocyclic aromatic rings that may have substituents in the group of aryl and halogen atoms, X ¹ represents a sulfur atom, an oxygen atom, a selenium atom, SiR ^a1 R ^a2 or NR ^a3 , R ^a1 to R ^a3 Each independently represents a hydrogen atom or a substituent, m1 and m2 each independently represent 0 or 1, n1 to n4 each independently represent 0 or 1, and R ¹ to R ¹² each independently represent an optionally substituted alkyl group, Substituent alkoxy group, optionally substituted alkylthio group, optionally substituted silyl group, optionally substituted aryl group, optionally substituted heteroaryl group, halogen atom or hydrogen atom, L ¹ to L ⁴ each independently represent a sulfur atom, an oxygen atom, a selenium atom, SiR ^a4 R ^a5 , NR ^a6 or CR ^a7 R ^a8 , R ^a4 to R ^a8 each independently represent a hydrogen atom or a substituent, Y ¹ and Y ² Each independently represents a nitrogen atom or CR ^a9 , R ^a9 represents a hydrogen atom or a substituent, wherein when n2 is 1, R ¹¹ does not exist, when n3 is 1, R ¹² does not exist, and n1 represents 0 In the case, L ¹ does not exist, Ar ¹ and Ar ² are only connected by the single bond shown in the aforementioned formula (1), and when n2 represents 0, L ² does not exist, and the single ring bonded to R ^{2 is} either The polycyclic aromatic ring and Ar ² are only connected by the single bond shown in the aforementioned formula (1). When n3 represents 0, L ³ does not exist, and the monocyclic or polycyclic aromatic ring bonded to R ^{3 is} connected with Ar ³ is connected only by the single bond explicitly shown in the aforementioned formula (1), and when n4 represents 0, L ⁴ does not exist, and Ar ⁴ and Ar ³ are only connected by the single bond explicitly shown in the aforementioned formula (1). The material for a photoelectric conversion element for a photo sensor according to claim 14, wherein the compound represented by the aforementioned formula (1) is a compound represented by the formula (2),

In formula (2), Ar ¹ and Ar ⁴ are each independently selected from the group consisting of an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, and a methyl group which may have a substituent. One or more of the silyl group, the optionally substituted aryl group, the optionally substituted heteroaryl group and the halogen atom group of the optionally substituted aromatic ring, Ar ² and Ar ³ are each independently selected from Including alkyl groups which may have substituents, alkoxy groups which may have substituents, alkylthio groups which may have substituents, silyl groups which may have substituents, aryl groups which may have substituents, heterocyclic groups which may have substituents One or more monocyclic aromatic rings that may have substituents in the group of aryl and halogen atoms, n1 and n4 each independently represent 0 or 1, R ² , R ³ , R ⁶ , R ⁷ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, and an optionally substituted alkyl group A silyl group, an aryl group that may have a substituent, a heteroaryl group that may have a substituent, a halogen atom or a hydrogen atom, L ¹ and L ⁴ each independently represent a sulfur atom, an oxygen atom, a selenium atom, SiR ^a4 R ^a5 , NR ^a6 or CR ^a7 R ^a8 , and R ^a4 to R ^a8 each independently represent a hydrogen atom or a substituent. When n1 represents 0, L ¹ does not exist, and Ar ¹ and Ar ² are only represented by the aforementioned formula (2) In the single-bond connection indicated, when n4 represents 0, L ⁴ does not exist, and Ar ⁴ and Ar ³ are only connected by the single-bond indicated in the aforementioned formula (2).

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