TW201419511A - Photoelectric conversion element, method of using same, optical sensor, image capture element - Google Patents

Abstract

A purpose of a first embodiment of this invention is to provide a photoelectric conversion element having excellent thermal resistance and responsivity and showing high photoelectric conversion efficiency, a method of using the same, and a photosensor and an image capture element including the photoelectric conversion element. The photoelectric conversion element of the first embodiment of this invention sequentially includes a conductive film, a photoelectric conversion film containing a photoelectric conversion material, and a transparent conductive film, wherein the photoelectric conversion material contains a compound (A) represented by the following formula (1).

Description

Photoelectric conversion element and method of use thereof, photosensor, and photographic element

The present invention relates to a photoelectric conversion element and a method of using the same, and a photosensor and an image pickup element.

A conventional photosensor is a device in which a photodiode (PD) is formed in a semiconductor substrate such as bismuth (Si), and a solid-state imaging device widely uses a planar solid-state imaging device, and the above-described planar solid-state imaging device is two-dimensionally The PDs are arranged, and the signal charges generated by the PDs are read by the circuit.

In order to realize a color solid-state image sensor, a color filter that transmits light of a specific wavelength is disposed on the light incident surface side of the planar solid-state image sensor. It is widely known that a single-plate solid-state imaging device widely used in digital cameras and the like is regularly arranged to transmit blue (B) light, green (G) light, and red (R) on each of two PDs arranged in two dimensions. Light color filter.

Further, in recent years, development of a solid-state image sensor having a structure in which an organic photoelectric conversion film is formed on a signal reading substrate has been carried out.

In such a solid-state image pickup element or photoelectric conversion element using an organic photoelectric conversion film, in particular, improvement in photoelectric conversion efficiency, responsiveness and heat resistance, and reduction in dark current Low becomes a problem.

Among them, Patent Document 1 to Patent Document 6, for example, disclose a photoelectric conversion element including a photoelectric conversion material having a specific structure.

Further, in such a solid-state image sensor or photoelectric conversion element using an organic photoelectric conversion film, in particular, improvement in photoelectric conversion efficiency and response speed and reduction in dark current have become problems.

Further, in the demand for application of the element to various applications, it is required to maintain characteristics (high photoelectric conversion efficiency, responsiveness, etc.) even when placed in a high temperature environment (for example, 90 ° C) for a long period of time. That is, excellent high temperature preservability is required.

Among them, for example, Patent Document 7 discloses a photoelectric conversion element using a compound having a specific structure of an amine, a thiophene, or a carbonyl group as a photoelectric conversion material.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2011-119745

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2011-213706

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2011-77198

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2009-200482

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2010-153764

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2009-88291

[Patent Document 7] Japanese Patent Laid-Open Publication No. 2011-77198

On the other hand, in order to apply a photoelectric conversion element to an image pickup element or photoelectric In various applications such as a pool, it is required that the photoelectric conversion element exhibits higher heat resistance in terms of the suitability of the self-made process. For example, as a process in the case of forming an image pickup element, there are many steps of performing a heat treatment (setting a color filter, providing a protective film, a soldering element, etc.), and it is required that the photoelectric conversion element exhibits excellent characteristics even after the steps. (High photoelectric conversion efficiency, low dark current characteristics).

Further, from the viewpoint of an increase in the number of pixels in the recent image pickup device, it is desired to further improve the photoelectric conversion efficiency or the responsiveness.

The inventors of the present invention have studied the photoelectric conversion elements described in Patent Literatures 1 to 6, and as a result, it has been found that the photoelectric conversion efficiency is deteriorated before and after the heat treatment (for example, 220 ° C), and the generation of dark current is increased. Meet the heat resistance required recently. Moreover, regarding the photoelectric conversion efficiency or responsiveness, the level required recently is not necessarily satisfied.

Furthermore, the inventors of the present invention have studied the photoelectric conversion element described in Patent Document 7, and as a result, it has been found that high-speed responsiveness (hereinafter also simply referred to as responsiveness) is not sufficient. Moreover, it is understood that the response speed is lowered when placed in a high temperature environment for a long time. That is, it is understood that the high-temperature storage property (hereinafter also referred to simply as high-temperature storage property) of the response speed is not sufficient.

In view of the above, the first embodiment of the present invention has an object to provide a photoelectric conversion element which is excellent in heat resistance and responsiveness and exhibits high photoelectric conversion efficiency.

Further, an object of the first embodiment of the present invention is to provide a method of using the above-described photoelectric conversion element, and a photosensor including the above photoelectric conversion element And imaging components.

Further, in view of the above-described facts, the second embodiment of the present invention has an object of providing a photoelectric conversion element excellent in responsiveness and high-temperature storage stability.

Further, an object of the second embodiment of the present invention is to provide a method of using the above-described photoelectric conversion element, and a photosensor and an image pickup element including the above-described photoelectric conversion element.

The present inventors have made intensive studies to solve the problems of the first embodiment, and as a result, it has been found that the compound (A) represented by the formula (1) described later is used as a photoelectric conversion material, and excellent heat resistance and responsiveness are obtained. Further, a photoelectric conversion element exhibiting high photoelectric conversion efficiency is completed, thereby completing the first embodiment of the present invention. In other words, the inventors of the present invention have found that the problems of the first embodiment described above can be solved by the following configuration.

(1) A photoelectric conversion element comprising, in order, a conductive film, a photoelectric conversion film containing a photoelectric conversion material, and a transparent conductive film, wherein the photoelectric conversion material contains the compound (A) represented by the formula (1) to be described later.

(2) The photoelectric conversion element according to the above (1), wherein the compound (A) is a compound (a1) represented by the formula (4) to be described later.

(3) The photoelectric conversion element according to the above (2), wherein Z ₁ is a group represented by the following general formula (Z1).

The photoelectric conversion element according to any one of the above aspects, wherein the Ar ¹¹ and/or Ar ¹² is an aryl group which may have a substituent.

(5) The photoelectric conversion element according to any one of (2) to (4) above, In the above, the compound (a1) is a compound (a2) represented by the formula (5) which will be described later.

The photoelectric conversion element according to any one of the above aspects, wherein the L is a hydrogen atom removed from any possible position of the compound represented by the formula (3) to be described later. The two-valent linkage.

(7) The photoelectric conversion element according to the above (5), wherein the compound (a2) is a compound (a3) represented by the formula (6) to be described later.

The photoelectric conversion element according to any one of the above aspects, wherein the n is 0.

The photoelectric conversion element according to any one of the above aspects, wherein the photoelectric conversion film further contains an n-type organic compound.

(10) The photoelectric conversion element according to the above (9), wherein the n-type organic compound contains a fullerene, and the fullerene is selected from the group consisting of fullerene and a derivative thereof.

(11) The photoelectric conversion element according to the above (10), wherein the content of the fullerene is based on the total content of the compound (A) and the fullerene (the thickness of the single layer of the fullerene) (The film thickness of the single layer of the compound (A) + the film thickness of the fullerene) is 50% by volume or more.

The photoelectric conversion element according to any one of the above aspects, wherein the electron blocking layer is further included between the conductive film and the transparent conductive film.

The photoelectric conversion element according to any one of the above aspects, wherein the photoelectric conversion film is formed by a vacuum deposition method.

The photoelectric conversion element according to any one of the above-mentioned (1), wherein the light is incident on the photoelectric conversion film via the transparent conductive film.

The photoelectric conversion element according to any one of the above aspects, wherein the transparent conductive film contains a transparent conductive metal oxide.

(16) A photosensor comprising the photoelectric conversion element according to any one of (1) to (15) above.

(17) An image pickup element comprising the photoelectric conversion element according to any one of (1) to (15) above.

(18) A method of using a photoelectric conversion element according to any one of (1) to (15), wherein the conductive film and the transparent conductive film are a pair of electrodes An electric field of 1 × 10 ^-4 V/cm to 1 × 10 ⁷ V/cm is applied between the pair of electrodes.

(19) A compound (a2) which is represented by the formula (5) which will be described later. In order to solve the problem of the second embodiment, the present inventors have conducted intensive studies, and as a result, it has been found that responsiveness and high-temperature storage can be obtained by using the compound (B) represented by the formula (11) described later as a photoelectric conversion material. The second embodiment of the present invention is completed by a photoelectric conversion element excellent in properties.

In other words, the inventors of the present invention have found that the problems of the second embodiment described above can be solved by the following configuration.

(20) A photoelectric conversion element comprising, in order, a conductive film, a photoelectric conversion film containing a photoelectric conversion material, and a transparent conductive film, wherein the photoelectric conversion material contains the compound (B) represented by the formula (11) to be described later.

The photoelectric conversion element according to the above (20), wherein the compound (B) is a compound (b2) represented by the formula (12) to be described later.

The photoelectric conversion element according to the above aspect (20), wherein, in the above formula (11), R ^3w and R ^5w and/or R ^6w and R ^8w are bonded to each other to form a ring.

The photoelectric conversion element according to any one of the above-mentioned (20), wherein the compound (B) is a compound (b3) represented by the formula (13) to be described later.

The photoelectric conversion element according to any one of the above aspects, wherein the photoelectric conversion film further includes an n-type organic semiconductor.

The photoelectric conversion element according to the above aspect (24), wherein the n-type organic semiconductor contains a fullerene, and the fullerene is selected from the group consisting of fullerenes and derivatives thereof.

The photoelectric conversion element according to any one of the above aspects, wherein the electron blocking layer is further included between the conductive film and the transparent conductive film.

(27) The photoelectric conversion element according to the above aspect, comprising the conductive film, the electron blocking layer, the photoelectric conversion film, the transparent conductive film, or the conductive film in the order, A photoelectric conversion film, the above electron blocking layer, and the transparent conductive film.

The photoelectric conversion element according to any one of the above aspects, wherein the q is an integer of 0 to 3.

The photoelectric conversion element according to any one of the above-mentioned (24), wherein the content of the fullerene is relative to the total content of the compound (B) and the fullerene (fullerene) Film thickness of single layer conversion / film thickness of single layer conversion of compound (B) + The film thickness of the fullerene-based single layer is) 50% by volume or more.

(30) The photoelectric conversion element according to any one of the above-mentioned, wherein the light is incident on the photoelectric conversion film via the transparent conductive film.

The photoelectric conversion element according to any one of the above aspects, wherein the transparent conductive film contains a transparent conductive metal oxide.

The photoelectric conversion element according to any one of the above aspects, wherein the transparent conductive film is directly laminated on the photoelectric conversion film.

(33) A photosensor comprising the photoelectric conversion element according to any one of (20) to (32) above.

(34) An image pickup device comprising the photoelectric conversion element according to any one of the above (20) to (32).

(35) A method of using a photoelectric conversion element according to any one of the above (20), wherein the conductive film and the transparent conductive film are a pair of electrodes An electric field of 1 × 10 ^-4 V/cm to 1 × 10 ⁷ V/cm is applied between the pair of electrodes.

(36) A compound (b2) which is represented by the following formula (12).

(37) A compound (b3) which is represented by the following formula (13).

As described below, according to the first embodiment of the present invention, it is possible to provide a photoelectric conversion element which is excellent in heat resistance and responsiveness and exhibits high photoelectric conversion efficiency.

Further, according to the first embodiment of the present invention, there is provided a method of using the photoelectric conversion element, and a photosensor including the photoelectric conversion element, and the above An imaging element of a photoelectric conversion element.

Further, as described below, according to the second embodiment of the present invention, it is possible to provide a photoelectric conversion element excellent in responsiveness and high-temperature storage stability.

Further, according to the second embodiment of the present invention, a method of using the photoelectric conversion element, an optical sensor including the photoelectric conversion element, and an imaging element including the photoelectric conversion element can be provided.

10a, 10b‧‧‧ photoelectric conversion components

11‧‧‧lower electrode (conductive film)

12‧‧‧Photoelectric conversion film

15‧‧‧Upper electrode (transparent conductive film)

16A‧‧‧Electronic barrier

16B‧‧‧ hole barrier

100‧‧‧Photographic components

101‧‧‧Substrate

102‧‧‧Insulation

103‧‧‧Connecting electrode

104‧‧‧ pixel electrodes (lower electrode)

105, 106‧‧‧Connecting Department

107‧‧‧Photoelectric conversion film

108‧‧‧ opposite electrode (upper electrode)

109‧‧‧buffer layer

110‧‧‧ Sealing layer

111‧‧‧Color Filter (CF)

112‧‧‧Baffle

113‧‧‧Lighting layer

114‧‧‧Protective layer

115‧‧‧ Counter electrode voltage supply unit

116‧‧‧Read circuit

(a) and (b) of FIG. 1 are schematic cross-sectional views each showing a configuration example of a photoelectric conversion element.

2 is a schematic cross-sectional view of one pixel of an image pickup element.

Fig. 3 is a ¹ H-NMR spectrum chart of the compound of (2).

4 is a ¹ H-NMR spectrum chart of the compound of (4).

Fig. 5 is a ¹ H-NMR spectrum chart of the compound of (10).

Hereinafter, the first embodiment and the second embodiment of the present invention will be described in order.

<<First embodiment>>

Hereinafter, a photoelectric conversion element according to a first embodiment of the present invention will be described with reference to the drawings. Fig. 1 (a) and Fig. 1 (b) are schematic cross-sectional views showing an embodiment of a photoelectric conversion element of the present invention.

The photoelectric conversion element 10a shown in (a) of Fig. 1 has the following laminated layers as follows A conductive film (hereinafter referred to as a lower electrode) 11 that functions as a lower electrode, an electron blocking layer 16A formed on the lower electrode 11, and a photoelectric conversion film 12 formed on the electron blocking layer 16A, A transparent conductive film (hereinafter also referred to as an upper electrode) 15 that functions as an upper electrode.

A configuration example of another photoelectric conversion element is shown in (b) of Fig. 1 . The photoelectric conversion element 10b shown in (b) of FIG. 1 has a configuration in which an electron blocking layer 16A, a photoelectric conversion film 12, a hole blocking layer 16B, and an upper electrode 15 are sequentially laminated on the lower electrode 11. Further, the order of lamination of the electron blocking layer 16A, the photoelectric conversion film 12, and the hole blocking layer 16B in (a) of FIG. 1 and (b) of FIG. 1 may be reversed depending on the use and characteristics.

In the configuration of the photoelectric conversion element 10a (10b), it is preferable that light is incident on the photoelectric conversion film 12 via the transparent conductive film 15.

Moreover, in the case where the photoelectric conversion element 10a (10b) is used, an electric field can be applied. In this case, the conductive film 11 and the transparent conductive film 15 are a pair of electrodes, and it is preferable to apply 1 × 10 ^-3 V / cm to 1 × 10 ⁷ V / cm between the pair of electrodes. The electric field is more preferably an electric field of 1 × 10 ^-4 V/cm to 1 × 10 ⁷ V/cm. From the viewpoint of performance and power consumption, it is preferred to apply an electric field of 1 × 10 ^-4 V / cm to 1 × 10 ⁶ V / cm, more preferably 1 × 10 ^-5 V / cm - 5 × 10 An electric field of ⁵ V/cm.

In addition, in the method of applying voltage, in (a) of FIG. 1 and (b) of FIG. 1, it is preferable to apply so that the side of the electron blocking layer 16A becomes a cathode and the side of the photoelectric conversion film 12 becomes an anode. In the case where the photoelectric conversion element 10a (10b) is used as the photo sensor, and in the case of being assembled into the image pickup element, the same can be used. The method applies a voltage.

Hereinafter, the form of each layer (photoelectric conversion film, lower electrode, upper electrode, electron blocking layer, hole blocking layer, and the like) constituting the photoelectric conversion element 10a (10b) will be described in detail.

First, the photoelectric conversion film will be described in detail.

[Photoelectric conversion film]

The photoelectric conversion film is a film containing the compound (A) represented by the formula (1) to be described later as a photoelectric conversion material.

In the first embodiment of the present invention, the compound (A) to be described later is used as the photoelectric conversion material, and therefore, it is a photoelectric conversion element which is excellent in heat resistance and responsiveness and exhibits high photoelectric conversion efficiency.

The reason for this is not clear, but it can be roughly estimated as follows.

According to the formula (1) to be described later, the compound (A) has a structure in which an amine moiety having a specific structure (aryl or heteroaryl group) and an acidic core site contain a specific structure (a 5-membered ring and a 6-membered ring-shaped ring). The connection portion (linkage group) of the formed structure is connected. Therefore, the planarity of the joint portion from the amine site is high, and the packing between molecules is strong. As a result, even if it is placed in a high temperature (for example, 220 ° C) environment, the change in the morphology of the photoelectric conversion film is small, and even if it is placed in a high temperature environment due to heat treatment or the like, the photoelectric conversion efficiency can be suppressed from being lowered. Or the deterioration of dark current. That is, it exhibits excellent heat resistance.

In the above, it is also estimated that the comparative examples 1 to 5 which will be described later having no specific structure at the joint portion or the joint portion having the above specific structure but amine The heat resistance of Comparative Example 6 and Comparative Example 7 in which the portions did not have a specific structure was insufficient.

In addition, as described above, since the compound (A) has a structure in which an electron-donating (donor-donating) amine moiety and an electron-accepting (acceptor) acidic core site are bonded to each other, it is absorbed by light absorption. The intramolecular production of the compound (A) results in good charge separation. As a result, the photoelectric conversion element using the compound (A) as a photoelectric conversion material exhibits high photoelectric conversion efficiency and excellent responsiveness.

<compound (A)>

In the first embodiment of the present invention, the compound (A) used as the photoelectric conversion material is represented by the following formula (1).

In the above formula (1), Ar ¹¹ and Ar ¹² each independently represent an aryl group which may have a substituent or a heteroaryl group which may have a substituent. Among them, from the viewpoint of further excellent light resistance and heat resistance, an aryl group which may have a substituent is preferred.

In the case where Ar ¹¹ or Ar ¹² is an aryl group, an aryl group having 6 to 30 carbon atoms is preferable, and an aryl group having 6 to 20 carbon atoms is more preferable. Specific examples of the ring constituting the aryl group include a benzene ring, a naphthalene ring, an anthracene ring, an anthracene ring, a phenanthrene ring, an anthracene ring, a linked triphenyl ring, a condensed tetraphenyl ring, a methylphenyl ring, and a dimethylphenyl ring. And a biphenyl ring (two phenyl groups may be linked by any linking means), a triphenyl group (three phenyl groups may be linked by any linking means), and the like.

Examples of the substituent of the aryl group include a substituent W and the like which will be described later.

In the case where Ar ¹¹ or Ar ¹² is a heteroaryl group, a heteroaryl group containing a ring of 5 members, 6 members or 7 members or a condensed ring thereof is preferred. Examples of the hetero atom contained in the heteroaryl group include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the ring constituting the heteroaryl group include a furan ring, a thiophene ring, a pyrrole ring, a pyrroline ring, a pyrrolidine ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, and an imidazoline ring. , imidazolium ring, pyrazole ring, pyrazoline ring, pyrazolidine ring, triazole ring, furazan ring, tetrazole ring, pyran ring, thiene ring, pyridine ring, piperidine ring, evil a azine ring, a morpholine ring, a thiazine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperazine ring, a triazine ring, a benzofuran ring, an isobenzofuran ring, a benzothiophene ring, an anthracene ring, Porphyrin ring, isoindole ring, benzoxazole ring, benzothiazole ring, oxazole ring, benzimidazole ring, quinoline ring, isoquinoline ring, porphyrin ring, pyridazine ring, quinazoline Ring, quinoxaline ring, dibenzofuran ring, dibenzothiophene ring, indazole ring, dibenzopyran ring, acridine ring, phenazin ring, phenanthroline ring, phenazine ring, phenoxazine ring , thiazide ring, pyridazine ring, quinazine ring, A pyridine ring, a naphthyridine ring, an anthracene ring, an acridine ring, and the like.

Examples of the substituent of the heteroaryl group include a substituent W and the like which will be described later.

In the above formula (1), R ¹¹ to R ¹³ each independently represent a hydrogen atom or a substituent. Examples of the substituent include a substituent W and the like which will be described later.

When R ¹¹ and R ¹² are a substituent, an alkyl group having 1 to 10 carbon atoms (particularly methyl group, ethyl group, propyl group, isopropyl group, and tert-butyl group) and carbon number are preferred. It is an alkenyl group of 2 to 10 (particularly a vinyl group, an allyl group), an alkoxy group having 1 to 10 carbon atoms, or an alkylthio group having 1 to 10 carbon atoms.

R ^{13 is} preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (particularly methyl or ethyl).

In the above formula (1), n represents an integer of 0 or more, and preferably represents an integer of 0 or more and 3 or less, and more preferably 0. In the case where n is increased, the absorption wavelength range can be made long wavelength, and the decomposition temperature due to heat becomes low. It is preferable that n = 0 in terms of having suitable absorption in the visible region and suppressing thermal decomposition at the time of vapor deposition film formation.

In the above formula (1), L represents a divalent linking group in which two hydrogen atoms are removed from any possible position of the compound represented by the following formula (2). L which is a divalent linking group, and a carbon atom bonded to the nitrogen atom in the above formula (1) and R ¹¹ (in the case of n=0, R ¹³ ) (in other words, R ¹¹ (n=0) In the case of the carbon atom of the root of R ¹³ )).

In the above formula (2), R ¹ to R ⁶ each independently represent a hydrogen atom or a substituent. Examples of the substituent include a substituent W and the like which will be described later. R ¹ to R ^{4 are} preferably a hydrogen atom.

In the above formula (2), X ¹ represents an oxygen atom, >CR ^1a R ^1b or >NR ^1c . Here, R ^1a , R ^1b and R ^1c each independently represent a hydrogen atom or a substituent (for example, a substituent W or the like described later), and among them, a hydrocarbon group or an aryl group is preferred, and a hydrocarbon group is more preferred, and further more preferably It is an alkyl group having a carbon number of 1 to 5. From the viewpoint of photoelectric conversion efficiency, X ^{1 is} preferably an oxygen atom or >CR ^1a R ^1b .

In the above formula (2), R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , and R ⁵ and R ⁶ may be bonded to each other to form a ring. Examples of the ring to be formed include a ring R and the like which will be described later. Among them, an aromatic hydrocarbon ring is preferred, and a benzene ring is more preferred. The ring formed may also have a substituent. Examples of the substituent include a substituent W and the like which will be described later.

As described above, in the formula (2), R ⁵ and R ⁶ may be bonded to each other to form a ring. The form in which R ⁵ and R ⁶ may form a ring may, for example, be a compound represented by the following formula (A).

In the formula (A), R ¹ to R ⁴ and X ¹ are synonymous with each group in the formula (2).

R ^5A and R ^6A each independently represent a hydrogen atom or a substituent. Examples of the substituent include a substituent W and the like which will be described later.

Q represents an aromatic ring. The aromatic ring may be a single ring or a polycyclic ring. Further, the number of rings of the ring to be included is not particularly limited, and may be a 5-member ring or a 6-member ring. Further, a hetero atom may be contained in the aromatic ring. In other words, it can also be a heteroaromatic ring. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, an anthracene ring, an anthracene ring, a furan ring, a benzofuran ring, a dibenzofuran ring, a pyrrole ring, an anthracene ring, and an indazole ring.

p represents 0 or 1. In the case where p is 0, R ^5A and R ^{6A are} directly bonded to the carbon atom of the 5-membered ring contained in X ¹ . When p is 1, the aromatic ring represented by Q and the 5-membered ring contained in X ¹ share a carbon atom and are bonded.

Two hydrogen atoms are removed from any possible position of the compound represented by the above formula (2) to form a divalent linking group. For example, when R ¹ to R ⁶ are a hydrogen atom and X ¹ is an oxygen atom, any two of the six hydrogen atoms of R ¹ to R ⁶ are removed to form a divalent linking group. Further, for example, when R ¹ is a methyl group, R ² to R ⁶ are a hydrogen atom, and X ¹ is >C(CH ₃ ) ₂ , three hydrogen atoms from R ¹ (methyl), R ² to R _Two hydrogen atoms of ^six , six hydrogen atoms of X ¹ (>C(CH ₃ ) ₂ ), and a total of 14 hydrogen atoms are removed by any two to form a divalent linking group.

Further, as described above, R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁵ and R ⁶ may be bonded to each other to form a ring. In the case where a ring is formed by the above combination, two hydrogen atoms are removed from any possible position in the compound containing the formed ring. Further, when the formed ring further has a substituent, when the substituent contains a hydrogen atom, the hydrogen atom may be removed.

The compound represented by the above formula (2) is preferably a compound represented by the following formula (3), because the heat resistance and the responsiveness are more excellent, and the photoelectric conversion efficiency is increased. In the above formula (1), L is preferably a divalent linking group obtained by removing two hydrogen atoms from any possible position of the compound represented by the following formula (3).

In the above formula (3), the definitions, specific examples, and suitable forms of R ¹ to R ⁴ are the same as those in the above formula (2).

In the above formula (3), the definition, specific examples, and suitable forms of X ¹ are the same as those of the above formula (2).

In the above formula (3), the definitions, specific examples, and suitable forms of R ⁷ to R ¹⁰ are the same as those of R ¹ to R ⁴ in the above formula (2).

In the above formula (1), A represents an acidic core. The acid nucleus referred to herein means when the lowest unoccupied Molecular Orbital (LUMO) value of the compound (A) is determined by the electron density functional method (B3LYP/6-31G(d) level). a substituent of less than -2.2 eV.

More specifically, those described in U.S. Patent No. 3,567,719, U.S. Patent No. 3,575,869, U.S. Patent No. 3,804,634, U.S. Patent No. 3,837,862, U.S. Patent No. 4,002,480, U.S. Patent No. 4,925,777,

In the formula (1), specific examples of A include the following.

(a) 1,3-dicarbonyl nucleus: for example, 1,3-indane diketone nucleus, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione , 1,3-dioxane-4,6-dione, and the like.

(b) pyrazolone nucleus: for example, 1-phenyl-2-pyrazolin-5-one, 3-methyl-1-phenyl-2-pyrazolin-5-one, 1-(2- Benzothiazolyl)-3-methyl-2-pyrazoline-5-one and the like.

(c) Isoxazolinone nucleus: for example, 3-phenyl-2-isoxazolin-5-one, 3-methyl-2-isoxazolin-5-one, and the like.

(d) anthrone nucleus: for example, 1-alkyl-2,3-dihydro-2-indanone or the like.

(e) 2,4,6-tris-oxy hexahydropyrimidine nucleus: for example, barbituric acid or 2-thiobarbituric acid and derivatives thereof. Examples of the derivative include a 1-alkyl group such as 1-methyl or 1-ethyl, and a 1,3-diox such as 1,3-dimethyl, 1,3-diethyl or 1,3-dibutyl. Base, 1,3-diphenyl, 1,3-di(p-chlorophenyl), 1,3-bis(p-ethoxycarbonylphenyl), etc., 1-ethyl- a 1-alkyl-1-aryl group such as 3-phenyl, a 1,3-diheteroaryl group such as 1,3-bis(2-pyridyl) or the like.

(f) 2-thio-2,4-thiazolidinone core: for example, rhodanine and its derivatives. Examples of the derivative include 3-methylcyclodanine, 3-ethylcyclodanning, 3-allyl cyclodanning, and the like, 3-alkylcyclodanning, 3-phenylcyclodanine, and the like. Around tannin, 3-(2-pyridyl) around tannin and other 3-heteroaryl groups around tannin.

(g) 2-thio-2,4-oxazolidinedione (2-thio-2,4-(3H,5H)-oxazolidinedione) nucleus: for example 3-ethyl-2-thio -2,4-oxazolidinedione and the like.

(h) Thiophenone core: for example, 3(2H)-thiophenone-1,1-dioxide or the like.

(i) 2-thio-2,5-thiazolidinone core: for example, 3-ethyl-2-thio-2,5-thiazolidinone or the like.

(j) 2,4-thiazolidinone core: for example 2,4-thiazolidinone, 3-ethyl-2,4-thiazolidinone, 3-phenyl-2,4-thiazolidinedione Wait.

(k) thiazolin-4-one core: for example, 4-thiazolinone, 2-ethyl-4-thiazolinone or the like.

(1) 2,4-imidazolidindione (ethylhydantoin) core: for example, 2,4-imidazolidinone, 3-ethyl-2,4-imidazolidinone, and the like.

(m) 2-thio-2,4-imidazolidindione (2-thioethyl carbazide) nucleus: for example 2-thio-2,4-imidazolidinone, 3-ethyl-2-sulfur Base-2,4-imidazolidinone and the like.

(n) Imidazoline-5-ketone nucleus: for example, 2-propyl decyl-2-imidazolin-5-one or the like.

(o) 3,5-pyrazolidinedione core: for example, 1,2-diphenyl-3,5-pyrazolidinedione, 1,2-dimethyl-3,5-pyrazolidinedione Wait.

(p) Benzothiophene-3(2H)-one nucleus: for example, benzothiophene-3(2H)-one, pendant oxybenzothiophene-3(2H)-one, di-sided benzobenzothiophene-3 (2H)-ketone and the like.

(q) indanone core: for example, 1-indanone, 3-phenyl-1-indanone, 3-methyl-1-indanone, 3,3-diphenyl-1 - Indoline, 3,3-dimethyl-1-indanone, and the like.

(r) a benzofuran-3-(2H)-one core: for example, a benzofuran-3-(2H)-one or the like.

(s) 2,2-dihydroindole-1,3-dione core and the like.

The acidic cores may further have a substituent, and may further condense other rings.

Further, in the case where A has a substituent, the substituent thereof may, for example, be enumerated Substituent W or the like described later.

In view of the reason that the photoelectric conversion efficiency is excellent, A is preferably a group represented by the following formula (Z1). * Represents R (1) in the formula ¹³ bonded carbon atoms (in other words a carbon atom R ¹³ is the root) a bonding position.

Z ₂ represents a ring containing at least 3 carbon atoms, and the ring is a 5-membered ring, a 6-membered ring, or a fused ring containing at least any of a 5-membered ring and a 6-membered ring.

In view of the reason that the photoelectric conversion efficiency is excellent, A is more preferably a group represented by the following formula (Z2) or a group represented by the following formula (Z3), and still more preferably represented by the formula (Z3). Base. * represents a bonding position of a carbon atom bonded to R ¹³ in the above formula (1).

[Chemical 6]

In the group represented by the formula (Z2), R ₁₁₁ to R ₁₁₄ each independently represent a hydrogen atom or a substituent. The substituent is, for example, a substituent W or the like described later, and a phenyl group, an alkyl group or a halogen atom is preferred, and an alkyl group having 1 to 6 carbon atoms or a chlorine atom is more preferred.

R ₁₁₁ and R ₁₁₂ , R ₁₁₂ and R ₁₁₃ , R ₁₁₃ and R ₁₁₄ may be bonded to each other to form a ring. Examples of the ring to be formed include a ring R and the like which will be described later. A suitable form of the ring to be formed is a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, an anthracene ring which may have a substituent, and the like. Examples of the substituent include a substituent W and the like which will be described later. A suitable form of the substituent may, for example, be a halogen atom (particularly a chlorine atom).

In the group represented by the formula (Z3), R ₂₁ to R ₂₆ each independently represent a hydrogen atom or a substituent. The substituent is, for example, a substituent W or the like described later, and a phenyl group, an alkyl group or a halogen atom is preferred, and an alkyl group having 1 to 6 carbon atoms or a chlorine atom is more preferred. R ₂₁ and R ₂₂ , R ₂₂ and R ₂₃ , R ₂₃ and R ₂₄ , R ₂₄ and R ₂₅ , and R ₂₅ and R ₂₆ may be bonded to each other to form a ring. Examples of the ring to be formed include a ring R and the like which will be described later. A suitable form of the ring formed is the same as the ring formed by bonding R ₁₁₁ and R ₁₁₂ , R ₁₁₂ and R ₁₁₃ , and R ₁₁₃ and R _{114 in} the above formula (Z2).

In the above formula (1), R ¹¹ and R ¹² , R ¹¹ and R ¹³ may be bonded to each other to form a ring. When n is 2 or more, a plurality of R ¹¹ and a plurality of R ¹² may be bonded to each other to form a ring. Examples of the ring to be formed include a ring R and the like which will be described later. Other rings (e.g., ring R) may also be condensed on the formed ring.

In the above formula (1), Ar ¹¹ and L, Ar ¹² and L, and Ar ¹¹ and Ar ¹² may be bonded to each other to form a ring. For reasons of further excellent heat resistance, it is preferred that Ar ¹¹ and L and/or Ar ¹² and L are bonded to each other to form a ring. The ring to be formed is, for example, a ring R to be described later, and is preferably a ring formed via a divalent linking group X ² from the viewpoint of photoelectric conversion efficiency. The divalent linking group X ² may, for example, be a single bond, an oxygen atom (-O-), a sulfur atom (-S-) or an alkylene group (preferably, >CR ^a R ^b : where R ^a and R ^b are a hydrogen atom or a hydrocarbon group), a silylene group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, a divalent heterocyclic group, or an imido group, among which an alkylene group is preferred. base.

In the above formula (1), L and A, L and R ¹¹ , L and R ¹² , L and R ¹³ may be bonded to each other to form a ring. Examples of the ring to be formed include a ring R and the like which will be described later. The ring formed by bonding L and A, L and R ¹¹ , L and R ¹² , and L and R ¹³ may have a substituent (for example, a substituent W or the like described later).

A suitable form of the compound (A) is, for example, a compound (a1) represented by the following formula (4).

[Chemistry 7]

In the above formula (4), the definitions, specific examples, and suitable forms of Ar ¹¹ and Ar ¹² are the same as those in the above formula (1).

In the above formula (4), the definitions, specific examples, and suitable forms of R ¹¹ to R ¹³ are the same as those of the above formula (1).

In the above formula (4), the definition of n and the appropriate form are the same as those of the above formula (1).

In the above formula (4), the definition, specific examples, and suitable forms of L are the same as those of the above formula (1).

In the above formula (4), Z ₁ represents a ring containing at least two carbon atoms, and the ring is a 5-membered ring, a 6-membered ring, or a condensed ring containing at least any of a 5-membered ring and a 6-membered ring. Z _{1 is} preferably a group represented by the above formula (Z1), more preferably a group represented by the above formula (Z2), and still more preferably a group represented by the above formula (Z3). .

A suitable form of the compound (a1) is, for example, a compound (a2) represented by the following formula (5).

[化8]

In the above formula (5), the definitions, specific examples, and suitable forms of Ar ¹¹ and Ar ¹² are the same as those in the above formula (1).

In the above formula (5), the definitions, specific examples, and suitable forms of R ¹¹ to R ¹³ are the same as those of the above formula (1).

In the above formula (5), the definition of n and the appropriate form are the same as those of the above formula (1).

In the above formula (5), the definition, specific examples, and suitable forms of L are the same as those of the above formula (1).

In the above formula (5), the definitions, specific examples, and suitable forms of R ⁵¹ to R ⁵⁴ are the same as those of R ₁₁₁ to R ₁₁₄ in the above formula (Z2).

A suitable form of the compound (a2) is, for example, a compound (a3) represented by the following formula (6).

In the above formula (6), the definitions, specific examples, and suitable forms of Ar ¹¹ and Ar ¹² are the same as those in the above formula (1).

In the above formula (6), the definitions, specific examples, and suitable forms of R ¹¹ to R ¹³ are the same as those of the above formula (1).

In the above formula (6), the definition of n and the appropriate form are the same as those of the above formula (1).

In the above formula (6), the definitions, specific examples, and suitable forms of R ¹ , R ³ and R ⁴ are the same as those in the above formula (2).

In the above formula (6), the definitions, specific examples, and suitable forms of R ⁷ , R ⁹ and R ¹⁰ are the same as those of R ¹ , R ³ and R ⁴ in the above formula (2).

In the above formula (6), the definition, specific examples, and suitable forms of X ¹ are the same as those in the above formula (2).

In the above formula (6), the definitions, specific examples, and suitable forms of R ⁵¹ to R ⁵⁴ are the same as those of R ₁₁₁ to R ₁₁₄ in the above formula (Z2).

In the above formula (6), R ³ and R ⁴ , R ⁹ and R ¹⁰ may be bonded to each other to form a ring. Examples of the ring to be formed include a ring R and the like which will be described later.

In the above formula (6), Ar ¹¹ and R ⁷ , Ar ¹¹ and R ⁹ , Ar ¹² and R ⁷ , Ar ¹² and R ⁹ , and Ar ¹¹ and Ar ¹² may be bonded to each other to form a ring. It is preferable that at least one of Ar ¹¹ and Ar ¹² and at least one of R ⁷ and R ⁹ are bonded to each other to form a ring, for the reason that the heat resistance is more excellent and the responsiveness is excellent. The ring to be formed is, for example, a ring R to be described later, and is preferably a ring formed through a divalent linking group X ² from the viewpoint of photoelectric conversion efficiency. Specific examples of X ² and suitable forms are the same as those of the above-mentioned divalent linking group X ² .

In the above formula (6), R ¹ and R ¹¹ , R ¹ and R ¹² , R ¹ and R ¹³ , R ³ and R ¹¹ , R ³ and R ¹² , R ³ and R ¹³ , R ⁴ and R ¹¹ , R ⁴ and R ¹² , R ⁴ and R ¹³ may be bonded to each other to form a ring. Examples of the ring to be formed include a ring R and the like which will be described later. The ring to be formed may have a substituent (for example, a substituent W or the like described later).

A suitable form of the compound (a3) is, for example, a compound (a4) represented by the following formula (7).

In the above formula (7), the definition, specific examples, and suitable forms of Ar ¹¹ are the same as those in the above formula (1).

In the above formula (7), the definitions, specific examples, and suitable forms of R ¹¹ to R ¹³ are the same as those in the above formula (1).

In the above formula (7), the definition of n and the appropriate form are the same as those of the above formula (1).

In the above formula (7), the definitions, specific examples, and suitable forms of R ¹ , R ³ and R ⁴ are the same as those in the above formula (2).

In the above formula (7), the definitions, specific examples, and suitable forms of R ⁷ and R ¹⁰ are the same as those of R ¹ and R ⁴ in the above formula (2).

In the above formula (7), the definition, specific examples, and suitable forms of X ¹ are the same as those in the above formula (2).

In the above formula (7), the definitions, specific examples, and suitable forms of R ⁵¹ to R ⁵⁴ are the same as those of R ₁₁₁ to R ₁₁₄ in the above formula (Z2).

In the above formula (7), R ⁷¹ to R ⁷⁴ each independently represent a hydrogen atom or a substituent. Examples of the substituent include a substituent W and the like which will be described later. R ⁷¹ to R ^{74 are} preferably a hydrogen atom.

In the above formula (7), specific examples of X ² and suitable forms are the same as those of the above-mentioned divalent linking group X ² .

In the above formula (7), Ar ¹¹ and R ⁷ , Ar ¹¹ and R ⁷¹ may be bonded to each other to form a ring. Examples of the ring to be formed include a ring R and the like which will be described later.

In the above formula (7), R ¹ and R ¹¹ , R ¹ and R ¹² , R ¹ and R ¹³ , R ³ and R ¹¹ , R ³ and R ¹² , R ³ and R ¹³ , R ⁴ and R ¹¹ , R ⁴ and R ¹² , R ⁴ and R ¹³ may be bonded to each other to form a ring. Examples of the ring to be formed include a ring R and the like which will be described later. The ring to be formed may have a substituent (for example, a substituent W or the like described later).

In the above formula (7), R ⁷¹ and R ⁷² , R ⁷² and R ⁷³ , R ⁷³ and R ⁷⁴ may be bonded to each other to form a ring. Examples of the ring to be formed include a ring R and the like which will be described later.

(substituent W)

The substituent W in the present specification is described.

Examples of the substituent W include a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group, a tricycloalkyl group), an alkenyl group (including a cycloalkenyl group, a bicycloalkenyl group), an alkynyl group, an aryl group, and a heterocyclic group ( Also known as heterocyclyl), cyano, hydroxy, nitro, carboxy, alkoxy, aryloxy, nonyloxy, heterocyclyloxy, decyloxy, aminecarakioxy, alkoxycarbonyl Oxyl, aryloxycarbonyloxy, amine (including anilino), ammonium, decylamino, aminocarbonylamino, alkoxycarbonylamino, aryloxycarbonylamino, amine sulfonamide Base, alkyl or arylsulfonylamino, fluorenyl, alkylthio, arylthio, heterocyclic thio, sulfonyl, sulfo, alkyl or arylsulfinyl, alkyl or aryl Sulfosyl, fluorenyl, aryloxycarbonyl, alkoxycarbonyl, aminemethanyl, aryl or heterocyclic azo, quinone imine, phosphino, phosphinyl, phosphinyloxy, Phosphoxylamino, phosphono, decyl, decyl, ureido, boronic acid (-B(OH) ₂ ), phosphate (-OPO(OH) ₂ ), sulfate (-OSO _{3 )} H), other known substituents, and the like.

Further, the details of the substituent are described in paragraph [0023] of JP-A-2007-234651.

(ring R)

The ring R in this specification is described.

Examples of the ring R include an aromatic hydrocarbon ring, an aromatic hetero ring, a non-aromatic hydrocarbon ring, a non-aromatic hetero ring, or a polycyclic fused ring formed by combining these rings. More specifically, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, an anthracene ring, a terphenylbenzene ring, a condensed tetraphenyl ring, a biphenyl ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, and an oxazole ring are exemplified. , thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, pyridazine ring, anthracene ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinoliz ring, quinoline ring , pyridazine ring, naphthyridine ring, quinoxaline ring, quinoxaline ring, isoquinoline ring, indazole ring, pyridine ring, acridine ring, phenanthroline ring, thiophene ring, benzopyran ring , dibenzopyran ring, thiophene ring, phenothiazine ring, phenazine ring, cyclopentane ring, cyclohexane ring, pyrrolidine ring, Piperidine ring, tetrahydrofuran ring, tetrahydropyran ring, tetrahydrothiophene ring, tetrahydrothiopyran ring and the like.

Ring R may also have the above substituent W.

The compound (A) can be produced by performing a partial change in accordance with a known method. Specific examples of the compound represented by the compound (A) are shown below, but the present invention is not limited to these specific examples.

[11]

[化12]

[Chemistry 13]

The ionization potential of the compound (A) (hereinafter sometimes abbreviated as IP) is preferably 6.0 eV or less, more preferably 5.8 eV or less, and particularly preferably 5.6 eV or less. If it is this range, it is preferable to carry out electrons with the material under a small electric resistance in the presence of an electrode and other materials. IP can be obtained by using AC-2 manufactured by Riken Keiki Co., Ltd.

The compound (A) is preferably one having a maximum absorption in the ultraviolet-visible absorption spectrum of 400 nm or more and less than 720 nm, and the peak wavelength of the absorption spectrum (maximum absorption wavelength) from the viewpoint of widely absorbing light in the visible region. It is preferably 450 nm or more and 700 nm or less, more preferably 480 nm or more and 650 nm or less, still more preferably 510 nm or more and 600 nm or less.

The maximum absorption wavelength of the compound (A) can be determined by measuring the chloroform solution of the compound (A) using UV-2550 manufactured by Shimadzu Corporation. The concentration of the chloroform solution is preferably 5 × 10 ^-5 mol / l to 1 × 10 ^-7 mol / l, more preferably 3 × 10 ^-5 mol / l ~ 2 × 10 ^-6 mol / l, particularly good It is 2 × 10 ^-5 mol / l ~ 5 × 10 ^-6 mol / l.

The compound (A) has a maximum absorption in the ultraviolet visible absorption spectrum of 400 nm or more and less than 720 nm, and the molar absorption coefficient of the maximum absorption wavelength is preferably 10,000 mol ^-1 . 1. In order to reduce the film thickness of the photoelectric conversion film by cm ^-1 or more, a device having high charge trapping efficiency and high-speed response is preferable, and a material having a large molar absorption coefficient is preferable. The molar absorption coefficient of the compound (A) is preferably 5000 mol ^-1 . 1. More than cm ^{-1 ,} more preferably 10,000 mol ^-1 . 1. More than cm ^-1 , especially 15000mol ^-1 . 1. Cm ^-1 or more. The molar absorption coefficient of the compound (A) is determined by using a chloroform solution.

The larger the difference between the melting point of the compound (A) and the vapor deposition temperature (melting point - vapor deposition temperature), the more difficult it is to decompose during vapor deposition, and it is preferable to apply a high temperature to increase the vapor deposition rate. Further, the difference between the melting point and the vapor deposition temperature (melting point - vapor deposition temperature) is preferably 40 ° C or higher, more preferably 50 ° C or higher, and still more preferably 60 ° C or higher.

Further, the melting point of the compound (A) is preferably 240 ° C or higher, more preferably 280 ° C or higher, still more preferably 300 ° C or higher. When the melting point is 240° C. or more, the melting before vapor deposition is small, the film formation can be stably performed, and the decomposition product of the compound is hard to be produced. Therefore, it is difficult to reduce the photoelectric conversion performance, which is preferable.

The vapor deposition temperature of the compound can be set to a temperature of 4 × 10 ^-4 Pa or less to heat the crucible, and the vapor deposition rate is 0.4 Å / s (0.4 × ^{10 -10} m / s).

The glass transition point (Tg) of the compound (A) is preferably 95 ° C or more. More preferably, it is 110 ° C or more, further preferably 135 ° C or more, particularly preferably 150 ° C or more, and most preferably 160 ° C or more. When the glass transition point becomes high, the heat resistance of the photoelectric conversion element is further improved, which is preferable.

The molecular weight of the compound (A) is preferably from 300 to 1,500, more preferably from 400 to 1,000, and particularly preferably from 500 to 800. When the molecular weight is too large, the vapor deposition temperature becomes high, and the molecules are easily decomposed. When the molecular weight is too small, the glass transition point of the photoelectric conversion film is lowered, and the heat resistance of the photoelectric conversion element is deteriorated.

The compound (A) is particularly useful as a material for a photoelectric conversion film used in an image pickup element, a photo sensor, or a photovoltaic cell. Further, in general, the compound (A) functions as a p-type organic semiconductor (compound) in the photoelectric conversion film and functions as a volatilization. Further, it can be used as a coloring material, a liquid crystal material, an organic semiconductor material, an organic light-emitting device material, a charge transport material, a medical material, a fluorescent diagnostic reagent material, or the like as another use.

The compound (A) is desirably subjected to sublimation purification before the production of the photoelectric conversion element or the image pickup element. The impurities or residual solvent contained before sublimation can be removed by sublimation purification. As a result, the performance of the photoelectric conversion element or the image pickup element can be stabilized. Moreover, it is easy to keep the vapor deposition rate constant.

The purity of the compound (A) before sublimation purification is preferably 99.0% or more, more preferably 99.5% or more, further preferably by high performance liquid chromatography (HPLC). It is more than 99.9%. In addition, the content of the residual solvent such as the reaction solvent or the purification solvent used in the step up to the obtaining of the compound (A) is preferably 3.0% or less, more preferably 1.0% or less, still more preferably 0.5% or less. Particularly good is below the detection limit. The content of the residual solvent (including moisture) is measured by ¹ H-NMR measurement, gas chromatography, Karl Fischer measurement, or the like. By increasing the purity and reducing the residual solvent, thermal decomposition during sublimation purification can be suppressed.

<Other materials>

The photoelectric conversion film may further contain a photoelectric conversion material of a p-type organic semiconductor (compound) or an n-type organic semiconductor (compound).

The p-type organic semiconductor (compound) is a donor organic semiconductor (compound), and mainly refers to an organic compound which is represented by a hole transporting organic compound and has a property of easily supplying electrons. More specifically, it means an organic compound having a small free potential when the two organic materials are brought into contact with each other. Therefore, if the donor organic compound is an organic compound having electron donating properties, any organic compound can be used. For example, a triarylamine compound, a benzidine compound, a pyrazoline compound, a styrylamine compound, an anthracene compound, a triphenylmethane compound, a carbazole compound, or the like can be used.

The n-type organic semiconductor (compound) is an acceptor organic semiconductor, and mainly refers to an organic compound represented by an electron-transporting organic compound and having a property of easily accepting electrons. More specifically, it means an organic compound having a large electron affinity when the two organic compounds are brought into contact with each other. Therefore, if the acceptor organic semiconductor is an organic compound having electron acceptability, any organic compound can be used. Preferably, a fullerene or a condensed aromatic carbocyclic compound (naphthalene derivative, an anthracene derivative, a phenanthrene derivative, a condensed tetraphenyl derivative, or an anthracene) selected from the group consisting of fullerenes and derivatives thereof is exemplified. a derivative, an anthracene derivative, a fluoranthene derivative), a nitrogen atom, a heterocyclic compound of an oxygen atom or a sulfur atom (for example, pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, pyridazine, porphyrin, isoquinoline, acridine, acridine) , phenazine, phenanthroline, tetrazole, pyrazole, imidazole, thiazole, oxazole, oxazole, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, anthracene, triazolopyrene Pyrazine, triazolopyrimidine, tetraazaindene, oxadiazole, imidazopyridine, pyrrolidine, pyrrolopyridine, thiadiazolopyridine, dibenzoazepine, tribenzoazepine, etc. A base compound, an anthracene compound, a cyclopentadiene compound, a decyl group compound, a metal complex having a nitrogen-containing heterocyclic compound as a ligand, and the like.

The above-mentioned n-type organic semiconductor (compound) is preferably a fullerene selected from the group consisting of fullerenes and derivatives thereof. The fullerene means fullerene C ₆₀ , fullerene C ₇₀ , fullerene C ₇₆ , fullerene C ₇₈ , fullerene C ₈₀ , fullerene C ₈₂ , fullerene C ₈₄ , Fuller The olefin C ₉₀ , the fullerene C ₉₆ , the fullerene C ₂₄₀ , the fullerene C ₅₄₀ , and the mixed fullerene are all a compound represented by adding a substituent to the fullerene. The substituent is preferably an alkyl group, an aryl group or a heterocyclic group. The fullerene derivative is preferably a compound described in JP-A-2007-123707.

The photoelectric conversion film is preferably a bulk heterostructure formed by mixing the compound (A) with a fullerene selected from the group consisting of fullerenes and derivatives thereof. The bulk heterostructure is a film in which a p-type organic compound (for example, a compound (A)) and an n-type organic compound are mixed and dispersed in a photoelectric conversion film, and can be formed by any of a wet method and a dry method. Preferably, it is formed by a co-evaporation method. Make up for light by containing a heterojunction structure The shortcoming of the carrier diffusion length of the electrotransformation film can improve the photoelectric conversion efficiency of the photoelectric conversion film. In addition, the bulk heterojunction structure is described in detail in [0013] to [0014] of JP-A-2005-303266.

The molar ratio of the n-type organic compound in the photoelectric conversion film to the above compound (A) (the number of moles of the n-type organic compound / the number of moles of the above compound (A)) is preferably 0.5 or more, more preferably It is 1 or more and 10 or less, and more preferably 2 or more and 5 or less.

From the viewpoint of the responsiveness of the photoelectric conversion element, the content of the fullerene is based on the total content of the compound (A) and the fullerene (= the thickness of the single layer of the fullerene) / (the compound (A) The film thickness of the single layer conversion + the film thickness of the fullerene-based single layer) is preferably 50% by volume or more, more preferably 55% by volume or more, still more preferably 65% by volume or more. The upper limit is not particularly limited, and is preferably 95% by volume or less, more preferably 90% by volume or less.

The photoelectric conversion film containing the compound (A) and the n-type organic compound of the present invention is a non-luminescent film and has characteristics different from those of an organic light-emitting element (OLED). The non-light-emitting film is a film having a light-emitting quantum efficiency of 1% or less, more preferably 0.5% or less, still more preferably 0.1% or less.

<film formation method>

The photoelectric conversion film 12 can be formed by a dry film formation method or a wet film formation method. Specific examples of the dry film formation method include vacuum vapor deposition, sputtering, ion plating, and physical vapor deposition (Molecular-Beam Epitaxy (MBE)). Vapor Deposition (PVD) method, or chemical vapor deposition (CVD) method such as plasma polymerization. The wet film formation method uses a casting method, a spin coating method, a dipping method, an LB method, or the like. A dry film forming method is preferred, and a vacuum evaporation method is more preferred. When the film formation is carried out by a vacuum deposition method, the production conditions such as the degree of vacuum and the vapor deposition temperature can be set in accordance with a usual method.

The thickness of the photoelectric conversion film 12 is preferably 10 nm or more and 1000 nm or less, more preferably 50 nm or more and 800 nm or less, and particularly preferably 100 nm or more and 500 nm or less. When it is 10 nm or more, a suitable dark current suppressing effect can be obtained, and by setting it as 1000 nm or less, suitable photoelectric conversion efficiency can be obtained.

[electrode]

The electrode (the upper electrode (transparent conductive film) 15 and the lower electrode (conductive film) 11) contains a conductive material. As the conductive material, a metal, an alloy, a metal oxide, a conductive compound, a mixture of these, or the like can be used.

In order to inject light from the upper electrode 15, the upper electrode 15 must be sufficiently transparent with respect to the light to be detected. Specific examples thereof include conductive metal oxides such as tin oxide (ATO, FTO), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO) doped with antimony or fluorine. a metal thin film of gold, silver, chromium, nickel, or the like, and a mixture or laminate of the metal and the conductive metal oxide, an inorganic conductive material such as copper iodide or copper sulfide, or an organic material such as polyaniline, polythiophene or polypyrrole. Conductive materials, and laminates of these with ITO, and the like. Among them, a transparent conductive metal oxide is preferred from the viewpoints of high conductivity, transparency, and the like.

In the case where a transparent conductive film such as TCO is used as the upper electrode 15, In the case of a DC short circuit or an increase in leakage current. One of the reasons is considered to be that the fine crack introduced into the photoelectric conversion film 12 is covered by a dense film such as TCO, and the conduction between the lower electrode 11 on the opposite side is increased. Therefore, in the case of an electrode having a relatively poor film quality such as aluminum, it is difficult to cause an increase in leakage current. The film thickness of the upper electrode 15 is controlled with respect to the film thickness of the photoelectric conversion film 12 (that is, the depth of the crack), and the increase in leakage current can be suppressed to a large extent. It is preferable that the thickness of the upper electrode 15 is 1/5 or less, preferably 1/10 or less of the thickness of the photoelectric conversion film 12.

In general, when the conductive film is made thinner than a certain range, the resistance value increases rapidly. In the solid-state image sensor in which the photoelectric conversion element of the present embodiment is incorporated, the sheet resistance is preferably 100 Ω/□ to 10000 Ω/ In other words, the degree of freedom in the range of the film thickness that can be thinned is large. Further, the thinner the thickness of the upper electrode (transparent conductive film) 15, the smaller the amount of light absorbed, and the light transmittance generally increases. The increase in light transmittance increases the light absorption in the photoelectric conversion film 12, and the photoelectric conversion capability is increased, so that it is excellent. With the thinning, considering the suppression of the leakage current, the increase in the resistance value of the film, and the increase in the transmittance, it is preferable that the film thickness of the upper electrode 15 is preferably 5 nm to 100 nm, and more preferably 5 nm. 20nm.

The lower electrode 11 may have a case where transparency is present depending on the use, and a case where a material that reflects light is opaque or the like is used instead. Specific examples thereof include conductive metal oxides such as tin oxide (ATO, FTO), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO) doped with antimony or fluorine. A conductive compound such as a metal such as gold, silver, chromium, nickel, titanium, tungsten or aluminum, or an oxide or nitride of the metal (titanium nitride (TiN) is exemplified), and further examples thereof include a mixture or laminate of a metal and a conductive metal oxide, an inorganic conductive material such as copper iodide or copper sulfide, an organic conductive material such as polyaniline, polythiophene or polypyrrole, and a laminate with the ITO or titanium nitride. Things and so on.

The method of forming the electrode is not particularly limited, and may be appropriately selected in consideration of the suitability of the electrode material. Specifically, it can be formed by a wet method such as a printing method or a coating method, a physical method such as a vacuum deposition method, a sputtering method, or an ion plating method, or a chemical method such as a CVD or plasma CVD method.

When the material of the electrode is ITO, the electron beam method, the sputtering method, the resistance heating vapor deposition method, the chemical reaction method (sol-gel method, etc.), or the dispersion of the indium tin oxide may be applied. form. Further, ultraviolet rays (UltraViolet, UV)-ozone treatment, plasma treatment, or the like can be applied to the film produced using ITO. When the material of the electrode is TiN, various methods including a reactive sputtering method are used, and UV-ozone treatment, plasma treatment, or the like can be performed.

[Charge blocking layer: electron blocking layer, hole blocking layer]

The photoelectric conversion element according to the first embodiment of the present invention may further include a charge blocking layer. By including this layer, the characteristics (photoelectric conversion efficiency, response speed, and the like) of the obtained photoelectric conversion element are more excellent. The charge blocking layer can be exemplified by an electron blocking layer and a hole blocking layer. The various layers are detailed below.

<Electronic barrier layer>

An electron-donating organic material can be used in the electron blocking layer. Specifically, the N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TPD) or 4,4'- can be used as the low molecular material. Aromatic diamine compound such as bis[N-(naphthyl)-N-phenyl-amino]biphenyl (α-NPD) , oxazole, oxadiazole, triazole, imidazole, imidazolidone, anthracene derivative, pyrazoline derivative, tetrahydroimidazole, polyarylalkane, butadiene, 4,4', 4" three (N -(3-methylphenyl)-N-phenylamino)triphenylamine (m-MTDATA), porphyrin, tetraphenylporphyrin copper, phthalocyanine, copper phthalocyanine, titanium phthalocyanine oxide, etc. Porphyrin compound, triazole derivative, oxadiazole derivative, imidazole derivative, polyarylalkane derivative, pyrazoline derivative, pyrazolone derivative, phenylenediamine derivative, arylamine derivative , an amine-substituted chalcone derivative, an oxazole derivative, a styryl hydrazine derivative, an anthrone derivative, an anthracene derivative, a decazane derivative, etc., and a phenylene vinylene, a phenylene vinylene, may be used as a polymer material. a polymer of hydrazine, carbazole, hydrazine, hydrazine, pyrrole, picoline, thiophene, acetylene, butadiyne or the like, or a derivative thereof, if not an electron-donating compound, a compound having sufficient hole transportability Further, it is also possible to use it. Specifically, it is preferably [0083] to [0089] of Japanese Patent Laid-Open Publication No. 2008-72090, and Japanese Patent Laid-Open No. 2011-176259. [0043] The compounds described in [0108] to [0156] of JP-A-2011-228615, and JP-A-2011-228615.

Further, the electron blocking layer may be composed of a plurality of layers.

An inorganic material can also be used for the electron blocking layer. In general, since the inorganic material has a larger dielectric constant than the organic material, when it is used in the electron blocking layer, a large voltage is applied to the photoelectric conversion film, and the photoelectric conversion efficiency can be improved. The material that can be used as the electron blocking layer is calcium oxide, chromium oxide, copper chromium oxide, manganese oxide, cobalt oxide, nickel oxide, copper oxide, copper oxide copper, copper beryllium oxide, cerium oxide, molybdenum oxide, indium copper oxide, and oxidation. Indium silver, yttrium oxide, and the like. In the case where the electron blocking layer is a single layer, The layer may be a layer containing an inorganic material, or in the case of a plurality of layers, one or two or more layers may be a layer containing an inorganic material.

<hole blocking layer>

An electron-accepting organic material can be used in the hole barrier layer.

The electron accepting material can be derived from an oxadiazole derivative such as 1,3-bis(4-tert-butylphenyl-1,3,4-oxadiazolyl)benzene (OXD-7) or deuterated methane. , biphenyl hydrazine derivative, bathocuproine, bathophenanthroline, and derivatives thereof, triazole compounds, tris(8-hydroxyquinoline) aluminum complex, bis (4) a -methyl-8-quinoline)aluminum complex, a distyryl arene derivative, a fluorene heterocyclic pentadiene compound, and the like. Further, even if it is not an electron-accepting organic material, it can be used as a material having sufficient electron transport properties. A porphyrin-based compound or a styrene-based system such as DCM (4-dicyanomethylidene-2-methyl-6-(4-(dimethylaminostyryl))-4Hpyran) can be used. Compound, 4H pyran compound. Specifically, a compound described in [0073] to [0078] of JP-A-2008-72090 is preferred.

The method for producing the charge blocking layer is not particularly limited, and the film can be formed by a dry film formation method or a wet film formation method. As the dry film formation method, a vapor deposition method, a sputtering method, or the like can be used. The vapor deposition may be any of physical vapor deposition (PVD) and chemical vapor deposition (CVD), and physical vapor deposition such as vacuum vapor deposition is preferred. For the wet film formation method, an inkjet method, a spray method, a nozzle printing method, a spin coating method, a dip coating method, a casting method, a die coating method, a roll coating method, a bar coating method, a gravure coating method, or the like can be used. From the viewpoint of patterning, an ink jet method is preferred.

The thickness of the charge blocking layer (electron blocking layer and hole blocking layer) is compared Preferably, it is 10 nm to 200 nm, more preferably 30 nm to 150 nm, and particularly preferably 50 nm to 100 nm. The reason for this is that if the thickness is too thin, the dark current suppressing effect is lowered, and if it is too thick, the photoelectric conversion efficiency is lowered.

[substrate]

The photoelectric conversion element according to the first embodiment of the present invention may further include a substrate. The type of the substrate to be used is not particularly limited, and a semiconductor substrate, a glass substrate, or a plastic substrate can be used.

Further, the position of the substrate is not particularly limited, and a conductive film, a photoelectric conversion film, and a transparent conductive film are usually laminated on the substrate in this order.

[sealing layer]

The photoelectric conversion element according to the first embodiment of the present invention may further include a sealing layer. The photoelectric conversion material has a phenomenon in which its performance is remarkably deteriorated due to the presence of deterioration factors such as water molecules, and the above deterioration can be prevented by dense metal oxide, metal nitride, metal oxynitride which does not penetrate water molecules. The sealing layer such as ceramic or diamond-like carbon (DLC) coats the entire photoelectric conversion film and seals it.

Further, the sealing layer can be selected and manufactured according to the description of paragraphs [0210] to [0215] of JP-A-2011-082508.

[Photo sensor]

The use of the photoelectric conversion element is, for example, a photovoltaic cell and a photosensor, and the photoelectric conversion element according to the first embodiment of the present invention is preferably used as a photosensor. The photo sensor may be a photo sensor using the above photoelectric conversion element alone, preferably the above The photoelectric conversion element is configured as a linear line sensor or a photosensor in a form of a two-dimensional sensor disposed on a plane. In the line sensor of the photoelectric conversion element according to the first embodiment of the present invention, the optical image information is converted into an electric signal by using an optical system and a driving unit as a scanner, and the like, and functions as an imaging element. In the two-dimensional sensor, the optical image information is converted into an electrical signal by imaging the optical system with the optical system as the imaging module, and functions as an imaging element.

The photovoltaic cell is a power generation device, so the efficiency of converting light energy into electrical energy becomes an important performance, but the current, which is a dark current in the dark, is not a problem in function. In addition, it is not necessary to provide a heating step in the subsequent stage of the color filter or the like. As a photosensor, it is important to convert the brightness signal into a high-precision signal with high precision. Therefore, the efficiency of converting the amount of light into a current is also an important performance. If the signal is output in the dark, it becomes noise, so the requirement is low. Dark current. In addition, tolerance to the latter step is also important.

[image sensor]

Next, a configuration example of the image pickup element including the photoelectric conversion element 10a will be described.

In the configuration examples described below, the description of the components and the like that are the same as those of the above-described components will be simplified or omitted from the drawings.

The imaging element is an element that converts optical information of an image into an electrical signal, and means that a plurality of photoelectric conversion elements are arranged on a matrix in the same plane, and the optical signal can be converted into an electrical signal in each photoelectric conversion element (pixel). , the telecommunication number according to each The pixels are sequentially output to components outside the imaging element. Therefore, each pixel contains one photoelectric conversion element and one or more transistors.

FIG. 2 is a schematic cross-sectional view showing a schematic configuration of an image pickup element according to an embodiment of the present invention. The imaging device can be used in an imaging device such as a digital camera or a digital video camera, an electronic endoscope, or an imaging module such as a mobile phone.

The imaging element includes a plurality of photoelectric conversion elements having the configuration shown in FIGS. 1(a) and 1(b), and a read circuit (the above-described read circuit read and photoelectric conversion film of each photoelectric conversion element) The circuit board of the signal corresponding to the charge generated in the circuit has a configuration in which the plurality of photoelectric conversion elements are arranged in a one-dimensional or two-dimensional shape on the same surface above the circuit board.

The image sensor 100 shown in FIG. 2 includes a substrate 101, an insulating layer 102, a connection electrode 103, a pixel electrode (lower electrode) 104, a connection portion 105, a connection portion 106, a photoelectric conversion film 107, and a counter electrode (upper electrode). 108. The buffer layer 109, the sealing layer 110, the color filter (CF) 111, the spacer 112, the light shielding layer 113, the protective layer 114, the counter electrode voltage supply unit 115, and the reading circuit 116.

The pixel electrode 104 has the same function as the lower electrode 11 of the photoelectric conversion element 10a shown in (a) of FIG. 1 and (b) of FIG. The counter electrode 108 has the same function as the upper electrode 15 of the photoelectric conversion element 10a shown in (a) of FIG. 1 and (b) of FIG. The configuration of the photoelectric conversion film 107 is the same as that provided between the lower electrode 11 and the upper electrode 15 of the photoelectric conversion element 10a shown in FIGS. 1(a) and 1(b).

The substrate 101 is a glass substrate or a semiconductor substrate such as Si. An insulating layer 102 is formed on the substrate 101. A plurality of pixel electrodes 104 and a plurality of connection electrodes 103 are formed on the surface of the insulating layer 102.

The photoelectric conversion film 107 is a layer common to all of the photoelectric conversion elements provided on the plurality of pixel electrodes 104.

The counter electrode 108 is one electrode common to all the photoelectric conversion elements provided on the photoelectric conversion film 107. The counter electrode 108 is formed on the connection electrode 103 disposed on the outer side of the photoelectric conversion film 107, and is electrically connected to the connection electrode 103.

The connection portion 106 is a plug or the like embedded in the insulating layer 102 to electrically connect the connection electrode 103 and the counter electrode voltage supply portion 115. The counter electrode voltage supply unit 115 is formed on the substrate 101, and a predetermined voltage is applied to the counter electrode 108 via the connection portion 106 and the connection electrode 103. When the voltage to be applied to the counter electrode 108 is higher than the power supply voltage of the image sensor, the booster circuit such as a charge pump boosts the power supply voltage to supply the predetermined voltage.

The reading circuit 116 is provided on the substrate 101 corresponding to each of the plurality of pixel electrodes 104, and reads a signal corresponding to the electric charge captured by the corresponding pixel electrode 104. The read circuit 116 includes, for example, a Charge Coupled Device (CCD), a Complementary Metal Oxide Semiconductor (CMOS) circuit, or a Thin Film Transistor (TFT) circuit, etc., by The light shielding layer (not shown) disposed in the insulating layer 102 is shielded from light. The read circuit 116 is electrically connected to the pixel electrode 104 corresponding thereto via the connection portion 105.

The buffer layer 109 covers the counter electrode 108 and is formed on the counter electrode 108. The sealing layer 110 covers the buffer layer 109 to be formed on the buffer layer 109. The color filter 111 is formed on the sealing layer 110 at a position opposed to each of the pixel electrodes 104. The spacer 112 is provided between the color filters 111 to improve the light transmission efficiency of the color filter 111.

The light shielding layer 113 is formed on a region other than the region where the color filter 111 and the spacer 112 are provided on the sealing layer 110, and prevents light from entering the photoelectric conversion film 107 formed outside the effective pixel region. The protective layer 114 is formed on the color filter 111, the spacer 112, and the light shielding layer 113 to protect the entire image pickup device 100.

In the imaging element 100 configured as described above, when light is incident, the light is incident on the photoelectric conversion film 107, and electric charges are generated therein. The hole in the generated charge is captured by the pixel electrode 104, and the voltage signal corresponding to the amount thereof is outputted to the outside of the image pickup element 100 by the reading circuit 116.

A method of manufacturing the image pickup element 100 is as follows.

The connection portion 105, the connection portion 106, the plurality of connection electrodes 103, the plurality of pixel electrodes 104, and the insulating layer 102 are formed on the circuit substrate on which the counter electrode voltage supply unit 115 and the read circuit 116 are formed. The plurality of pixel electrodes 104 are arranged on the surface of the insulating layer 102, for example, in a square lattice shape.

Next, the photoelectric conversion film 107 is formed on the plurality of pixel electrodes 104 by, for example, vacuum heating deposition. Next, the counter electrode 108 is formed under vacuum in the photoelectric conversion film 107 by, for example, sputtering. Next, the buffer layer 109 and the sealing layer 110 are sequentially formed on the counter electrode 108 by, for example, vacuum heating vapor deposition. Secondly, at After the color filter 111, the spacer 112, and the light shielding layer 113 are formed, the protective layer 114 is formed to complete the image pickup element 100.

In the method of manufacturing the image pickup device 100, a step of placing the image pickup element 100 in the middle of production between non-vacuum may be added between the step of forming the photoelectric conversion film 107 and the step of forming the sealing layer 110 to prevent a plurality of photoelectric conversions. The performance of the component deteriorates. By adding this step, it is possible to prevent the performance of the image pickup element 100 from deteriorating and to suppress the manufacturing cost.

<<2th embodiment>>

Hereinafter, a photoelectric conversion element according to a second embodiment of the present invention will be described. The photoelectric conversion element according to the second embodiment of the present invention has photoelectric conversion of the first embodiment shown in (a) of FIG. 1 and (b) of FIG. 1 except for the photoelectric conversion material in the photoelectric conversion film. The components are constructed in the same layer.

In other words, as one embodiment of the photoelectric conversion element of the second embodiment, as shown in FIG. 1( a ), a structure in which a conductive film that functions as a lower electrode is laminated is sequentially laminated (hereinafter also The lower electrode 11 is referred to as an electron blocking layer 16A formed on the lower electrode 11, the photoelectric conversion film 12 formed on the electron blocking layer 16A, and a transparent conductive film functioning as an upper electrode (hereinafter also referred to as an upper electrode). ) 15.

Further, as another embodiment of the photoelectric conversion element according to the second embodiment of the present invention, as shown in FIG. 1(b), an electron blocking layer 16A, a photoelectric conversion film 12, and electricity are sequentially laminated on the lower electrode 11. The structure of the hole blocking layer 16B and the upper electrode 15.

In the voltage application method of the photoelectric conversion element according to the second embodiment of the present invention, the application conditions similar to those of the voltage application method of the photoelectric conversion element according to the first embodiment described above are applied.

As described above, the photoelectric conversion element according to the second embodiment of the present invention has the same configuration as the photoelectric conversion element of the first embodiment except for the photoelectric conversion material in the photoelectric conversion film. Therefore, the same constituent elements (for example, the lower electrode, Description of the charge blocking layer (electron blocking layer, hole blocking layer), upper electrode, substrate, sealing layer, etc., the photoelectric conversion film will be mainly described below.

[Photoelectric conversion film]

The photoelectric conversion film is a film containing a compound (B) represented by the formula (11) to be described later as a photoelectric conversion material.

In the second embodiment of the present invention, since the compound (B) to be described later is used as the photoelectric conversion material, it is a photoelectric conversion element excellent in responsiveness and high-temperature storage stability.

The reason for this is not clear, but it can be roughly estimated as follows.

According to the formula (11) to be described later, the compound (B) has a structure in which an amine moiety and an acidic core site are linked by a linking site containing a thiophene, and the amine moiety and the linking site are condensed. Since the compound (B) has a structure in which the amine moiety and the linking site are condensed as described above, the molecular structure of the linking site from the amine site is higher than that of the compound which is not condensed. Moreover, it becomes a rigid structure with a small degree of freedom. Since the planarity is high, the accumulation between molecules becomes strong, and the movement of electrons or holes between molecules can be made rapid. As a result, the photoelectric conversion element using the compound (B) as a photoelectric conversion material exhibits excellent responsiveness. In addition, due to Since the degree of freedom is small and the structure is straight, the change in the morphology of the photoelectric conversion film is small even when left in a high temperature environment for a long period of time, and it can be maintained in a state of excellent responsiveness. That is, it exhibits excellent high temperature preservability.

It is presumed that the reason is that responsiveness and high-temperature preservability are not sufficient in Comparative Examples 1B to 4B which will be described later in the case where a compound having no amine ring portion and a linking site is not condensed.

In addition, as described above, the compound (B) has a structure in which an electron-donating (donating) amine moiety and an electron accepting (acceptor) acidic core site are linked by a linking site containing a thiophene. Absorption produces good charge separation in the molecule of compound (B). As a result, the photoelectric conversion element using the compound (B) as a photoelectric conversion material exhibits high photoelectric conversion efficiency.

<compound (B)>

In the second embodiment of the present invention, the compound (B) used as the photoelectric conversion material is represented by the following formula (11).

In the above formula (11), R ^1w and R ^2w each independently represent an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent. Among them, from the viewpoint of photoelectric conversion efficiency and responsiveness, an aryl group which may have a substituent is preferred.

When R ^1w or R ^2w is an alkyl group, an alkyl group having 1 to 22 carbon atoms is preferred, and an alkyl group having 1 to 8 carbon atoms is more preferred. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group and the like.

Examples of the substituent of the alkyl group include a substituent W and the like which will be described later.

In the case where R ^1w or R ^2w is an aryl group, an aryl group having 6 to 30 carbon atoms is preferable, and an aryl group having 6 to 20 carbon atoms is more preferable. Specific examples of the ring constituting the aryl group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, an anthracene ring, a linked triphenyl ring, a condensed tetraphenyl ring, and a biphenyl ring (two phenyl groups may be bonded by any The method is linked to), triphenylene (three phenyl groups may be linked by any means of attachment), and the like.

Examples of the substituent of the aryl group include a substituent W and the like which will be described later.

In the case where R ^1w or R ^2w is a heteroaryl group, a heteroaryl group containing a ring of 5 members, 6 members or 7 members or a fused ring thereof is preferred. Examples of the hetero atom contained in the heteroaryl group include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the ring constituting the heteroaryl group include a furan ring, a thiophene ring, a pyrrole ring, a pyrroline ring, a pyrrolidine ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, and an imidazoline ring. , imidazolium ring, pyrazole ring, pyrazoline ring, pyrazolidine ring, triazole ring, furazan ring, tetrazole ring, pyran ring, thiene ring, pyridine ring, piperidine ring, evil a azine ring, a morpholine ring, a thiazine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperazine ring, a triazine ring, a benzofuran ring, an isobenzofuran ring, a benzothiophene ring, an anthracene ring, Porphyrin ring, isoindole ring, benzoxazole ring, benzothiazole ring, carbazole ring, benzimidazole ring, quinoline ring, isoquinoline ring, porphyrin ring, pyridazine ring, quinazoline Ring, quinoxaline ring, dibenzofuran ring, dibenzothiophene ring, indazole ring, dibenzopyran ring, acridine ring, phenazin ring, phenanthroline ring, phenazine ring, phenoxazine ring , thiazide ring, pyridazine ring, quinazine ring, A pyridine ring, a naphthyridine ring, an anthracene ring, an acridine ring, and the like.

Examples of the substituent of the heteroaryl group include a substituent W and the like which will be described later.

In the above formula (11), R ^3w to R ^9w each independently represent a hydrogen atom or a substituent. Examples of the substituent include the above-mentioned substituent W and the like.

In the case where R ^3w to R ^8w is a substituent, an alkyl group having 1 to 10 carbon atoms (particularly methyl group, ethyl group, propyl group, isopropyl group, and tert-butyl group) and carbon number are preferred. It is an alkenyl group of 2 to 10 (particularly a vinyl group, an allyl group), an alkoxy group having 1 to 10 carbon atoms, or an alkylthio group having 1 to 10 carbon atoms.

R ^{9w is} preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (particularly methyl or ethyl), more preferably a hydrogen atom.

In the above formula (11), p represents 0 or 1. In order to exhibit higher photoelectric conversion efficiency, p is preferably 1.

In the above formula (11), q represents an integer of 0 or more. From the standpoint of exhibiting more excellent responsiveness, q is preferably an integer of 0 to 3, more preferably 0.

In the above formula (11), R ^1w and R ^2w , R ^3w and R ^4w , R ^3w and R ^5w , R ^5w and R ^6w , R ^6w and R ^8w , R ^7w and R ^8w , R ^7w and R ^9w may also be used. They are bonded to each other to form a ring. When q is 2 or more, a plurality of R ^7w and a plurality of R ^8w may be bonded to each other to form a ring.

Examples of the ring to be formed include a ring R and the like which will be described later. The formed ring can also be shrunk Loop other rings (such as ring R above).

When p or q is 1 or more, from the viewpoint of photoelectric conversion efficiency and high-temperature storage stability, it is preferred that R ^3w and R ^5w and/or R ^6w and R ^8w are bonded to each other to form a ring. In the case where R ^3w and R ^5w and/or R ^6w and R ^8w are bonded to each other to form a ring, the ring formed is preferably an aromatic hydrocarbon ring or an aromatic heterocyclic ring (especially having a sulfur atom as a hetero atom). An aromatic heterocyclic ring of an atom), more preferably an aromatic hydrocarbon ring (particularly a benzene ring).

In the above formula (11), A ^1w represents an acid core. Here, the acid nucleus is a substituent which is less than -2.2 eV when the LUMO value of the compound (B) is determined by the electron density functional method (B3LYP/6-31G (d) level).

More specifically, those described in U.S. Patent No. 3,567,719, U.S. Patent No. 3,575,869, U.S. Patent No. 3,804,634, U.S. Patent No. 3,837,862, U.S. Patent No. 4,002,480, U.S. Patent No. 4,925,777,

In the formula (11), specific examples of A ^1w include (a) to (s) described in A ¹ of the above-described first embodiment.

In the case where A ^1w has a substituent, examples of the substituent include the above-mentioned substituent W and the like.

In view of the reason that the self-responsibility is more excellent and the photoelectric conversion efficiency is high, A ^{1w is} preferably a group represented by the following formula (Z1). * represents a bonding position with a carbon atom at the root of R ^9w in the above formula (11) (in other words, a carbon atom to which R ^9w is bonded).

Z ² represents a ring containing at least 3 carbon atoms, and the ring is a 5-membered ring, a 6-membered ring, or a fused ring containing at least any of a 5-membered ring and a 6-membered ring.

In view of the reason that the self-responsibility is more excellent and the photoelectric conversion efficiency is high, A ^{1w is more} preferably a group represented by the following formula (Z12) or a group represented by the following formula (Z13), and further Preferred is a group represented by the formula (Z13). * represents a bonding position with a carbon atom at the root of R ^9w in the above formula (11).

In the group represented by the formula (Z12), R _11w to R _14w each independently represent a hydrogen atom or a substituent. A suitable form of the substituent may, for example, be a halogen atom (particularly a chlorine atom).

R _11w and R _12w , R _12w and R _13w , R _13w and R _14w may be bonded to each other to form a ring. Examples of the ring to be formed include the above-mentioned ring R and the like. A suitable form of the ring to be formed is a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, an anthracene ring which may have a substituent, and the like. Examples of the substituent include the above-mentioned substituent W and the like. A suitable form of the substituent may, for example, be a halogen atom (particularly a chlorine atom).

In the group represented by the formula (Z13), R _21w to R _26w each independently represent a hydrogen atom or a substituent. Examples of the substituent include the above-mentioned substituent W and the like, and an alkyl group is preferred, and an alkyl group having 1 to 6 carbon atoms is more preferred. R _21w and R _22w , R _22w and R _23w , R _23w and R _24w , R _24w and R _25w , and R _25w and R _26w may be bonded to each other to form a ring. Examples of the ring to be formed include the above-mentioned ring R and the like. A suitable form of the ring to be formed is the same as the ring formed by bonding R _11w to R _12w , R _12w to R _13w , and R _13w to R _14w in the above formula (Z12).

In the above formula (11), at least one of R ^1w and R ^2w is bonded to any of R ^3w , R ^4w and R ^5w to form a ring. Thereby, the compound (B) has a structure in which the amine moiety and the thiophene-containing linking site are condensed. As a result, the effects (excellent responsiveness and high-temperature preservability) of the second embodiment of the present invention are obtained as described above.

Examples of the ring formed by bonding at least one of R ^1w and R ^2w to any of R ^3w , R ^4w and R ^5w include the above-mentioned ring R and the like.

The ring formed may also have a divalent linking group X. In other ^words , when at least one of R ^1w and R ^2w is bonded to any of R ^3w , R ^4w and R ^5w , they may be directly bonded to each other or may be bonded via a linking group X to form a ring. The linking group X may, for example, be an oxygen atom (-O-), a sulfur atom (-S-) or an alkylene group (preferably, >CR ^a R ^b : where R ^a and R ^b are a hydrogen atom or a hydrocarbon group), A decylene group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an extended aryl group, a divalent heterocyclic group, or -NR ^C - (R ^C represents a hydrogen atom or a substituent (for example, the above substituent W) ))Wait.

Further, at least one of R ^1w and R ^2w is preferably a ring formed by bonding an alkyl group to any of R ^3w , R ^4w and R ^5w , and more preferably by a dimethylmethylene group. Any one of R ^3w , R ^4w and R ^5w is bonded to form a ring.

A suitable form of the compound (B) is, for example, a compound (b4) represented by the following formula (14).

In the above formula (14), the definition, specific examples, and suitable forms of R ^1w to R ^9w are the same as those of the above formula (11).

In the above formula (14), the definitions of p and q and suitable forms are the same as those of the above formula (11).

In the above formula (14), R ^10w and R ^11w each independently represent a hydrogen atom or a substituent. Examples of the substituent include the above-mentioned substituent W and the like.

R ^10w and R ^11w may also be bonded to each other to form a ring. Examples of the ring to be formed include the above-mentioned ring R and the like.

In the case where R ^10w and R ^11w are bonded to each other to form a ring, a suitable form of the ring to be formed is 1,3-indanedione ring, 1,3-benzoindanedion ring, and 1, 3-cyclohexanedione ring, 5,5-dimethyl-1,3-cyclohexanedione ring, 1,3-dioxane-4,6-dione ring, 1-phenyl-2-pyridyl Oxazoline-5-one ring, 3-methyl-1-phenyl-2-pyrazolin-5-one ring, 1-(2-benzothiazolyl)-3-methyl-2-pyrazoline -5-ketone ring, pyrimidine-2,4,6-trione ring and the like.

A suitable form of the compound (b4) is, for example, a compound (b5) represented by the following formula (15).

In the above formula (15), the definition, specific examples, and suitable forms of R ^1w to R ^9w are the same as those of the above formula (11).

In the above formula (15), the definitions of p and q and suitable forms are the same as those of the above formula (11).

In the above formula (15), R ^11w and R ^12w each independently represent a hydrogen atom or a substituent. Examples of the substituent include the above-mentioned substituent W and the like.

R ^11w and R ^12w may also be bonded to each other to form a ring. Examples of the ring to be formed include the above-mentioned ring R and the like. A suitable form of the formed ring is the same as the ring formed by the bonding of R ^10w and R ^11w in the above formula (14).

A suitable form of the compound (b5) is, for example, a compound (b6) represented by the following formula (16).

In the above formula (16), the definition, specific examples, and suitable forms of R ^1w to R ^9w are the same as those of the above formula (11).

In the above formula (16), the definitions of p and q and the appropriate forms are the same as those of the above formula (11).

In the above formula (16), R ^13w and R ^14w each independently represent a hydrogen atom or a substituent. Examples of the substituent include the above-mentioned substituent W and the like.

R ^13w and R ^14w may also be bonded to each other to form a ring. Examples of the ring to be formed include the above-mentioned ring R and the like. A suitable form of the ring to be formed is a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, an anthracene ring which may have a substituent, and the like. Examples of the substituent include the above-mentioned substituent W and the like. A suitable form of the substituent may, for example, be a halogen atom (particularly a chlorine atom).

A suitable form of the compound (b6) is, for example, a compound (b2) represented by the following formula (12).

In the above formula (12), the definition, specific examples, and suitable forms of R ^1w to R ^9w are the same as those of the above formula (11).

In the above formula (12), the definitions of p and q and the appropriate forms are the same as those of the above formula (11).

In the above formula (12), R ^15w to R ^18w each independently represent a hydrogen atom or a substituent. Examples of the substituent include the above-mentioned substituent W and the like. A suitable form of the substituent may, for example, be a halogen atom (particularly a chlorine atom).

R ^15w and R ^16w , R ^16w and R ^17w , and R ^17w and R ^18w may be bonded to each other to form a ring. Examples of the ring to be formed include the above-mentioned ring R and the like. A suitable form of the formed ring is the same as the ring formed by bonding R ^13w and R ^14w in the above formula (16) to each other.

A suitable form of the compound (b2) is, for example, a compound (b3) represented by the following formula (13). When the compound (b2) is the above compound (b3), the photoelectric conversion efficiency is improved.

In the above formula (13), the definition, specific examples, and suitable forms of R ^1w to R ^9w are the same as those of the above formula (11).

In the above formula (13), the definitions of p and q and suitable forms are the same as those of the above formula (11).

In the above formula (13), R ^15w and R ^18w to R ^22w each independently represent a hydrogen atom or a substituent. Examples of the substituent include the above-mentioned substituent W and the like. A suitable form of the substituent may, for example, be a halogen atom (particularly a chlorine atom).

R ^15w and R ^19w, R ^19w and R ^20w, R ^20w and R ^21w, R ^21w and R ^22w, R ^22w and R ^18w may be bonded to each other to form a ring. Examples of the ring to be formed include the above-mentioned ring R and the like. A suitable form of the formed ring is the same as the ring formed by bonding R ^13w and R ^14w in the above formula (16) to each other.

Other suitable examples of the compound (B) include the compound (b7) represented by the following formula (17), the compound (b8) represented by the following formula (18), and the following formula (19). Compound (b9) and the like.

In the above formula (17), the definition, specific examples, and suitable forms of R ^6w to R ^9w are the same as those of the above formula (11).

In the above formula (17), the definition of q and the appropriate form are the same as those of the above formula (11).

In the above formula ^{(17), R 71w ~ R} 74w each independently represent a hydrogen atom or a substituent. Examples of the substituent include the above-mentioned substituent W and the like. Among them, preferred are hydrogen atoms.

In the above formula (17), the definition and the suitable range of R ^75w are the same as those of R ^1w and R ^{2w in the} above formula (11).

^R 71w and R ^72w, R ^72w and ^R 73w, R 73w and ^R 74w, R 71w and R ^75w may be bonded to each other to form a ring. Examples of the ring to be formed include the above-mentioned ring R and the like.

In the above formula (17), X ^1w represents an oxygen atom (-O-), a sulfur atom (-S-), a nitrogen atom having a substituent (-NR'-), a carbon atom having a substituent (-CR'R). "-), a halogen atom having a substituent (-SiR'R"-). Among them, a sulfur atom is preferred. R' and R" each independently represent a substituent, and the definition thereof is the same as the above-mentioned substituent W. Among them, R' and R" are preferably an alkyl group.

In the above formula (17), X ^2w represents a single bond or a linking group. The specific example of the linking group is the same as X described above.

In the above formula (17), the definition of A ^1w and a suitable form are the same as those of the above formula (11).

In the above formula (18), the definition, specific examples, and suitable forms of R ^6w to R ^9w are the same as those of the above formula (11).

In the above formula (18), the definition of q and the appropriate form are the same as those of the above formula (11).

In the above formula (18), the definition of ^R 71w ~ R 74w and a suitable morphology and the above equation (17) the same.

In the above formula (18), the definition of R ^75w and a suitable form are the same as those of the above formula (17).

R ^71w and R ^75w , R ^75w and R ^81w may be bonded to each other to form a ring. Examples of the ring to be formed include the above-mentioned ring R and the like.

In the above formula (18), X ^2w represents a single bond or a linking group. The specific example of the linking group is the same as X described above.

In the above formula (18), the definition of A ^1w and a suitable form are the same as those of the above formula (11).

In the above formula (18), R ^81w and R ^82w represents a hydrogen atom or a substituent. Examples of the substituent include the above-mentioned substituent W and the like. Among them, preferred are hydrogen atoms. R ^81w and R ^82w may bond to each other to form a ring. Examples of the ring to be formed include the above-mentioned ring R and the like.

In the above formula (19), the definition, specific examples, and suitable forms of R ^6w to R ^9w are the same as those of the above formula (11).

In the above formula (19), the definition of q and the appropriate form are the same as those of the above formula (11).

In the above formula (19), the definition of ^R 71w ~ R 74w and a suitable morphology and the above equation (17) the same.

In the above formula (19), the definition of R ^75w and a suitable form are the same as those of the above formula (17).

In the above formula (19), X ^2w represents a single bond or a linking group. The specific example of the linking group is the same as X described above.

In the above formula (19), the definition of A ^1w and a suitable form are the same as those of the above formula (11).

The compound (B) can be produced by performing a partial change in accordance with a known method. Specific examples (1) to (62) of the compound represented by the compound (B) are shown below, but the present invention is not limited to these specific examples.

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[Chem. 26]

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The free potential of the compound (B) (hereinafter sometimes abbreviated as IP) is preferably 6.0 eV or less, more preferably 5.8 eV or less, and particularly preferably 5.6 eV or less. If it is this range, it is preferable to carry out electrons with the material under a small electric resistance in the presence of an electrode and other materials. IP can be obtained using AC-2 manufactured by Riken Keiki Co., Ltd.

The compound (B) is preferably one having a maximum absorption in the ultraviolet-visible absorption spectrum of 400 nm or more and less than 720 nm, and the peak wavelength of the absorption spectrum (maximum absorption wavelength) from the viewpoint of widely absorbing light in the visible region. More It is preferably 450 nm or more and 700 nm or less, more preferably 480 nm or more and 650 nm or less, still more preferably 510 nm or more and 600 nm or less.

The maximum absorption wavelength of the compound (B) can be determined by measuring the chloroform solution of the compound (B) using UV-2550 manufactured by Shimadzu Corporation. The concentration of the chloroform solution is preferably 5 × 10 ^-5 mol / l to 1 × 10 ^-7 mol / l, more preferably 3 × 10 ^-5 mol / l ~ 2 × 10 ^-6 mol / l, particularly good It is 2 × 10 ^-5 mol / l ~ 5 × 10 ^-6 mol / l.

The compound (B) has a maximum absorption in the ultraviolet-visible absorption spectrum of 400 nm or more and less than 720 nm, and the molar absorption coefficient of the maximum absorption wavelength is preferably 10,000 mol ^-1 . 1. In order to reduce the film thickness of the photoelectric conversion film by cm ^-1 or more, a device having high charge trapping efficiency and high-speed response is preferable, and a material having a large molar absorption coefficient is preferable. The molar absorption coefficient of the compound (B) is preferably 5000 mol ^-1 . 1. More than cm ^{-1 ,} more preferably 10,000 mol ^-1 . 1. More than cm ^-1 , especially 15000mol ^-1 . 1. Cm ^-1 or more. The molar absorption coefficient of the compound (B) was measured with a chloroform solution.

The larger the difference between the melting point of the compound (B) and the vapor deposition temperature (melting point-vapor deposition temperature), the more difficult it is to decompose during vapor deposition, and it is preferable to apply a high temperature to increase the vapor deposition rate. Further, the difference between the melting point and the vapor deposition temperature (melting point - vapor deposition temperature) is preferably 40 ° C or higher, more preferably 50 ° C or higher, and still more preferably 60 ° C or higher.

Further, the melting point of the compound (B) is preferably 200 ° C or higher, more preferably 220 ° C or higher, still more preferably 240 ° C or higher. When the melting point is 200° C. or higher, the melting before vapor deposition is small, the film formation can be stably performed, and the decomposition product of the compound is hardly generated. Therefore, it is difficult to reduce the photoelectric conversion performance, which is preferable.

The vapor deposition temperature of the compound can be set to a temperature of 4 × 10 ^-4 Pa or less to heat the crucible, and the vapor deposition rate is 0.4 Å / s (0.4 × ^{10 -10} m / s).

The glass transition point (Tg) of the compound (B) is preferably 95 ° C or higher, more preferably 110 ° C or higher, still more preferably 135 ° C or higher, particularly preferably 150 ° C or higher, and most preferably 160 ° C. the above. When the glass transition point becomes high, the heat resistance of the photoelectric conversion element is improved, which is preferable.

The molecular weight of the compound (B) is preferably from 300 to 1,500, more preferably from 400 to 1,000, and particularly preferably from 500 to 800. When the molecular weight is too large, the vapor deposition temperature becomes high, and the molecules are easily decomposed. When the molecular weight is too small, the glass transition point of the photoelectric conversion film is lowered, and the heat resistance of the photoelectric conversion element is deteriorated.

The compound (B) is particularly useful as a material for a photoelectric conversion film used in an image pickup element, a photo sensor, or a photovoltaic cell. Further, in general, the compound (B) functions as a p-type organic semiconductor (compound) in the photoelectric conversion film. Further, it can be used as a coloring material, a liquid crystal material, an organic semiconductor material, an organic light-emitting device material, a charge transport material, a medical material, a fluorescent diagnostic reagent material, or the like as another use.

<Other materials>

The photoelectric conversion film may further contain a photoelectric conversion material of a p-type organic semiconductor (compound) or an n-type organic semiconductor (compound).

Examples of the p-type organic semiconductor and the n-type organic semiconductor include the p-type organic semiconductor and the n-type organic semiconductor described in the first embodiment.

An n-type organic semiconductor in the photoelectric conversion film relative to the above compound (B) The molar ratio (n-type organic semiconductor / the above compound (B)) is preferably 0.5 or more, more preferably 1 or more, 10 or less, still more preferably 2 or more and 5 or less.

From the viewpoint of the responsiveness of the photoelectric conversion element, the content of the fullerene is based on the total content of the compound (B) and the fullerene (= the film thickness of the single layer of the fullerene) (the compound (B) The film thickness of the single layer conversion + the film thickness of the fullerene-based single layer) is preferably 50% by volume or more, more preferably 55% by volume or more, still more preferably 65% by volume or more. The upper limit is not particularly limited, and is preferably 95% by volume or less, more preferably 90% by volume or less.

The photoelectric conversion film (otherwise, the n-type organic semiconductor may be mixed) containing the compound (B) of the present invention is a non-luminescent film, and has characteristics different from those of an organic light-emitting element (OLED). The non-light-emitting film is a film having a light-emitting quantum efficiency of 1% or less, more preferably 0.5% or less, still more preferably 0.1% or less.

<film formation method>

The photoelectric conversion film can be formed by a dry film formation method or a wet film formation method. Specific examples of the dry film formation method include a physical vapor deposition (PVD) method such as a vacuum deposition method, a sputtering method, an ion plating method, or a Molecular-Beam Epitaxy (MBE) method, or Chemical Vapor Deposition (CVD) method such as plasma polymerization. The wet film formation method uses a casting method, a spin coating method, a dipping method, an LB method, or the like. A dry film forming method is preferred, and a vacuum evaporation method is more preferred. When the film formation is carried out by a vacuum deposition method, the production conditions such as the degree of vacuum and the vapor deposition temperature can be set in accordance with a usual method.

The thickness of the photoelectric conversion film is preferably 10 nm or more and 1000 nm or less, more preferably 50 nm or more and 800 nm or less, and particularly preferably 100 nm or more and 500 nm or less. When it is 10 nm or more, a suitable dark current suppressing effect can be obtained, and by setting it as 1000 nm or less, suitable photoelectric conversion efficiency can be obtained.

The use of the photoelectric conversion element of the second embodiment is the same as that of the photoelectric conversion element of the first embodiment, and examples thereof include a photo sensor or an image sensor.

Similarly to the photoelectric conversion element of the first embodiment, the photoelectric conversion element of the second embodiment can be applied as an imaging element as shown in FIG. 2 .

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples, but the invention should not be construed as limited.

<<First embodiment>>

<Example 1 to Example 17, Comparative Example 1 to Comparative Example 7>

A photoelectric conversion element of the form of Fig. 1(a) was produced. Here, the photoelectric conversion element includes the lower electrode 11, the electron blocking layer 16A, the photoelectric conversion film 12, and the upper electrode 15.

Specifically, the lower electrode 11 (thickness: 30 nm) is formed by depositing amorphous ITO on a glass substrate by a sputtering method, and the following compound is further formed on the lower electrode 11 by vacuum heating evaporation ( EB-1) forms an electron blocking layer 16A (thickness: 100 nm). Further, in the state where the temperature of the substrate is controlled to 25 ° C, the electron blocking layer 16A is formed by 114 nm and 286 nm in a single layer conversion of the compound of the following (1) and fullerene (C ₆₀ ), respectively. The film was formed by co-evaporation by vacuum heating vapor deposition to form a photoelectric conversion film 12. Further, amorphous ITO was formed on the photoelectric conversion film 12 by a sputtering method to form an upper electrode 15 (transparent conductive film) (thickness: 10 nm). After forming an SiO film as a sealing layer on the upper electrode 15 by heating evaporation, an aluminum oxide (Al ₂ O ₃ ) layer is formed thereon by an Atomic Layer Chemical Vapor Deposition (ALCVD) method. A photoelectric conversion element is produced.

<Example 2 to Example 17, Comparative Example 1 to Comparative Example 7>

A photoelectric conversion element was produced in the same manner as in Example 1 except that the following compounds (2) to (17) and the comparative compound 1 to the comparative compound 7 were used instead of the compound (1).

Further, the following (1) to (17) correspond to the compound (A) represented by the above formula (1).

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The compounds of the above (1) to (17) can be synthesized by a known method. Identification of the compound can be carried out by MS spectrum and ¹ H-NMR.

Hereinafter, a specific synthesis scheme will be shown regarding the compounds of the above (2), (4), and (10). Further, Fig. 3 shows a ¹ H-NMR spectrum of the compound of the above (2), and Fig. 4 shows a ¹ H-NMR spectrum of the compound of the above (4). Fig. 5 shows a ¹ H-NMR spectrum chart of the compound of the above (10).

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<Confirmation of component drive (measurement of dark current)>

Each of the obtained photoelectric conversion elements was confirmed whether or not it functions as a photoelectric conversion element. Specifically, a voltage was applied to the lower electrode and the upper electrode of the photoelectric conversion element so as to have an electric field intensity of 2.5 × 10 ⁵ V/cm, and the current value in the dark place and the bright place was measured. As a result, in any of the photoelectric conversion elements, a dark current of 100 nA/cm ² or less is displayed in a dark place, but a current of 10 μA/cm ² or more is displayed in a bright place, and it is confirmed that it functions as a photoelectric conversion element.

<Evaluation of photoelectric conversion efficiency (external quantum efficiency)>

The photoelectric conversion efficiency of each of the obtained photoelectric conversion elements was evaluated.

Specifically, a voltage is applied to the photoelectric conversion element so as to have an electric field intensity of 2.0 × 10 ⁵ V/cm, and the external quantum efficiency of the maximum absorption wavelength at the voltage is measured. The results are shown in Table 1.

In addition, when the external quantum efficiency of the first embodiment is set to 1, the relative value of 0.90 or more is referred to as "A", the case of 0.85 or more and less than 0.90 is referred to as "B", and the case where 0.80 or more and less than 0.85 is used as " In the case of C", the case of 0.70 or more and less than 0.80 is referred to as "D", and the case of less than 0.70 is referred to as "E". Practically preferred is A~C.

<Responsive evaluation>

The responsiveness of each of the obtained photoelectric conversion elements was evaluated.

Specifically, an electric field of 1.5 × 10 ⁵ V/cm was applied to the photoelectric conversion element, and the photocurrent when the light was irradiated from the upper electrode (transparent conductive film) side was measured, and the rise time from 0 to 90% of the signal intensity was determined. . The results are shown in Table 1.

In addition, the case where the relative value when the rise time of the first embodiment is 1 is less than 0.8 is referred to as "A", the case where 0.8 or more and less than 1.3 is referred to as "B", and the case where 1.3 or more is less than 2.0 is referred to as "C". The case of 2.0 or more and less than 3.0 is referred to as "D", and the case of 3.0 or more is referred to as "E". Practically preferred is A~C.

The relative value is calculated by the following formula.

(relative value) = (the rise time of 0 to 90% of the signal intensity in each embodiment or each comparative example / the rise time of 0 to 90% of the signal intensity in the first embodiment)

<Evaluation of heat resistance>

The heat resistance (220 ° C) of each of the obtained photoelectric conversion elements was evaluated.

Specifically, changes in external quantum efficiency and dark current before and after the thermal annealing treatment (heat treatment) were investigated. The thermal annealing treatment was performed by holding the photoelectric conversion element on a hot plate at 220 ° C for 30 minutes. When the external quantum efficiency and the dark current were measured, a voltage was applied to the lower electrode and the upper electrode so as to have an electric field intensity of 2.5 × 10 ⁵ V/cm. Measurement of external quantum efficiency and dark current after thermal annealing treatment after returning to room temperature.

The rate of decrease in external quantum efficiency due to thermal annealing treatment is determined according to the external quantum efficiency before and after the thermal annealing treatment (= (external quantum efficiency before thermal annealing treatment - external quantum efficiency after thermal annealing treatment) / thermal annealing treatment The former external quantum efficiency × 100 (%)).

Moreover, according to the dark current value before and after the thermal annealing treatment, it is determined that the thermal annealing is performed The rate of increase of dark current caused by the treatment (= (dark current value after thermal annealing treatment - dark current value before thermal annealing treatment) / dark current value before thermal annealing treatment × 100 (%)).

The results are shown in Table 1.

In addition, when the rate of reduction of the external quantum efficiency and the rate of increase of the dark current are less than 2.0%, the case of "A" is less than 3.5%, and any case of 2.0% or more is regarded as "B", and both are less than 5.0%. In the case where any of them is 3.5% or more, "C" is used, and when any of them is 5.0% or more, "D" is used. Preferred in practice is A or B.

According to Table 1, it is understood that a compound having no specific linking group L is used instead of the compound (A) represented by the above formula (1) as Comparative Example 1 to Comparative Example 5 as a photoelectric conversion material, or a specific linking group L is used. In the case of the compound of the formula (1), the compound (A) represented by the above formula (1) is used as the photoelectric conversion material, and the comparative example 6 and the comparative example 7 (the form of the patent document 1 - patent document 6). Both are insufficient in heat resistance.

On the other hand, the examples of the present application which use the compound (A) represented by the above formula (1) having a specific linking group L and having a specific structure of the amine moiety as the photoelectric conversion material all exhibit excellent heat resistance. Moreover, it exhibits high photoelectric conversion efficiency and excellent responsiveness.

Among them, Examples 1 to 11 and Examples 13 to 17 in which the linking group L is represented by the above formula (3) exhibit more excellent heat resistance and responsiveness, and higher photoelectric conversion efficiency. Wherein, a ring formed by Ar ¹¹ and L, and/or Ar ¹² and L bonded to each other is a ring formed by an alkyl group, and X1 is >CR ^1a R ^1b , and Example 4 and Example 5 of n=0. Further, Example 13 and Example 14 showed more excellent effects.

<Production of imaging element>

The same imaging element as that shown in Fig. 2 was produced. That is, after the amorphous TiN is formed on the CMOS substrate by sputtering, 30 nm is formed by photolithography on the photodiode (PD) on the CMOS substrate. The pattern was patterned to form a lower electrode, and after the formation of the electron blocking material, the same manner as in the first to seventh embodiments and the comparative examples 1 to 7 was carried out. The evaluation was similarly performed, and the same results as in Table 1 were obtained, and it was found that the image pickup device was also suitable for production and exhibited excellent performance.

<<2th embodiment>>

(Synthesis of Compound (1))

2-Isopropenylaniline (18.6 g, 140 mmol), palladium acetate (1.57 g, 7.00 mmol), tris(t-butyl)phosphine (2.83 g, 14.0 mmol), sodium butoxide (33.64) g, 350 mmol) and 6-bromo-benzothiophene (14.9 g, 70 mmol) were dissolved in toluene (560 mL), and the mixture was refluxed under a nitrogen atmosphere for 2 hours to cause a reaction. After returning to room temperature, a saturated aqueous solution of ammonium chloride was added thereto, and extracted with ethyl acetate. The oil layer was washed with saturated brine, dried over magnesium sulfate, and filtered. After concentration, the reaction mixture was separated by a silica gel column (developing solvent: dichloromethane /hexane = 1 / 14) to give Compound 1 (16.2 g).

Compound 1 (7.96 g, 30.0 mmol) was added to a mixed solvent of acetic acid (270 mL) and hydrochloric acid (30 mL), and stirred at 70 ° C for 1.5 hours. After returning to room temperature, the reaction solution was added to water (1500 mL), and the precipitated solid was filtered and dried. The reaction mixture was separated by a silica gel column (developing solvent: ethyl acetate /hexane = 1 / 9) to afford Compound 2 (3.80 g).

1 M toluene solution (2.40 mL, 2.40 mmol) and sodium butoxide (5.76 g, 60.0) of iodobenzene (3.67 g, 18.0 mmol), palladium acetate (269 mg, 1.20 mmol), tris(t-butyl)phosphine. Methyl) and the compound 2 (3.18 g, 12.0 mmol) were dissolved in toluene (96 mL), and the mixture was refluxed under a nitrogen atmosphere for 1.5 hours to cause a reaction. After returning to room temperature, a saturated aqueous solution of ammonium chloride was added thereto, and extracted with ethyl acetate. The oil layer was washed with saturated brine, dried over magnesium sulfate, and filtered. After concentration, the reaction mixture was separated by a silica gel column (developing solvent: chloroform/hexane = 1/9) to give Compound 3 (3.45 g).

Compound 3 (2.75 mg, 8.05 mmol) was dissolved in THF (120 mL) under nitrogen and cooled to -78. n-Butyllithium (1.6 M hexane solution) (8.05 mL, 12.9 mmol) was added dropwise to the reaction solution, and the mixture was stirred for 1 hour. N,N-dimethylformamide (2.0 mL, 25.9 mmol). After the reaction solution was warmed to room temperature, it was quenched with saturated aqueous ammonium chloride (50 mL) and extracted with ethyl acetate. The oil layer was washed with saturated brine and dried by magnesium sulfate to filter. After concentration, compound 4 (2.1 g) was obtained by recrystallization from acetonitrile.

Compound 4 (500 mg, 1.35 mmol), 1,3-benzoindanedione (292 mg, 1.49 mmol), and N-methylpiperazine (4.10 mg, 0.041 mmol) were dissolved in octane (10 mL). The reaction was allowed to proceed at 125 ° C for 4 hours. After returning to room temperature, it was filtered and washed with hexane. The filtrate was recrystallized from anisole to obtain the exemplified compound (1) (610 mg).

(Synthesis of Compound (3))

Compound 4 (500 mg, 1.35 mmol), 6,7-dichloro-1,3-indanedione (320) Methyl, 1.49 mmol) and N-methylpiperazine (4.10 mg, 0.041 mmol) were dissolved in octane (10 mL) and allowed to react at 125 ° C for 4 hours. After returning to room temperature, it was filtered and washed with hexane. The filtrate was recrystallized from anisole to obtain the exemplified compound (3) (580 mg).

(Synthesis of Compound (10))

Compound 4 (1.98 g, 5.35 mmol), o-hydroxyacetophenone (874 mg, 6.42 mmol), and piperidine (547 mg, 6.42 mmol) were dissolved in ethanol (40 mL), and the reaction was carried out at 90 ° C for 12 hours. After returning to room temperature, filtration was carried out, and the filtrate was separated by a silica gel column (developing solvent: chloroform/hexane = 9/1) to obtain compound 5 (1.56 g).

Compound 5 (1.22 g, 2.50 mmol) and iodine (1.02 g, 4.00 mmol) were dissolved in pyridine, and the reaction was carried out at 90 ° C for 4 hours. After returning to room temperature, 1 M aqueous sodium hydrogensulfite solution was added thereto, and extracted with ethyl acetate. The oil layer was washed with saturated brine, dried over magnesium sulfate, and filtered. After concentration, the reaction mixture was separated by a silica gel column (developing solvent: chloroform/hexane = 9/1) to afford compound 6 (724 mg).

Compound 6 (710 mg, 1.46 mmol), 1,3-indanedione (320 mg, 2.19 mmol), and N-methylpiperazine (4.10 mg, 0.041 mmol) were dissolved in acetic anhydride (10 mL) at 100 The reaction was carried out for 6 hours at °C. After returning to room temperature, the filtrate was recrystallized from anisole to obtain the exemplified compound (10) (542 mg).

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(Synthesis of Compound (35))

Dissolve thieno[3,2-b]thiophene (1.40 g, 10.0 mmol), N-bromosuccinimide (1.78 g, 10.0 mmol) in N,N-dimethylformamide (20 mL) The reaction was carried out for 4 hours in an ice bath. Water was added, and the mixture was extracted with ethyl acetate. The oil layer was washed with saturated brine, dried over magnesium sulfate, and filtered. After concentration, the reaction mixture was separated by a silica gel column (developing solvent: toluene/hexane = 1/9) to give 2-bromothieno[3,2-b]thiophene (1.56 g).

The exemplified compound (35) was synthesized by the same method as the exemplified compound (1) using 2-bromothieno[3,2-b]thiophene instead of 6-bromo-benzothiophene.

(Synthesis of Compound (47))

The exemplified compound (47) was synthesized by the same method as the exemplified compound (1), using 2-bromothiophene (manufactured by Tokyo Chemical Industry Co., Ltd.) in place of 6-bromo-benzothiophene.

(Synthesis of Compound (51))

2-bromothiophene (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 6-bromo-benzothiophene, and 1,3-benzoindanedione was used instead of 1,3-indanedione, by exemplified compound (10) The exemplified compound (51) was synthesized in the same manner.

(Synthesis of Compound (56))

The exemplified compound (56) was synthesized by a combination of the method described in Patent Document 1 and the synthesis method of the exemplified compound (1) using 6-bromobenzothiophene (manufactured by Tokyo Chemical Industry Co., Ltd.).

Further, the exemplified compound (1), the exemplified compound (3), and the exemplified compound (10), the exemplified compound (35), the exemplified compound (39), the exemplified compound (47), the exemplified compound (51), and the exemplified compound (56) correspond to specific examples of the compound represented by the above compound (A). (1), specific example (3), specific example (10), specific example (35), specific example (39), specific example (47), specific example (51), and specific example (56).

<Example 1B>

A photoelectric conversion element of the form of Fig. 1(a) was produced. Here, the photoelectric conversion element includes the lower electrode 11, the electron blocking layer 16A, the photoelectric conversion film 12, and the upper electrode 15.

Specifically, the lower electrode 11 (thickness: 30 nm) is formed by depositing amorphous ITO on a glass substrate by a sputtering method, and the following compound is further formed on the lower electrode 11 by vacuum heating evaporation ( EB-1) forms an electron blocking layer 16A (thickness: 100 nm). Further, in the state where the temperature of the substrate is controlled to 25 ° C, the electron blocking layer 16A is vacuumed so that the compound (1) and the fullerene (C ₆₀ ) are 120 nm and 280 nm in a single layer, respectively. The film was formed by co-evaporation by heating and vapor deposition to form a photoelectric conversion film 12. Further, amorphous ITO was formed on the photoelectric conversion film 12 by a sputtering method to form an upper electrode 15 (transparent conductive film) (thickness: 10 nm). After forming an SiO film as a sealing layer on the upper electrode 15 by heating evaporation, an aluminum oxide (Al ₂ O ₃ ) layer is formed thereon by an Atomic Layer Chemical Vapor Deposition (ALCVD) method. A photoelectric conversion element is produced.

<Example 2B to Example 8B, Comparative Example 1B to Comparative Example 4B>

A photoelectric conversion element was produced in the same manner as in Example 1B except that the photoelectric conversion material shown in Table 2 was used instead of the exemplified compound (1).

Further, Comparative Compound (63) to Comparative Compound (66) used as a photoelectric conversion material in Comparative Example 1B to Comparative Example 4B are as follows. The comparative compound (63) to the comparative compound (66) correspond to a compound disclosed in Patent Document 7 as a photoelectric conversion material.

[化40]

<Confirmation of drive (measurement of dark current)>

Each of the obtained photoelectric conversion elements was confirmed whether or not it functions as a photoelectric conversion element. Specifically, a voltage was applied to the lower electrode and the upper electrode of the photoelectric conversion element so as to have an electric field intensity of 2.5 × 10 ⁵ V/cm, and the current value in the dark place and the bright place was measured. As a result, in any of the photoelectric conversion elements, a dark current of 100 nA/cm ² or less is displayed in a dark place, but a current of 10 μA/cm ² or more is displayed in a bright place, and it is confirmed that it functions as a photoelectric conversion element.

<Evaluation of photoelectric conversion efficiency (external quantum efficiency)>

The photoelectric conversion efficiency of each of the obtained photoelectric conversion elements was evaluated.

First, a voltage is applied to the photoelectric conversion element so as to have an electric field intensity of 1.0 × 10 ⁵ V/cm. Thereafter, light was irradiated from the side of the upper electrode (transparent conductive film) to measure the external quantum efficiency at 580 nm. The external quantum efficiency was measured using a constant energy quantum efficiency measuring device manufactured by OPTEL. The amount of light that was irradiated was 50 uW/cm ² . Further, in order to remove the influence of the reflected light on the surface of the photoelectric conversion element, the external quantum efficiency at 580 nm was divided by the light absorption rate at 580 nm as the external quantum efficiency. The results are shown in Table 2.

In addition, the case where the relative value of the external quantum efficiency of the example 1B is 1 or more is 0.9 or more, and the case where the relative value of 0.8 or more is less than 0.9 is referred to as "B", and the case where 0.7 or more is less than 0.8 is referred to as "". C", the case of less than 0.7 is taken as "D".

<Responsive evaluation>

The responsiveness of each of the obtained photoelectric conversion elements was evaluated.

Specifically, a voltage is applied to the photoelectric conversion element so as to have an electric field intensity of 2.0 × 10 ⁵ V/cm. Thereafter, the LED was instantaneously lit, and light was irradiated from the upper electrode (transparent conductive film) side, and the photocurrent at this time was measured by an oscilloscope to obtain a rise time from 0 to 95% of the signal intensity. The results are shown in Table 2.

In addition, the case where the relative value when the rise time of the first embodiment is 1 is less than 1.5 is "A", the case where 1.5 or more and less than 2.0 is "B", and the case where 2.0 or more is less than 3.0 is referred to as "C". , the case of 3.0 or more is taken as "D". Practically preferred is A or B.

The relative value is calculated by the following formula.

(relative value) = (the rise time of 0 to 95% of the signal intensity in each embodiment or each comparative example / the rise time of 0 to 95% of the signal intensity in the embodiment 1B)

<Evaluation of high temperature storage stability>

The high temperature storage stability of each of the obtained photoelectric conversion elements was evaluated.

Specifically, the photoelectric conversion element was stored in a thermostatic chamber maintained at 90 ° C for 1,000 hours, and thereafter, the rise time from 0 to 90% of the signal intensity was obtained by the same method as the evaluation of the responsiveness described above.

According to the rise time before and after the high temperature storage, the rate of change (deterioration rate) of the responsiveness due to the high temperature storage is determined (=the rise time after the high temperature storage/the rise time before the high temperature storage). The smaller the rate of change, the more excellent the high temperature storage property. The results are shown in Table 2.

In addition, the case where the relative value of the change rate of the first embodiment is 1 is less than 1.2, the case where the relative value is less than 1.2 is "A", the case of 1.2 or more and less than 1.5 is "B", and the case where the change rate is 1.5 or more and less than 2.0 is "C". , the case of 2.0 or more is referred to as "D". Practically preferred is A or B.

In addition, the relative value is calculated by the following formula.

(relative value) = (deterioration rate in each embodiment or each comparative example / deterioration rate in Example 1B)

According to Table 2, it is understood that the compound (B) in which the amine moiety and the linking site are not condensed is used instead of the compound (B) represented by the above formula (11) as the photoelectric conversion material, and the comparative example 1B to the comparative example 4B (the form of the patent document 7) It is responsive and has insufficient heat preservation.

On the other hand, the examples of the present application using the compound (B) represented by the above formula (11) in which the amine moiety and the linking moiety are condensed as the photoelectric conversion material all exhibit excellent responsiveness and high-temperature preservability. Among them, Examples 1B to 5B and Example 8B in which R ^3w and R ^5w in the above formula (11) and/or R ^6w and R ^8w are bonded to each other to form a ring exhibit higher photoelectric conversion efficiency. Among them, Examples 1B to 3B in which the ring formed was an aromatic hydrocarbon ring exhibited more excellent high-temperature storage stability.

According to the comparison between Example 1B and Example 2B, the compound (B) is of the above formula Example 1B of the compound (b3) represented by (13) showed higher photoelectric conversion efficiency.

According to the comparison between Example 1B and Example 6B, Example 1B in which m is 1 in the above formula (11) exhibits higher photoelectric conversion efficiency and more excellent high-temperature preservability.

According to the comparison of Example 1B to Example 3B and the comparison of Example 6B to Example 8B, Example 1B, Example 2B and Example 6B with q=0 showed more excellent responsiveness.

<Production of imaging element>

The same imaging element as that shown in Fig. 2 was produced. That is, after the amorphous TiN is formed on the CMOS substrate by sputtering, 30 nm is formed by photolithography on the photodiode (PD) on the CMOS substrate. The pattern was patterned to form a lower electrode, and an image pickup element was produced in the same manner as in Example 1B to Example 8B and Comparative Example 1B to Comparative Example 4B after the formation of the electron blocking material. The evaluation was similarly performed, and the same results as in Table 2 were obtained, and it was found that the image pickup device was also suitable for production and exhibited excellent performance.

10a, 10b‧‧‧ photoelectric conversion components

11‧‧‧lower electrode (conductive film)

12‧‧‧Photoelectric conversion film

15‧‧‧Upper electrode (transparent conductive film)

16A‧‧‧Electronic barrier

16B‧‧‧ hole barrier

Claims (38)

A photoelectric conversion element comprising, in order, a conductive film, a photoelectric conversion film containing a photoelectric conversion material, and a transparent conductive film, wherein the photoelectric conversion material contains the compound (A) represented by the following formula (1): In the formula (1), Ar ¹¹ and Ar ¹² each independently represent an aryl group which may have a substituent or a heteroaryl group which may have a substituent; and R ¹¹ to R ¹³ each independently represent a hydrogen atom or a substituent; An integer of 0 or more; L represents a divalent linking group from which two hydrogen atoms are removed from any possible position of the compound represented by the following formula (2); A represents an acidic core; and R ¹¹ and R ¹² and R ¹¹ are R ¹³ may be bonded to each other to form a ring; in the case where n is 2 or more, a plurality of R ¹¹ and a plurality of R ¹² may be bonded to each other to form a ring; Ar ¹¹ and L Ar ¹² and L, Ar ¹¹ and Ar ¹² may be bonded to each other to form a ring; L and A, L and R ¹¹ , L and R ¹² , L and R ¹³ may be bonded to each other to form a ring; L and A a ring formed by bonding L and R ¹¹ , L and R ¹² , and L and R ^{13 to} each other may have a substituent, [Chemical 2] In the formula (2), R ¹ to R ⁶ each independently represent a hydrogen atom or a substituent; X ¹ represents an oxygen atom, >CR ^1a R ^1b , or >NR ^1c , where R ^1a , R ^1b and R ^1c are respectively Independently representing a hydrogen atom or a substituent; R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁵ and R ⁶ may be bonded to each other to form a ring; R ¹ in the formula (2) The ring formed by bonding R ² , R ² and R ³ , R ³ and R ⁴ , and R ⁵ and R ⁶ may have a substituent. The photoelectric conversion element according to the above aspect of the invention, wherein the compound (A) is a compound (a1) represented by the following formula (4): In the formula (4), Ar ¹¹ and Ar ¹² each independently represent an aryl group which may have a substituent or a heteroaryl group which may have a substituent; and R ¹¹ to R ¹³ each independently represent a hydrogen atom or a substituent; An integer of 0 or more; L represents a divalent linking group from which two hydrogen atoms are removed from any possible position of the compound represented by the following formula (2); and Z ₁ represents a ring containing at least 2 carbon atoms, and The ring is a 5-membered ring, a 6-membered ring, or a condensed ring containing at least any of a 5-membered ring and a 6-membered ring; R ¹¹ and R ¹² , R ¹¹ and R ¹³ may be bonded to each other to form a ring; In the case of 2 or more, a plurality of R ¹¹ and a plurality of R ¹² may be bonded to each other to form a ring; Ar ¹¹ and L, Ar ¹² and L, Ar ¹¹ and Ar ¹² may also be mutually Bonding to form a ring; L and R ¹¹ , L and R ¹² , L and R ¹³ may be bonded to each other to form a ring; L and R ¹¹ , L and R ¹² , L and R ¹³ are bonded to each other to form a ring May also have a substituent, In the formula (2), R ¹ to R ⁶ each independently represent a hydrogen atom or a substituent; X ¹ represents an oxygen atom, >CR ^1a R ^1b , or >NR ^1c , where R ^1a , R ^1b and R ^1c are respectively Independently representing a hydrogen atom or a substituent; R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁵ and R ⁶ may be bonded to each other to form a ring; R ¹ and R ² , R ² The ring formed by bonding R ³ , R ³ and R ⁴ , and R ⁵ and R ^{6 to} each other may have a substituent. The photoelectric conversion element according to claim 2, wherein, in the above formula (4), Z ₁ is a group represented by the following formula (Z1): [Chemical 5] In the formula (Z1), Z ₂ represents a ring containing at least 3 carbon atoms, and the ring is a 5-membered ring, a 6-membered ring, or a condensed ring containing at least any of a 5-membered ring and a 6-membered ring; * indicates A bonding position of a carbon atom bonded to R ¹³ in the above formula (4). The photoelectric conversion element according to claim 1 or 2, wherein the Ar ¹¹ and/or Ar ¹² is an aryl group which may have a substituent. The photoelectric conversion element according to the above-mentioned item (1), wherein the compound (a1) is a compound (a2) represented by the following formula (5): In the formula (5), Ar ¹¹ and Ar ¹² each independently represent an aryl group which may have a substituent or a heteroaryl group which may have a substituent; and R ¹¹ to R ¹³ each independently represent a hydrogen atom or a substituent; An integer of 0 or more; L represents a divalent linking group from which two hydrogen atoms are removed from any possible position of the compound represented by the following formula (2); and R ⁵¹ to R ⁵⁴ each independently represent a hydrogen atom or a substituent R ¹¹ and R ¹² , R ¹¹ and R ¹³ may be bonded to each other to form a ring; in the case where n is 2 or more, a plurality of R ¹¹ and a plurality of R ¹² may be mutually mutually Bonding to form a ring; Ar ¹¹ and L, Ar ¹² and L, Ar ¹¹ and Ar ¹² may be bonded to each other to form a ring; L and R ¹¹ , L and R ¹² , L and R ¹³ may be bonded to each other. a ring formed; L and R ¹¹ , L and R ¹² , L and R ^{13 may} be bonded to each other to form a ring; R ⁵¹ and R ⁵² , R ⁵² and R ⁵³ , R ⁵³ and R ⁵⁴ may also be respectively Bonding to each other to form a ring, In the formula (2), R ¹ to R ⁶ each independently represent a hydrogen atom or a substituent; X ¹ represents an oxygen atom, >CR ^1a R ^1b , or >NR ^1c , where R ^1a , R ^1b and R ^1c are respectively Independently representing a hydrogen atom or a substituent; R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁵ and R ⁶ may be bonded to each other to form a ring; R ¹ in the formula (2) The ring formed by bonding R ² , R ² and R ³ , R ³ and R ⁴ , and R ⁵ and R ⁶ may have a substituent. The photoelectric conversion element according to the first or second aspect of the invention, wherein the L is a divalent linking group from which two hydrogen atoms are removed from any possible position of the compound represented by the following formula (3). :[化8] In the formula (3), R ¹ to R ⁴ and R ⁷ to R ¹⁰ each independently represent a hydrogen atom or a substituent; X ¹ represents an oxygen atom, >CR ^1a R ^1b , or >NR ^1c , where R ^1a , R ^1b and R ^1c each independently represent a hydrogen atom or a substituent; R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ They may be bonded to each other to form a ring; R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ are bonded to each other to form a ring. The ring may also have a substituent. The photoelectric conversion element according to claim 5, wherein the compound (a2) is a compound (a3) represented by the following formula (6): In the formula (6), Ar ¹¹ and Ar ¹² each independently represent an aryl group which may have a substituent or a heteroaryl group which may have a substituent; and R ¹¹ to R ¹³ each independently represent a hydrogen atom or a substituent; An integer of 0 or more; R ¹ , R ³ , R ⁴ , R ⁷ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a substituent; X ¹ represents an oxygen atom, >CR ^1a R ^1b , or >NR ^1c , Here, R ^1a , R ^1b and R ^1c each independently represent a hydrogen atom or a substituent; R ⁵¹ to R ⁵⁴ each independently represent a hydrogen atom or a substituent; and R ¹¹ and R ¹² , R ¹¹ and R ¹³ may also be respectively When n is 2 or more, a plurality of R ¹¹ and a plurality of R ¹² may be bonded to each other to form a ring; R ³ and R ⁴ and R ⁹ are R ¹⁰ may be bonded to each other to form a ring; Ar ¹¹ and R ⁷ , Ar ¹¹ and R ⁹ , Ar ¹² and R ⁷ , Ar ¹² and R ⁹ , Ar ¹¹ and Ar ¹² may be bonded to each other to form a ring; ¹ and R ¹¹ , R ¹ and R ¹² , R ¹ and R ¹³ , R ³ and R ¹¹ , R ³ and R ¹² , R ³ and R ¹³ , R ⁴ and R ¹¹ , R ⁴ and R ¹² , R ⁴ and R ¹³ may be bonded to each other to form a ring; R ¹ and R ^11, R ¹ and R ^12, R ¹ and R ^13, R ³ R ^11, R ³ and R ^12, R ³ and R ^13, R ⁴ and ring R ^11, R ⁴ and R ^12, R ⁴ and R ¹³ bonded to each other to form a group may have a substituent; R ⁵¹ and R ⁵² R ⁵² and R ⁵³ , R ⁵³ and R ⁵⁴ may be bonded to each other to form a ring. The photoelectric conversion element according to claim 1 or 2, wherein the above n is 0. The photoelectric conversion element according to claim 5, wherein the above n is 0. The photoelectric conversion element according to claim 1 or 2, wherein the photoelectric conversion film further contains an n-type organic compound. The photoelectric conversion element according to claim 10, wherein the n-type organic compound comprises a fullerene selected from the group consisting of fullerenes and derivatives thereof. The photoelectric conversion element according to claim 11, wherein the content of the fullerene is a total of the total content of the compound (A) and the fullerene (= single layer conversion of the fullerene) The film thickness / (the film thickness in the single layer of the compound (A) + the film thickness in terms of the single layer of the fullerene) is 50% by volume or more. The photoelectric conversion element according to claim 1 or 2, further comprising an electron blocking layer between the conductive film and the transparent conductive film. The photoelectric conversion element according to the first or second aspect of the invention, wherein the photoelectric conversion film is formed by a vacuum deposition method. The photoelectric conversion element according to the first or second aspect of the invention, wherein the light is incident on the photoelectric conversion film via the transparent conductive film. The photoelectric conversion element according to claim 1 or 2, wherein the transparent conductive film contains a transparent conductive metal oxide. A photosensor comprising the photoelectric conversion element according to any one of claims 1 to 16. An image pickup element comprising the photoelectric conversion element according to any one of claims 1 to 16. A method of using a photoelectric conversion element according to any one of claims 1 to 16, wherein the conductive film and the transparent conductive film are a pair of electrodes. An electric field of 1 × 10 ^-4 V / cm to 1 × 10 ⁷ V / cm is applied between the pair of electrodes. A compound (a2) which is represented by the following formula (5): In the formula (5), Ar ¹¹ and Ar ¹² each independently represent an aryl group which may have a substituent or a heteroaryl group which may have a substituent; and R ¹¹ to R ¹³ each independently represent a hydrogen atom or a substituent; An integer of 0 or more; L represents a divalent linking group from which two hydrogen atoms are removed from any possible position of the compound represented by the following formula (2); and R ⁵¹ to R ⁵⁴ each independently represent a hydrogen atom or a substituent R ¹¹ and R ¹² , R ¹¹ and R ¹³ may be bonded to each other to form a ring; in the case where n is 2 or more, a plurality of R ¹¹ and a plurality of R ¹² may be mutually mutually Bonding to form a ring; Ar ¹¹ and L, Ar ¹² and L, Ar ¹¹ and Ar ¹² may be bonded to each other to form a ring; L and R ¹¹ , L and R ¹² , L and R ¹³ may be bonded to each other. a ring formed; L and R ¹¹ , L and R ¹² , L and R ^{13 may} be bonded to each other to form a ring; R ⁵¹ and R ⁵² , R ⁵² and R ⁵³ , R ⁵³ and R ⁵⁴ may also be respectively Bonding each other to form a ring, [Chem. 11] In the formula (2), R ¹ to R ⁶ each independently represent a hydrogen atom or a substituent; X ¹ represents an oxygen atom, >CR ^1a R ^1b , or >NR ^1c , where R ^1a , R ^1b and R ^1c are respectively Independently representing a hydrogen atom or a substituent; R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁵ and R ⁶ may be bonded to each other to form a ring; R ¹ in the formula (2) The ring formed by bonding R ² , R ² and R ³ , R ³ and R ⁴ , and R ⁵ and R ⁶ may have a substituent. A photoelectric conversion element comprising, in order, a conductive film, a photoelectric conversion film containing a photoelectric conversion material, and a transparent conductive film, wherein the photoelectric conversion material comprises a compound (B) represented by the following formula (11): In the formula (11), R ^1w and R ^2w each independently represent an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent; R ^3w to R ^9w respectively Independently represents a hydrogen atom or a substituent; p represents 0 or 1; q represents an integer of 0 or more; R ^1w and R ^2w , R ^3w and R ^4w , R ^3w and R ^5w , R ^5w and R ^6w , R ^6w and R ^8w , R ^7w and R ^8w , R ^7w and R ^9w may be bonded to each other to form a ring; when q is 2 or more, a plurality of R ^7w and a plurality of R ^8w may be respectively separated from each other. A ring is bonded to each other to form a ring; A ^1w represents an acid nucleus; and at least one of R ^1w and R ^2w is bonded to any of R ^3w , R ^4w and R ^5w to form a ring. The photoelectric conversion element according to claim 21, wherein the compound (B) is a compound (b2) represented by the following formula (12): In the formula (12), R ^1w and R ^2w each independently represent an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent; R ^3w to R ^9w respectively Independently represents a hydrogen atom or a substituent; p represents 0 or 1; q represents an integer of 0 or more; R ^1w and R ^2w , R ^3w and R ^4w , R ^3w and R ^5w , R ^5w and R ^6w , R ^6w and R ^8w , R ^7w and R ^8w , R ^7w and R ^9w may be bonded to each other to form a ring; when q is 2 or more, a plurality of R ^7w and a plurality of R ^8w may be respectively separated from each other. Bonding to each other to form a ring; at least one of R ^1w and R ^2w is bonded to any of R ^3w , R ^4w and R ^5w to form a ring; and R ^15w to R ^18w each independently represent a hydrogen atom or a substituent; R ^15w and R ^16w , R ^16w and R ^17w , and R ^17w and R ^18w may be bonded to each other to form a ring. The photoelectric conversion element according to claim 21, wherein in the above formula (11), R ^3w and R ^5w and/or R ^6w and R ^8w are bonded to each other to form a ring. The photoelectric conversion element according to claim 21, wherein the compound (B) is a compound (b3) represented by the following formula (13): In the formula (13), R ^1w and R ^2w each independently represent an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent; R ^3w to R ^9w respectively Independently represents a hydrogen atom or a substituent; p represents 0 or 1; q represents an integer of 0 or more; R ^1w and R ^2w , R ^3w and R ^4w , R ^3w and R ^5w , R ^5w and R ^6w , R ^6w and R ^8w , R ^7w and R ^8w , R ^7w and R ^9w may be bonded to each other to form a ring; when q is 2 or more, a plurality of R ^7w and a plurality of R ^8w may be respectively separated from each other. Bonding to each other to form a ring; at least one of R ^1w and R ^2w is bonded to any of R ^3w , R ^4w and R ^5w to form a ring; R ^15w and R ^18w to R ^22w each independently represent a hydrogen atom or substituent group; R ^15w and R ^19w, R ^19w and R ^20w, R ^20w and R ^21w, R ^21w and R ^22w, R ^22w and R ^18w may be bonded to each other to form a ring. The photoelectric conversion element according to claim 21, wherein the photoelectric conversion film further comprises an n-type organic semiconductor. The photoelectric conversion element according to claim 25, wherein the n-type organic semiconductor comprises a fullerene selected from the group consisting of fullerenes and derivatives thereof. The photoelectric conversion element according to claim 21 or 22, further comprising an electron blocking layer. The photoelectric conversion element according to claim 27, comprising the conductive film, the electron blocking layer, the photoelectric conversion film, the transparent conductive film, or the conductive film and the photoelectric layer in this order. a conversion film, the above electron blocking layer, and the transparent conductive film. The photoelectric conversion element according to claim 21, wherein the q is an integer of 0 to 3. The photoelectric conversion element according to claim 26, wherein the content of the fullerene is a total of the total content of the compound (B) and the fullerene (= single layer conversion of the fullerene) The film thickness / (the film thickness in the single layer of the compound (B) + the film thickness in terms of the single layer of the fullerene) is 50% by volume or more. The photoelectric conversion element according to claim 21, wherein the light is incident on the photoelectric conversion film via the transparent conductive film. The photoelectric conversion element according to claim 21, wherein the transparent conductive film contains a transparent conductive metal oxide. The photoelectric conversion element according to claim 21, wherein the transparent conductive film is directly laminated on the photoelectric conversion film. A photosensor comprising the photoelectric conversion element according to any one of claims 21 to 33. An image pickup element comprising the photoelectric conversion element according to any one of claims 21 to 33. A method of using a photoelectric conversion element according to any one of claims 21 to 33, wherein the conductive film and the transparent conductive film are a pair of electrodes. An electric field of 1 × 10 ^-4 V / cm to 1 × 10 ⁷ V / cm is applied between the pair of electrodes. A compound (b2) which is represented by the following formula (12): In the formula (12), R ^1w and R ^2w each independently represent an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent; R ^3w to R ^9w respectively Independently represents a hydrogen atom or a substituent; p represents 0 or 1; q represents an integer of 0 or more; R ^1w and R ^2w , R ^3w and R ^4w , R ^3w and R ^5w , R ^5w and R ^6w , R ^6w and R ^8w , R ^7w and R ^8w , R ^7w and R ^9w may be bonded to each other to form a ring; when q is 2 or more, a plurality of R ^7w and a plurality of R ^8w may be respectively separated from each other. Bonding to each other to form a ring; at least one of R ^1w and R ^2w is bonded to any of R ^3w , R ^4w and R ^5w to form a ring; and R ^15w to R ^18w each independently represent a hydrogen atom or a substituent; R ^15w and R ^16w , R ^16w and R ^17w , and R ^17w and R ^18w may be bonded to each other to form a ring. A compound (b3) which is represented by the following formula (13): In the formula (13), R ^1w and R ^2w each independently represent an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent; R ^3w to R ^9w respectively Independently represents a hydrogen atom or a substituent; p represents 0 or 1; q represents an integer of 0 or more; R ^1w and R ^2w , R ^3w and R ^4w , R ^3w and R ^5w , R ^5w and R ^6w , R ^6w and R ^8w , R ^7w and R ^8w , R ^7w and R ^9w may be bonded to each other to form a ring; when q is 2 or more, a plurality of R ^7w and a plurality of R ^8w may be respectively separated from each other. Bonding to each other to form a ring; at least one of R ^1w and R ^2w is bonded to any of R ^3w , R ^4w and R ^5w to form a ring; R ^15w and R ^18w to R ^22w each independently represent a hydrogen atom or substituent group; R ^15w and R ^19w, R ^19w and R ^20w, R ^20w and R ^21w, R ^21w and R ^22w, R ^22w and R ^18w may be bonded to each other to form a ring.