JP4825925B2 - PHOTOELECTRIC CONVERSION ELEMENT AND ITS MANUFACTURING METHOD, OPTICAL SENSOR, IMAGING ELEMENT AND ITS DRIVING METHOD - Google Patents

Description

  The present invention relates to a photoelectric conversion element and a manufacturing method thereof, an optical sensor, an imaging element, and a driving method thereof. The present invention also relates to a compound useful as a material for a photoelectric conversion element.

As a solid-state imaging device, there is a planar light-receiving device in which photoelectric conversion sites are two-dimensionally arranged in a semiconductor to form pixels, and signals generated by photoelectric conversion in each pixel are transferred and read out by a CCD circuit or a CMOS circuit. Widely used. As a conventional photoelectric conversion site, generally used is a semiconductor in which a photodiode portion using a PN junction is formed in a semiconductor such as Si.
In recent years, as the number of pixels has increased, the pixel size has been reduced, the area of the photodiode portion has been reduced, and the reduction in aperture ratio, the reduction in light collection efficiency, and the resulting sensitivity reduction have become issues. As a technique for improving the aperture ratio or the like, a solid-state imaging device having an organic photoelectric conversion film using an organic material has been studied.

  In an organic photoelectric conversion film, a technique for introducing a bulk heterostructure using a fullerene or a fullerene derivative is known in order to exhibit high photoelectric conversion efficiency (high exciton dissociation efficiency). For example, Patent Document 1 discloses a photoelectric conversion film containing fullerene or a fullerene derivative.

In addition, in the organic photoelectric conversion element used in the solar cell, no external electric field is applied for the purpose of taking out electric power. However, in the photoelectric conversion element used as the visible light sensor of the solid-state imaging element, the photoelectric conversion efficiency is maximized. In order to improve the photoelectric conversion efficiency and response speed, a voltage may be applied from the outside.
When a voltage is applied from the outside in order to improve the photoelectric conversion efficiency and the response speed, hole injection or electron injection from the electrode is caused by an external electric field, thereby increasing the dark current.

Many materials that are usually used as electrodes in a photoelectric conversion element have a work function (WF) of about 4.5 eV (for example, ITO). For example, fullerene (C ₆₀ ) is used as a material for a photoelectric conversion film. In this case, since the energy gap between the WF of the electrode and the fullerene (C ₆₀ ) LUMO becomes small, electrons are particularly likely to be injected from the electrode into the photoelectric conversion film portion, and the increase in dark current becomes significant.
Regarding prevention of increase in dark current due to injected current, a technique for efficiently preventing injected carriers and reducing dark current by providing a charge blocking layer that suppresses charge injection into the photoelectric conversion layer is disclosed. (Patent Document 2).

  Patent Documents 1 and 2 do not mention heat resistance that is an important factor in practical use, and do not sufficiently describe a compound structure having high heat resistance.

Patent Documents 3 to 9 describe organic materials having hole transport properties such as fluorene and carbazole and use of the organic materials for electroluminescent elements, but there is no description regarding photoelectric conversion elements. An electroluminescent element utilizes light emission that occurs when a voltage is applied to the element. However, a photoelectric conversion element emits substantially no light because its photoelectric conversion efficiency decreases when it emits light. In the photoelectric conversion element, the electron blocking material made of an organic material receives holes generated in the photoelectric conversion layer and injects holes into the negatively applied electrode. In the electroluminescent element, the positive electrode is applied positively. Receive holes from the electrodes. In other words, the photoelectric conversion element and the electroluminescent element have different hole movement directions and different actions, so the performance required for the material is different, and the material used in the electroluminescent element is good for the photoelectric conversion element. Not necessarily functional.
Further, since the photoelectric conversion element outputs a signal according to the amount of incident light, a constant voltage is applied to the element. Since a negative voltage is applied to the electrode adjacent to the electron blocking material, electron injection from the electrode also occurs. When this occurs in a state where light does not enter the photoelectric conversion element, a dark current is generated and the element performance is deteriorated. An important function of the electron blocking material is to suppress injection of electrons from the electrode. This is a physical property and function that are not required for materials for electroluminescent elements, and the organic materials disclosed in Patent Documents 3 to 9 have no description regarding dark current and heat resistance.
Patent Document 10 describes an organic material having a fluorene skeleton, and describes that the organic material is used for a dye-sensitized solar cell. However, since the characteristics required for a solar cell are different from those of a photoelectric conversion element intended for an image sensor element, the description relating to dark current and heat resistance as in the present invention is not sufficiently disclosed.
In addition, when a film is formed using the compound described in Patent Document 10, grain boundaries are generated due to crystallization and irregularities may be formed on the film surface due to low amorphousness. It is not suitable as a material for the photoelectric conversion element.

JP 2007-123707 A JP 2008-72090 A JP 2005-2900000 A Japanese Patent No. 3508984 JP 2005-2900000 A US Pat. No. 6,649,772 JP 2007-314509 A JP 2010-13444 A JP 2007-308474 A JP 2007-115665 A

In the material for the photoelectric conversion element, in order to realize high photoelectric conversion efficiency and high-speed response, not only the blocking ability against the charge injection from the electrode for reducing the dark current but also generated in the photoelectric conversion film A high charge transport capability that can transport charges to the electrode is also required. In a photoelectric conversion element using a material having a poor charge transporting ability, no photocurrent is observed. Furthermore, in consideration of application to a manufacturing process having a heating process such as color filter installation, protective film installation, element soldering, and improvement in storage stability, the material for the photoelectric conversion element needs to have high heat resistance. .
In general, a high molecular weight material with high van der Waals force is selected as a material having high heat resistance. However, a molecule with a large molecular weight has a molecular form associated with the internal rotation of the molecule due to an increase in the degree of freedom and a decrease in symmetry. Because the variation in the energy state of the molecule increases and the energy state of the molecule increases, the mobility of the charge tends to decrease (OLED and its industrialization front line, Volume 1, Section 3, p25-p27). It was difficult to realize a material with high mobility.
In other words, in the case of a material for a photoelectric conversion element having a diarylamine partial skeleton utilizing hole transport, the material design should satisfy a small value of Ea (electron affinity), high hole (hole) transportability, and high heat resistance. Although there is a need to do so, the structure is severely limited to meet these requirements.

In addition, it is necessary to consider molecular design so that the position of the energy level becomes a preferable value so that it can be used appropriately in the device configuration.
When a material having a small value of Ip (ionization potential) and a material having a large value of Ea (for example, fullerene C ₆₀ ) are brought into contact, the HOMO of the material layer having a small value of Ip is changed to the LUMO of the material layer having a large value of Ea. Electric charges (electrons and holes) are generated in the photoelectric conversion element due to thermal excitation, and dark current as a noise source increases. The Ip of the electron blocking layer in contact with the fullerene C ₆₀ needs to be sufficiently large and small enough to receive holes without barriers from the HOMO of the material that transports holes in the fullerene C ₆₀ bulk heterolayer. In other words, the Ip of the electron blocking layer has to be designed to have a fairly limited value, and a greater restriction must be imposed on the material design that originally had a small degree of freedom as described above.

The present invention was made to improve the above problems, and when applied to a photoelectric conversion element, functions as a photoelectric conversion element, exhibits a low dark current, and heat-treats the element In addition, a photoelectric conversion element capable of reducing the increase width of the dark current and an imaging element including such a photoelectric conversion element are provided.
Furthermore, the present invention provides a compound suitable for forming an electron blocking layer in a photoelectric conversion element capable of reducing an increase in dark current and reducing the increase in dark current even when the element is subjected to heat treatment.

  As a result of intensive studies according to the present invention, it has been found that the above object can be achieved by using a compound having a specific structure.

  The compound represented by the following general formula (F-1) in the present invention is a dicyclic diarylamine (substituent represented by the following general formula (A-1)) and the following divalent linking group (D-1). ) Is a compound having a structure connected by Conventionally, as the electron blocking layer material, a structure in which a condensed diarylamine is connected by a linking group (D-2) has been proposed, and the conventional electron blocking layer material has high charge collection efficiency, high-speed response, low Although it had dark current characteristics, the heat resistance was not sufficient. In order to improve heat resistance, there are generally means such as increasing the molecular weight to increase the interaction between molecules (intermolecular force), introducing many condensed ring structures, and reducing the degree of molecular freedom. Be taken. However, materials with large interactions and materials with a condensed ring structure have a large p-conjugated system, interacting with the photoelectric conversion layer containing deep Ea (large Ea) material, and boiling charges are formed at the interface. The dark current was likely to increase. In addition, steric hindrance can be imparted for the purpose of suppressing intermolecular interaction and increasing the molecular weight, but if the substituent that becomes steric hindrance is too bulky, it will lead to a decrease in charge transport ability. In order to impair the high-speed responsiveness of the element, it is preferable that many bulky substituents are not included. However, in the present invention, by connecting the condensed diarylamine (substituent represented by the general formula (A-1)) with the following divalent linking group (D-1), high charge collection efficiency, high speed Heat resistance can be improved without impairing responsiveness and low dark current characteristics.

  The compound represented by the general formula (F-1) in which the fused diarylamine is linked with the linking group (D-1) has a higher molecular weight than the electron blocking material linked in (D-2), and has a high heat resistance. Can be improved. In addition, since the bond between the skeletons is twisted and the conjugated system is cut, it is estimated that the dark current is kept low without interacting with the photoelectric conversion layer. Moreover, since the diarylamine structure which is a charge transport unit is introduced not at the inside of the molecule but at both ends, it is considered to have a high charge transport property.

(Y each _{independently, -C (R 21) (R} 22) -, - Si (R 23) (R 24) -, - N (R 20) -, an oxygen atom or a sulfur _{atom, R 20} to R ₂₄ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxyl group, an amino group, or mercapto group.)

Furthermore, as a result of studies by the present inventors, the coupling position of the coupling group (D-1), the bonding position of the substituent represented by the general formula (A-1), the substitution position of the following substituent (S ₁₁ ), and By examining the type of the substituent (S ₁₁ ), the electron blocking layer could be made highly heat resistant without causing a decrease in response speed. Connecting position of the connecting groups (D-1), general formula bonding position of the substituent represented by (A-1), the substitution position of substituents below _{(S 11),} and the optimum point of the substituents _{(S 11)} As a result, the effect of increasing the intermolecular force between the compounds represented by the general formula (F-1) due to the suppression of the interaction with the photoelectric conversion layer and the increase in the molecular weight is strongly expressed, and it is considered that the heat resistance has been increased.
That is, the above problem can be solved by the following means.
The present invention relates to the following [1] to [17], but other matters (for example, the matters described in [18] to [20] below) are also described for reference.

[1]
A photoelectric conversion element having a transparent conductive film, a photoelectric conversion film, and a conductive film in this order,
The photoelectric conversion film includes a photoelectric conversion layer and an electron blocking layer,
The photoelectric conversion element in which the said electron blocking layer contains the compound represented by the following general formula (F-1).

(In General Formula (F-1), R _{11 to} R ₁₈ , R ′ _{11 to} R ′ ₁₈ are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxyl group, an amino group, or It represents a mercapto group, which may further have a substituent. _However, any one in R 15 _{to R 18} is coupled with any one in R _'15 ~R' _18, single bond A ₁₁ and A ₁₂ each independently represent a substituent represented by the following general formula (A-1), any one of R _{11 to} R ₁₄ , and R ′ _{11 to} R ′ _14. And each Y is independently a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, or a silicon atom, which may further have a substituent.

(In General Formula (A-1), Ra _{1 to} Ra ₈ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, and these may further have a substituent. At least two members out of Ra _{1 to} Ra ₈ may be bonded to each other to form a ring, and * represents a substituent represented by the general formula (A-1) as R ₁₁ in the general formula (F-1). any one in to R _14, and .Xa representing the binding position when substituted as any one of R _'11 to R' of ₁₄ represents a single bond, an oxygen atom, a sulfur atom, an alkylene group, a silylene group, alkenylene group, cycloalkylene group, cycloalkenylene group, an arylene group, a divalent heterocyclic group or an imino group, which may further have a substituent .S ₁₁ each independently represent the following substituents (S ₁₁ ) and Ra _{1 to} R a is substituted as any one of _8. Each n independently represents an integer of 1 to 4.)

(R _{1 to} R ₃ each independently represents a hydrogen atom or an alkyl group. At least two of R _{1 to} R ₃ may be bonded to each other to form a ring.)
[2]
The photoelectric conversion element according to the above [1], wherein the compound represented by the general formula (F-1) is a compound represented by the following general formula (F-2).

(In General Formula (F-2), R _{11 to} R ₁₆ , R ₁₈ , R ′ _{11 to} R ′ ₁₆ and R ′ ₁₈ are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. , A hydroxyl group, an amino group, or a mercapto group, which may further have a substituent, A ₁₁ and A ₁₂ each independently represent a substituent represented by the general formula (A-1); Substitute as any one of R _{11 to} R ₁₄ and any one of R ′ _{11 to} R ′ _14. Y is independently a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, or silicon. Represents an atom, which may further have a substituent.)
[3]
In the general formula (F-1) or the general formula (F-2), the substituent represented by the general formula (A-1) is independently substituted with R ₁₂ and R ′ ₁₂ , respectively, [1] or [2] The photoelectric conversion element according to [2].
[4]
The photoelectric conversion element according to any one of the above [1] to [3], wherein n in the general formula (A-1) represents 1 or 2.
[5]
The method according to any one of [1] to [4], wherein at least one of Ra ₃ and Ra ₆ in General Formula (A-1) independently represents the substituent (S ₁₁ ). Photoelectric conversion element.
[6]
In the above general formula (F-1) or general formula (F-2), Y represents —N (R ₂₀ ) —, and R ₂₀ represents an alkyl group, an aryl group, or a heterocyclic group, [1] The photoelectric conversion element according to any one of to [5].
[7]
Y in the general formula (F-1) or the general formula (F-2) represents —C (R ₂₁ ) (R ₂₂ ) —, and each of R ₂₁ and R ₂₂ independently represents an alkyl group, an aryl group, or The photoelectric conversion element according to any one of [1] to [5], which represents a heterocyclic group.
[8]
Any one of said [1]-[7] whose ionization potential (Ip) of the compound represented by said general formula (F-1) and (F-2) is 4.9 eV or more and 5.8 eV or less. The photoelectric conversion element as described in 2.
[9]
The photoelectric conversion element according to any one of [1] to [8] above, wherein the compounds represented by the general formulas (F-1) and (F-2) have a molecular weight of 500 or more and 2000 or less.
[10]
The photoelectric conversion element according to any one of [1] to [9], wherein the photoelectric conversion layer includes an n-type organic semiconductor.
[11]
The photoelectric conversion element according to [10], wherein the n-type organic semiconductor is fullerene or a fullerene derivative.
[12]
The photoelectric conversion element according to any one of the above [1] to [11], wherein the photoelectric conversion film contains a compound of the following general formula (I).
Formula (I)

(In the formula, Z ₁ represents an atomic group necessary for forming a 5- or 6-membered ring. L ₁ , L ₂ , and L ₃ each independently represent an unsubstituted methine group or a substituted methine group. D ₁ represents an atomic group, and n ₁ represents an integer of 0 or more.)
[13]
The photoelectric conversion element according to any one of the above [1] to [12], wherein a conductive film, an electron blocking layer, a photoelectric conversion layer, and a transparent conductive film are laminated in this order.
[14]
It is a manufacturing method of the photoelectric conversion element of any one of said [1]-[13], Comprising: The manufacturing method including the process which forms the said photoelectric converting layer and the said electronic blocking layer by vacuum heating vapor deposition, respectively. .
[15]
The optical sensor containing the photoelectric conversion element of any one of said [1]-[13].
[16]
The image pick-up element containing the photoelectric conversion element of any one of said [1]-[13].
[17]
The photoelectric conversion element according to any one of [1] to [13], the optical sensor according to [15], or the image sensor driving method according to [16], wherein the electronic blocking is performed. A driving method in which a voltage is applied with an electrode in contact with a layer as a cathode and the other electrode as an anode.
[18]
The compound represented by the following general formula (F-1).

(In General Formula (F-1), R _{11 to} R ₁₈ , R ′ _{11 to} R ′ ₁₈ are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxyl group, an amino group, or It represents a mercapto group, which may further have a substituent. _However, any one in R 15 _{to R 18} is coupled with any one in R _'15 ~R' _18, single bond A ₁₁ and A ₁₂ each independently represent a substituent represented by the following general formula (A-1), any one of R _{11 to} R ₁₄ , and R ′ _{11 to} R ′ _14. And each Y is independently a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, or a silicon atom, which may further have a substituent.

(In General Formula (A-1), Ra _{1 to} Ra ₈ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, and these may further have a substituent. At least two of Ra _{1 to} Ra ₈ may be bonded to each other to form a ring, * represents a bonding position, and Xa represents a single bond, an oxygen atom, a sulfur atom, an alkylene group, a silylene group, or an alkenylene. Represents a group, a cycloalkylene group, a cycloalkenylene group, an arylene group, a divalent heterocyclic group, or an imino group, which may further have a substituent, and each of S ₁₁ independently represents the following substituent (S ₁₁ ) And substituted as any one of Ra _{1 to} Ra _8. Each n independently represents an integer of 1 to 4.)

(R _{1 to} R ₃ each independently represents a hydrogen atom or an alkyl group. At least two of R _{1 to} R ₃ may be bonded to each other to form a ring.)
[19]
An electron blocking material comprising the compound according to the above [18].
[20]
The film | membrane containing the compound as described in said [18].

  According to the present invention, when a compound having a specific structure is applied to a photoelectric conversion element, it functions as a photoelectric conversion element, the element exhibits a low dark current, and even when the element is heated, It is possible to provide a photoelectric conversion element capable of reducing the increase width and an imaging element including such a photoelectric conversion element.

FIG. 1A and FIG. 1B are schematic cross-sectional views each showing a configuration example of a photoelectric conversion element. The cross-sectional schematic diagram for 1 pixel of an image pick-up element.

[Photoelectric conversion element]
The photoelectric conversion element of the present invention is a photoelectric conversion element having a transparent conductive film, a photoelectric conversion film, and a conductive film in this order,
The photoelectric conversion film includes a photoelectric conversion layer and an electron blocking layer,
The electron blocking layer contains a compound represented by the following general formula (F-1).

(In General Formula (F-1), R _{11 to} R ₁₈ , R ′ _{11 to} R ′ ₁₈ are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxyl group, an amino group, or It represents a mercapto group, which may further have a substituent. _However, any one in R 15 _{to R 18} is coupled with any one in R _'15 ~R' _18, single bond A ₁₁ and A ₁₂ each independently represent a substituent represented by the following general formula (A-1), any one of R _{11 to} R ₁₄ , and R ′ _{11 to} R ′ _14. And each Y is independently a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, or a silicon atom, which may further have a substituent.

(In General Formula (A-1), Ra _{1 to} Ra ₈ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, and these may further have a substituent. At least two of Ra _{1 to} Ra ₈ may be bonded to each other to form a ring, * represents a bonding position, and Xa represents a single bond, an oxygen atom, a sulfur atom, an alkylene group, a silylene group, or an alkenylene. Represents a group, a cycloalkylene group, a cycloalkenylene group, an arylene group, a divalent heterocyclic group, or an imino group, which may further have a substituent, and each of S ₁₁ independently represents the following substituent (S ₁₁ ) And substituted as any one of Ra _{1 to} Ra _8. Each n independently represents an integer of 1 to 4.)

(R _{1 to} R ₃ each independently represents a hydrogen atom or an alkyl group. At least two of R _{1 to} R ₃ may be bonded to each other to form a ring.)

Although it does not specifically limit as an aspect which contains the compound of the said general formula (F-1) in a photoelectric converting film, The material (preferably material whose Ea is 4.0 eV or more) is still larger in a photoelectric converting film. It is preferable that the material having a large electron affinity (Ea) is brought into contact with the compound of the general formula (F-1). By containing the compound of the general formula (F-1) in contact with a material having a high electron affinity (Ea), the generation of spring-out charges (electrons, holes) at the interface between the two materials is effectively suppressed. be able to. In addition, as a material with an electron affinity (Ea) of 4.0 eV or more, a fullerene or a fullerene derivative described later is preferable.
More specifically, a photoelectric conversion element having the following aspect is preferable.
(1) The photoelectric conversion film includes a photoelectric conversion layer and a charge blocking layer (one of or both of an electron blocking layer and a hole blocking layer), the photoelectric conversion layer contains a material having a high electron affinity (Ea), and an electron The aspect in which a blocking layer consists of a compound of general formula (F-1).
(2) The photoelectric conversion film includes a photoelectric conversion layer and a charge blocking layer (one or both of an electron blocking layer and a hole blocking layer), the photoelectric conversion layer contains a material having a high electron affinity (Ea), and an electron A mode in which the blocking layer is composed of a plurality of layers, and the compound of the general formula (F-1) is contained in the electron blocking layer in direct contact with the photoelectric conversion layer.
In the above aspect (1), the electron blocking layer made of the compound of the general formula (F-1) suppresses the boiling charge between the electron blocking layer and the photoelectric conversion layer and prevents the injection of electrons from the electrode. In the aspect (2), the electron blocking layer made of the compound of the general formula (F-1) and the photoelectric conversion layer are in direct contact with each other, thereby preventing the generation of boiling electric charges between the layers. Can do. Since the compound of general formula (F-1) generally has a small Ea, it is preferably used as an electron blocking layer.

Hereinafter, preferred embodiments of the photoelectric conversion element according to the present invention will be described. Although a conductive film, a photoelectric conversion layer, an electron blocking layer, and a transparent conductive film may be laminated in this order, preferred embodiments include a conductive film, an electron blocking layer, a photoelectric conversion layer, and a transparent conductive film. Are stacked in this order.
In FIG. 1, the structural example of the photoelectric conversion element which concerns on this embodiment is shown.
In the photoelectric conversion element 10a shown in FIG. 1A, an electron blocking layer 16A, a photoelectric conversion layer 12, and an upper electrode 15 are laminated on a lower electrode 11 in this order.
In the photoelectric conversion element 10b shown in FIG. 1B, an electron blocking layer 16A, a photoelectric conversion layer 12, a hole blocking layer 16B, and an upper electrode 15 are laminated on a lower electrode 11 in this order. . The stacking order of the electron blocking layer, the photoelectric conversion layer, and the hole blocking layer in FIGS. 1A and 1B may be reversed depending on applications and characteristics.

The elements constituting the photoelectric conversion element according to this embodiment will be described.
(electrode)
The electrodes (upper electrode (transparent conductive film) 15 and lower electrode (conductive film) 11) are made of a conductive material. As the conductive material, a metal, an alloy, a metal oxide, an electrically conductive compound, or a mixture thereof can be used.
Since light is incident from the upper electrode 15, the upper electrode 15 needs to be sufficiently transparent to the light to be detected. Specifically, conductive metal oxides such as tin oxide (ATO, FTO) doped with antimony or fluorine, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), Metal thin films such as gold, silver, chromium and nickel, and mixtures or laminates of these metals and conductive metal oxides, inorganic conductive materials such as copper iodide and copper sulfide, organic materials such as polyaniline, polythiophene and polypyrrole Examples thereof include conductive materials and laminates of these with ITO. Among these, conductive metal oxides are preferable from the viewpoint of high conductivity and transparency. Since the upper electrode 15 is formed on the photoelectric conversion layer 12, it is preferably formed by a method that does not deteriorate the characteristics of the photoelectric conversion layer 12.

  Depending on the application, the lower electrode 11 may have transparency, or conversely, may use a material that does not have transparency and reflects light. Specifically, conductive metal oxides such as tin oxide (ATO, FTO) doped with antimony or fluorine, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), Metals such as gold, silver, chromium, nickel, titanium, tungsten, and aluminum, and conductive compounds such as oxides and nitrides of these metals, and mixtures or laminates of these metals and conductive metal oxides, iodine Examples thereof include inorganic conductive materials such as copper halide and copper sulfide, organic conductive materials such as polyaniline, polythiophene, and polypyrrole, and laminates of these with ITO.

The method for forming the electrode is not particularly limited, and can be appropriately selected in consideration of suitability with 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 CVD or plasma CVD method.
When the material of the electrode is ITO, it can be formed by a method such as an electron beam method, a sputtering method, a resistance heating vapor deposition method, a chemical reaction method (sol-gel method or the like), or a dispersion of indium tin oxide. Furthermore, UV-ozone treatment, plasma treatment, or the like can be performed on a film formed using ITO.

  The upper electrode 15 is preferably made plasma-free. By creating the upper electrode 15 in a plasma-free manner, the influence of plasma on the substrate can be reduced, and the photoelectric conversion characteristics can be improved. Here, plasma free means that no plasma is generated during the deposition of the upper electrode 15 or that the distance from the plasma generation source to the substrate is 2 cm or more, preferably 10 cm or more, more preferably 20 cm or more. It means a state in which the plasma that reaches is reduced.

  Examples of an apparatus that does not generate plasma during the formation of the upper electrode 15 include an electron beam vapor deposition apparatus (EB vapor deposition apparatus) and a pulse laser vapor deposition apparatus. Regarding EB deposition equipment or pulse laser deposition equipment, “Surveillance of Transparent Conductive Films” supervised by Yutaka Sawada (published by CMC, 1999); ), "Transparent conductive film technology" by the Japan Society for the Promotion of Science (Ohm Co., 1999), and the references attached thereto, etc. can be used. Hereinafter, a method of forming a transparent electrode film using an EB vapor deposition apparatus is referred to as an EB vapor deposition method, and a method of forming a transparent electrode film using a pulse laser vapor deposition apparatus is referred to as a pulse laser vapor deposition method.

  For an apparatus that can realize a state in which the distance from the plasma generation source to the substrate is 2 cm or more and the arrival of plasma to the substrate is reduced (hereinafter referred to as a plasma-free film forming apparatus), for example, an opposed target sputtering Equipment, arc plasma deposition, etc. can be considered, and these are supervised by Yutaka Sawada “New development of transparent conductive film” (published by CMC, 1999), and supervised by Yutaka Sawada “New development of transparent conductive film II” (published by CMC) 2002), “Transparent conductive film technology” (Ohm Co., 1999) by the Japan Society for the Promotion of Science, and references and the like attached thereto can be used.

  When a transparent conductive film such as TCO is used as the upper electrode 15, a DC short circuit or an increase in leakage current may occur. One reason for this is thought to be that fine cracks introduced into the photoelectric conversion layer 12 are covered by a dense film such as TCO, and conduction between the first electrode film 11 on the opposite side is increased. For this reason, in the case of an electrode having a poor film quality such as Al, an increase in leakage current hardly occurs. By controlling the film thickness of the upper electrode 15 with respect to the film thickness of the photoelectric conversion layer 12 (that is, the depth of cracks), an increase in leakage current can be largely suppressed. It is desirable 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 layer 12.

  Usually, when the conductive film is made thinner than a certain range, a rapid increase in resistance value is caused. However, in the solid-state imaging device incorporating the photoelectric conversion element according to the present embodiment, the sheet resistance is preferably 100 to 10,000 Ω / □. Well, the degree of freedom in the range of film thickness that can be made thin is great. Further, as the thickness of the upper electrode (transparent conductive film) 15 decreases, the amount of light absorbed decreases, and the light transmittance generally increases. The increase in light transmittance is very preferable because it increases the light absorption in the photoelectric conversion layer 12 and increases the photoelectric conversion ability. Considering the suppression of leakage current, the increase in the resistance value of the thin film, and the increase in transmittance due to the thinning, the thickness of the upper electrode 15 is preferably 5 to 100 nm, more preferably 5 to 20 nm. Things are desirable.

(Charge blocking layer)
The charge blocking layer according to this embodiment contains a compound represented by the following general formula (F-1). One of the embodiments of the present invention is to use the material of the general formula (F-1) as the material of the blocking layer in contact with the photoelectric conversion layer containing a material having a large Ea.

(Electron blocking layer, hole blocking layer)
The electron blocking layer in this invention contains the compound represented by general formula (F-1).

(In General Formula (F-1), R _{11 to} R ₁₈ , R ′ _{11 to} R ′ ₁₈ are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxyl group, an amino group, or It represents a mercapto group, which may further have a substituent. _However, any one in R 15 _{to R 18} is coupled with any one in R _'15 ~R' _18, single bond A ₁₁ and A ₁₂ each independently represent a substituent represented by the following general formula (A-1), any one of R _{11 to} R ₁₄ , and R ′ _{11 to} R ′ _14. And each Y is independently a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, or a silicon atom, which may further have a substituent.

(In General Formula (A-1), Ra _{1 to} Ra ₈ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, and these may further have a substituent. At least two of Ra _{1 to} Ra ₈ may be bonded to each other to form a ring, * represents a bonding position, and Xa represents a single bond, an oxygen atom, a sulfur atom, an alkylene group, a silylene group, or an alkenylene. Represents a group, a cycloalkylene group, a cycloalkenylene group, an arylene group, a divalent heterocyclic group, or an imino group, which may further have a substituent, and each of S ₁₁ independently represents the following substituent (S ₁₁ ) And substituted as any one of Ra _{1 to} Ra _8. Each n independently represents an integer of 1 to 4.)

(R _{1 to} R ₃ each independently represents a hydrogen atom or an alkyl group. At least two of R _{1 to} R ₃ may be bonded to each other to form a ring.)

In general formula (F-1), R _{11 to} R ₁₈ , R ′ _{11 to} R ′ ₁₈ are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxyl group, an amino group, or a mercapto. Represents a group, and these may further have a substituent. Specific examples of the further substituent include the substituent W described later, preferably a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxyl group, an amino group, or a mercapto group, more preferably a halogen atom or an alkyl group. , An aryl group, and a heterocyclic group, more preferably a fluorine atom, an alkyl group, and an aryl group, particularly preferably an alkyl group and an aryl group, and most preferably an alkyl group.
R _{11 to} R ₁₈ and R ′ _{11 to} R ′ ₁₈ are preferably a hydrogen atom, an alkyl group optionally having a substituent, an aryl group, from the viewpoint of chemical stability, charge mobility, and heat resistance, A heterocyclic group, more preferably a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a heterocyclic group having 4 to 16 carbon atoms. It is. Among these, from the viewpoint of charge mobility and heat resistance, the substituent represented by the general formula (A-1) is preferably independently substituted with R ₁₂ and R ′ ₁₂ , and is represented by the general formula (A-1). And R ₁₂ and R ′ ₁₂ are each independently substituted, and R ₁₁ , R _{13 to} R ₁₈ , R ′ ₁₁ , R ′ _{13 to} R ′ ₁₈ have a hydrogen atom or a substituent. More preferably an alkyl group having 1 to 18 carbon atoms, particularly preferably a substituent represented by the general formula (A-1) is independently substituted with R ₁₂ and R ′ ₁₂ , and R ₁₁ , _{R 13 ~R 18, R '11} , R' 13 ~R '18 are hydrogen atoms.

Y independently represents a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, or a silicon atom, and these may further have a substituent. That is, Y represents a divalent linking group composed of a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, or a silicon atom. Examples of the substituent include the substituent W described later.
Y is _{independently, -C (R 21) (R} 22) -, - Si (R 23) (R 24) -, - N (R 20) -, an oxygen atom or a sulfur _{atom, R 20} ~ Each R ₂₄ preferably independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxyl group, an amino group, or a mercapto group. Among these, from the viewpoint of chemical stability, charge mobility, and heat resistance, —C (R ₂₁ ) (R ₂₂ ) —, —Si (R ₂₃ ) (R ₂₄ ) —, —N (R ₂₀ ) —, -C (R ₂₁ ) (R ₂₂ )-and -N (R ₂₀ )-are more preferable, and -C (R ₂₁ ) (R ₂₂ )-is particularly preferable.

In the —C (R ₂₁ ) (R ₂₂ ) —, R ₂₁ and R ₂₂ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxyl group, an amino group, or a mercapto group. To express. R ₂₁ and R ₂₂ may further have a substituent, and specific examples of the further substituent include a substituent W, preferably an alkyl group, an aryl group, or an alkoxy group.
R ₂₁ and R ₂₂ are preferably a hydrogen atom, an alkyl group which may have a substituent, an aryl group or a heterocyclic group, more preferably a hydrogen atom or an optionally substituted carbon number. An alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a heterocyclic group having 4 to 16 carbon atoms, more preferably a hydrogen atom and optionally having 1 to 18 carbon atoms. An alkyl group, particularly preferably an alkyl group having 1 to 18 carbon atoms.

In the —Si (R ₂₃ ) (R ₂₄ ) —, R ₂₃ and R ₂₄ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxyl group, an amino group, or a mercapto group. To express. R ₂₃ and R ₂₄ may further have a substituent, and specific examples of the further substituent include a substituent W, preferably an alkyl group, an aryl group, or an alkoxy group.
R ₂₃ and R ₂₄ are preferably a hydrogen atom, an alkyl group that may have a substituent, an aryl group, or a heterocyclic group, and more preferably a hydrogen atom or a carbon number that may have a substituent. An alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a heterocyclic group having 4 to 16 carbon atoms, more preferably a hydrogen atom and optionally having 1 to 18 carbon atoms. An alkyl group, particularly preferably an alkyl group having 1 to 18 carbon atoms.
R ₂₃ and R ₂₄ may combine to form a ring, and the ring is preferably an aliphatic hydrocarbon ring, more preferably an aliphatic hydrocarbon ring having 4 to 10 carbon atoms.

In the —N (R ₂₀ ) —, R ₂₀ preferably represents an alkyl group, an aryl group, or a heterocyclic group. R ₂₀ may further have a substituent, and specific examples of the further substituent include the substituent W, preferably an alkyl group or an aryl group.
R ₂₀ is more preferably a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a heterocyclic group having 4 to 16 carbon atoms, More preferably, they are a hydrogen atom and the C1-C18 alkyl group which may have a substituent, Especially preferably, it is a C1-C18 alkyl group.

Ra _{1 to} Ra ₈ in the general formula (A-1) each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ra _{1 to} Ra ₈ may further have a substituent, and specific examples of the further substituent include the substituent W, and an alkyl group is preferable. Further, at least two of Ra _{1 to} Ra ₈ may be bonded to each other to form a ring. The ring to be formed is a cycloalkyl ring having 5 to 18 carbon atoms, benzene ring, naphthalene ring, indane ring, anthracene ring, pyrene ring, phenanthrene ring, perylene ring, pyridine ring, quinoline ring, isoquinoline ring, phenanthridine ring. , Pyrimidine ring, pyrazine ring, pyridazine ring, triazine ring, cinnoline ring, acridine ring, phthalazine ring, quinazoline ring, quinoxaline ring, naphthyridine ring, pteridine ring, pyrrole ring, pyrazole ring, triazole ring, indole ring, carbazole ring, indazole Ring, benzimidazole ring, oxazole ring, thiazole ring, oxadiazole ring, thiadiazole ring, benzoxazole ring, benzothiazole ring, imidazopyridine ring, thiophene ring, benzothiophene ring, furan ring, benzofuran ring, pho Hall ring, a phosphinine ring, and a silol ring. Preferably, a C5-C18 cycloalkyl ring, benzene ring, naphthalene ring, indane ring, anthracene ring, pyrene ring, phenanthrene ring, perylene ring, pyrrole ring, indole ring, carbazole ring, indazole ring, thiophene ring, benzo A thiophene ring, a furan ring, and a benzofuran ring, more preferably a cycloalkyl ring having 5 to 18 carbon atoms, a benzene ring, a naphthalene ring, an indane ring, an indole ring, a carbazole ring, and an indazole ring, particularly preferably a carbon A cycloalkyl ring having 5 to 10 carbon atoms, a benzene ring, a naphthalene ring, an indane ring, and an anthracene ring, and more preferably a cycloalkyl ring having 5 to 10 carbon atoms, a benzene ring, a naphthalene ring, and an indane ring, most preferably , C5-C6 cycloalkyl ring, benzene ring Indane ring. These rings may further have a substituent W described later.

Ra _{1 to} Ra ₈ are preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a carbon number from the viewpoint of chemical stability, charge mobility, and heat resistance. A heterocyclic group having 4 to 16 carbon atoms is preferable, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and an aryl group having 6 to 14 carbon atoms are more preferable, and a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and 6 to 6 carbon atoms. 10 aryl groups are more preferred. The alkyl group may be branched.
Specific preferred examples of Ra _{1 to} Ra ₈ include a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, a phenyl group, and a naphthyl group.
Further, when at least one of Ra ₃ and Ra ₆ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and Ra ₁ , Ra ₂ , Ra ₄ , Ra ₅ , Ra ₇ , Ra ₈ are a hydrogen atom Or at least one of Ra ₂ and Ra ₇ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and Ra ₁ , Ra ₃ , Ra ₄ , Ra ₅ , Ra ₆ , Ra ₈ are a hydrogen atom In particular, Ra ₃ and Ra ₆ are hydrogen atoms or alkyl groups having 1 to 6 carbon atoms, and Ra ₁ , Ra ₂ , Ra ₄ , Ra ₅ , Ra ₇ , Ra ₈ are particularly hydrogen atoms. preferable.

Xa represents a single bond, an oxygen atom, a sulfur atom, an alkylene group, a silylene group, an alkenylene group, a cycloalkylene group, a cycloalkenylene group, an arylene group, a divalent heterocyclic group, or an imino group, and these further represent a substituent. You may have. Specific examples of the further substituent include a substituent W, preferably an alkyl group or an aryl group.
Xa is a single bond, an alkylene group having 1 to 12 carbon atoms, an alkenylene group having 2 to 12 carbon atoms, an arylene group having 6 to 14 carbon atoms, a heterocyclic group having 4 to 13 carbon atoms, an oxygen atom, a sulfur atom, carbon An imino group (for example, phenylimino group, methylimino group, t-butylimino group) having a hydrocarbon group of 1 to 12 (preferably an aryl group or an alkyl group) or a silylene group is preferable, a single bond, an oxygen atom, or a carbon number of 1 6 alkylene group (e.g. methylene, 1,2-ethylene group, 1,1-dimethylmethylene group), an alkenylene group having 2 carbon atoms (e.g., _-CH 2 = _CH 2 -), an arylene of 6 to 10 carbon atoms More preferably a group (for example, 1,2-phenylene group or 2,3-naphthylene group) or a silylene group, a single bond, an oxygen atom, or an alkylene group having 1 to 6 carbon atoms (for example, a methylene group, 1, 2-ethylene group and 1,1-dimethylmethylene group) are more preferable.

In the substituent (S ₁₁ ), R ₁ represents a hydrogen atom or an alkyl group. R ₁ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, from the viewpoints of chemical stability, charge mobility, and heat resistance. A methyl group, an ethyl group, a propyl group, an iso-propyl group, a butyl group, or a tert-butyl group is preferable, and a methyl group, an ethyl group, a propyl group, an iso-propyl group, or a tert-butyl group is more preferable. More preferred is a methyl group, an ethyl group, an iso-propyl group, or a tert-butyl group, and particularly preferred is a methyl group, an ethyl group, or a tert-butyl group.

R ₂ represents a hydrogen atom or an alkyl group. R ₂ is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, from the viewpoints of chemical stability, charge mobility, and heat resistance. Specifically, a hydrogen atom, a methyl group, an ethyl group, a propyl group, an iso-propyl group, a butyl group, or a tert-butyl group, more preferably a hydrogen atom, a methyl group, an ethyl group, or a propyl group. Group, more preferably a hydrogen atom or a methyl group, and particularly preferably a methyl group.

R ₃ represents a hydrogen atom or an alkyl group. R ₃ is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, from the viewpoints of chemical stability, charge mobility, and heat resistance. Specifically, it is a hydrogen atom or a methyl group, more preferably a methyl group.

Further, at least two of R _{1 to} R ₃ may be bonded to each other to form a ring. The ring is preferably an aliphatic hydrocarbon ring. The number of ring members is not particularly limited, but is preferably a 5- to 12-membered ring, more preferably a 5- or 6-membered ring, and still more preferably a 6-membered ring. Specific examples of the ring include a cyclopentane ring, a cyclohexane ring, an adamantane ring, and the like.

S ₁₁ represents the above substituent (S ₁₁ ) and is substituted as any one of R _{a1 to} R _a8 . It is preferable that at least one of Ra ₃ and Ra ₆ in the general formula (A-1) independently represents the substituent (S ₁₁ ).
Preferred examples of the substituent (S ₁₁ ) include the following (a) to (x), (a) to (j) are more preferable, (a) to (h) are more preferable, and (a) to ( f) is particularly preferable, (a) to (c) are more preferable, and (a) is most preferable.

n independently represents an integer of 1 to 4, preferably 1 to 3, more preferably 1 or 2, and particularly preferably 2. By introducing the substituent represented by S ₁₁ , the interaction with the photoelectric conversion layer is suppressed, the dark current is reduced, and the compounds represented by the general formula (F-1) are increased by high molecular weight. The intermolecular force increases, and the device has high heat resistance.

As one of the preferable embodiments in the present invention, in the group represented by the general formula (A-1), Ra _{1 to} Ra ₈ each independently represents a hydrogen atom, a halogen atom, or an alkyl group. .

In the group represented by the general formula (A-1), when Ra _{1 to} Ra ₈ each independently represents a hydrogen atom, a halogen atom, or an alkyl group, one of preferred forms is the general formula (A-1 Is a group represented by the following general formulas (A-3) to (A-5).

(In the general formulas (A-3) to (A-5), Ra _{33 to} Ra ₃₈ , Ra ₄₁ , Ra _{44 to} Ra ₄₈ , Ra ₅₁ , Ra ₅₂ , Ra _{55 to} Ra ₅₈ are each independently a hydrogen atom. * Represents a bonding position, Xa represents a single bond, oxygen atom, sulfur atom, alkylene group, silylene group, alkenylene group, cycloalkylene group, cycloalkenylene group, arylene group, 2 Represents a valent heterocyclic group or an imino group, each of S ₁₁ independently represents the substituent (S ₁₁ ), Ra _{33 to} Ra ₃₈ , Ra ₄₁ , Ra _{44 to} Ra ₄₈ , Ra ₅₁ , Ra ₅₂ , Ra; _.Z 31 to replace the one of in _{55 ~Ra 58, Z 41, Z} 51 is a cycloalkyl ring, aromatic hydrocarbon ring, or .n representing an aromatic heterocyclic ring Representing a to 4 integer.)

The _{Xa, S 11,} and n in the general formula (A-3) ~ (A -5) general formula (A-1) of _{Xa, S 11,} and have the same meanings as n, preferred ones are also similar. Ra ₃₃ to Ra ₃₈ , Ra ₄₁ , Ra _{44 to} Ra ₄₈ , Ra ₅₁ , Ra ₅₂ , Ra _{55 to} Ra ₅₈ in the general formulas (A-3) to (A-5) are represented by Ra in the general formula (A-1). ₂₁ to Ra ₂₈ represents a hydrogen atom, has the same meaning as the halogen atom, or an alkyl group, preferable ones are also same.

Z ₃₁ , Z ₄₁ and Z _{51 each} represents a cycloalkyl ring, an aromatic hydrocarbon ring, or an aromatic heterocyclic ring. The ring represented by Z ₃₁ , Z ₄₁ and Z ₅₁ is preferably a cycloalkyl ring having 5 to 18 carbon atoms, a benzene ring, a naphthalene ring, an indane ring, an anthracene ring, a pyrene ring, a phenanthrene ring, a perylene ring, or a pyridine ring. Quinoline ring, isoquinoline ring, phenanthridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, triazine ring, cinnoline ring, acridine ring, phthalazine ring, quinazoline ring, quinoxaline ring, naphthyridine ring, pteridine ring, pyrrole ring, pyrazole ring , Triazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, oxazole ring, thiazole ring, oxadiazole ring, thiadiazole ring, benzoxazole ring, benzothiazole ring, imidazopyridine ring, thiophene ring, benzothi Fen ring, a furan ring, benzofuran ring, a phosphole ring, a phosphinine ring, and a silol ring. More preferably, a C5-C18 cycloalkyl ring, benzene ring, naphthalene ring, indane ring, anthracene ring, pyrene ring, phenanthrene ring, perylene ring, pyrrole ring, indole ring, carbazole ring, indazole ring, thiophene ring, A benzothiophene ring, a furan ring and a benzofuran ring, more preferably a cycloalkyl ring having 5 to 18 carbon atoms, a benzene ring, a naphthalene ring, an indane ring, an indole ring, a carbazole ring and an indazole ring, particularly preferably A cycloalkyl ring having 5 to 10 carbon atoms, a benzene ring, a naphthalene ring, an indane ring, and an anthracene ring. Among them, a cycloalkyl ring having 5 to 10 carbon atoms, a benzene ring, a naphthalene ring, and an indane ring are most preferable. Is a cycloalkyl ring having 5 to 6 carbon atoms, benze Ring, indane ring. These rings may further have a substituent W described later.

Specific examples of the group represented by the general formula (A-1) include groups represented by the following N-1 to N-135. However, the present invention is not limited to these. The group represented by formula (A-1) is preferably N-1 to N-93, more preferably N-1 to N-79, still more preferably N-1 to N-37, and N- 1 to N-3, N-12 to N-22, and N-24 to N-35 are particularly preferable, and N-1 to N-3, N-17 to N-22, and N-30 to N-35 are particularly preferable. N-1 to N-3, N-17 to N-19, and N-30 to N-32 are most preferable. In the figure, (S) represents the aforementioned substituent (S ₁₁ ), n ′ and n ″ each independently represents an integer of 1 to 4, and n ′ + n ″ is an integer of 1 to 4.

As a compound represented by general formula (F-1), one of the preferable forms is a compound represented by the following general formula (F-2). By having a structure such as the general formula (F-2), the interaction with the photoelectric conversion layer is suppressed, the dark current is reduced, the intermolecular force is increased by increasing the molecular weight, and the device has high heat resistance. .
It is preferable that the compound represented by general formula (F-1) is a compound represented by general formula (F-2).

(In General Formula (F-2), R _{11 to} R ₁₆ , R ₁₈ , R ′ _{11 to} R ′ ₁₆ and R ′ ₁₈ are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. , A hydroxyl group, an amino group, or a mercapto group, which may further have a substituent, A ₁₁ and A ₁₂ each independently represent a substituent represented by the general formula (A-1); Substitute as any one of R _{11 to} R ₁₄ and any one of R ′ _{11 to} R ′ _14. Y is independently a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, or silicon. Represents an atom, which may further have a substituent.)

In General Formula (F-2), R _{11 to} R ′ ₁₆ , R ₁₈ , R ′ _{11 to} R ′ ₁₆ , R ′ ₁₈ , Y, A ₁₁ , and A ₁₂ are R ₁₁ in General Formula (F-1). _{~R '16, R 18, R} ' 11 ~R '16, R' 18, Y, a 11, and have the same meanings as _{a 12,} the preferred ranges are also the same.

One of the preferable forms of the compound represented by the general formula (F-1) is that in the general formula (F-1), each Y is independently —C (R ₂₁ ) (R ₂₂ ) —, —Si. In the group represented by (R ₂₃ ) (R ₂₄ ) —, an oxygen atom, or a sulfur atom and represented by the general formula (A-1), Ra _{1 to} Ra ₈ are each independently a hydrogen atom, This is a case where a halogen atom or an alkyl group is represented. By using the compound in such an embodiment for the electron blocking layer, the interaction with the photoelectric conversion layer is suppressed, the dark current is reduced, the intermolecular force is increased by the increase in the molecular weight, and the device has high heat resistance.

Furthermore, as another embodiment of the compound represented by the general formula (F-1), it is also preferable that, in the general formula (F-1), Y independently represents —N (R ₂₀ ) —. By using such a compound in the electron blocking layer, an effect of obtaining an element having a high response speed can be obtained.

When the ionization potential (Ip) of the compound according to the present invention is used for the electron blocking layer, it is necessary to receive holes without any barrier from the material responsible for hole transport in the photoelectric conversion layer. It needs to be smaller than Ip of the material to carry. In particular, when an absorbing material having sensitivity in the visible range is selected, the ionization potential of the compound according to the present invention is preferably 5.8 eV or less in order to adapt to more materials. When Ip is 5.8 eV or less, an effect of exhibiting high charge collection efficiency and high-speed response without generating a barrier to charge transport can be obtained.
Further, Ip is preferably 4.9 eV or more, and more preferably 5.0 eV or more. When Ip is 4.9 eV or more, a higher dark current suppressing effect can be obtained.
The Ip of each compound can be measured by ultraviolet photoelectron spectroscopy (UPS) or an atmospheric photoelectron spectrometer (for example, AC-2 manufactured by Riken Keiki Co., Ltd.).
Ip of the compound according to the present invention can be within the above range by changing the substituent bonded to the skeleton.

[Compound represented by formula (F-1)]
The present invention also relates to a compound represented by the following general formula (F-1). Since the compound represented by the general formula (F-1) has excellent heat resistance and high charge transportability, it is suitable for forming an electron blocking layer.

(In General Formula (F-1), R _{11 to} R ₁₈ , R ′ _{11 to} R ′ ₁₈ are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxyl group, an amino group, or It represents a mercapto group, which may further have a substituent. _However, any one in R 15 _{to R 18} is coupled with any one in R _'15 ~R' _18, single bond A ₁₁ and A ₁₂ each independently represent a substituent represented by the following general formula (A-1), any one of R _{11 to} R ₁₄ , and R ′ _{11 to} R ′ _14. And each Y is independently a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, or a silicon atom, which may further have a substituent.

(In General Formula (A-1), Ra _{1 to} Ra ₈ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, and these may further have a substituent. At least two of Ra _{1 to} Ra ₈ may be bonded to each other to form a ring, * represents a bonding position, and Xa represents a single bond, an oxygen atom, a sulfur atom, an alkylene group, a silylene group, or an alkenylene. Represents a group, a cycloalkylene group, a cycloalkenylene group, an arylene group, a divalent heterocyclic group, or an imino group, which may further have a substituent, and each of S ₁₁ independently represents the following substituent (S ₁₁ ) And substituted as any one of Ra _{1 to} Ra _8. Each n independently represents an integer of 1 to 4.)

(R _{1 to} R ₃ each independently represents a hydrogen atom or an alkyl group. At least two of R _{1 to} R ₃ may be bonded to each other to form a ring.)

R _{11 to} R ₁₈ , R ′ _{11 to} R ′ ₁₈ , A ₁₁ , A ₁₂ , Y, Xa, Ra _{1 to} Ra ₈ , R _{1 to} R in the compound represented by the general formula (F-1) of the present invention. ₃ and n are R _{11 to} R ₁₈ , R ′ _{11 to} R ′ ₁₈ , A ₁₁ , A ₁₂ , Y, Xa in General Formula (F-1) contained in the photoelectric conversion element of the present invention described above. _{ra 1 ~Ra 8, R 1 ~R} 3, and have the same meanings as n, preferred ranges are also the same.
It is preferable that the compound represented by general formula (F-1) is a compound represented by the said general formula (F-2). Further, in the compound represented by the general formula (F-1), in the general formula (F-1), each Y is independently —C (R ₂₁ ) (R ₂₂ ) — or —Si (R ₂₃ ). In the group represented by (R ₂₄ ) —, an oxygen atom, or a sulfur atom, and represented by the general formula (A-1), Ra _{1 to} Ra ₈ are each independently a hydrogen atom, a halogen atom, or It is also preferred when it represents an alkyl group.

Hereinafter, although the specific example of a compound represented by general formula (F-1) based on this invention is shown, this invention is not limited to the following specific examples. In the formulas (a) to (t), “A ₁₁ and A ₁₂ ”, “R ₂₀ and R ′ ₂₀ ”, “R ₂₃ , R ₂₄ and R ′ ₂₃ , R ′ ₂₄ ” and the like are not the same. A combination other than the illustrated structure is also possible.
In addition, the partial structure of B-1 to B-51 in the following compound examples shows the following. Further, Me: methyl group, Et: ethyl group, i-Pr: isopropyl group, n-Bu: n-butyl group, t-Bu: tert-butyl group, Ph: phenyl group, 2-tol: 2-toluyl group , 3-tol: 3-toluyl group, 4-tol: 4-toluyl group, 1-Np: 1-naphthyl group, 2-Np: 2-naphthyl group, 2-An: 2-anthryl group, 2-Fn: 2-Fluorenyl group.

The molecular weight of the compound according to the present invention is preferably 500 or more and 2000 or less, more preferably 500 or more and 1500 or less, and still more preferably 700 or more and 1300 or less. When the molecular weight is 500 or more and 2000 or less, the material can be deposited and the heat resistance can be further increased.
From the viewpoint of the effect of the photoelectric conversion element, the compound according to the present invention preferably has less impurities such as halogen ions and metal ions.
The compound according to the present invention can be synthesized by applying a known method.

  The present invention also relates to an electron blocking material containing the compound represented by the general formula (F-1) and a film containing the compound represented by the general formula (F-1).

  When used as a charge blocking layer, the amount of the compound of the general formula (F-1) is preferably from 10 nm to 300 nm, more preferably from 30 nm to 150 nm, particularly preferably from 50 nm to 100 nm, in terms of a single layer. . When used as a layer inserted between the photoelectric conversion layer and the charge blocking layer, it is preferably 100 nm or less, more preferably 50 nm or less, and still more preferably 20 nm or less in terms of a single layer.

  The photoelectric conversion element of this invention contains the compound of general formula (F-1) in an electron blocking layer. In the electron blocking layer, the portion in contact with the electrode needs to have a sufficiently small Ea to suppress the electron injection from the electrode, and accordingly, the Ip of the portion tends to be relatively small as a result. In the portion of the electron blocking layer in contact with the photoelectric conversion layer, in order to receive holes from the photoelectric conversion layer to the electron blocking layer without an energy barrier, the Ip must be designed to be smaller than the Ip of the hole transport portion in the photoelectric conversion layer. In many cases, the material constituting the electron blocking is inevitably designed to have a relatively small Ip. In that case, if the material of the general formula (F-1) is used, When contacted with a material having a large Ea, the same Ip can be used in a form in which the boiling charge is further suppressed. The compound represented by the general formula (F-1) in the electron blocking layer is 10% by mass to 100% by mass with respect to the total compound mass forming the electron blocking layer from the viewpoints of heat resistance, response speed, and efficiency. It is preferable that it is 20 mass% or more and 100 mass% or less. More preferably, they are 30 to 100 mass%.

In addition, when it has a hole blocking layer like the aspect shown in FIG.1 (b), it is preferable to use an electron-accepting material as a material for forming a hole blocking layer.
Examples of the electron-accepting material include 1,3-bis (4-tert-butylphenyl-1,3,4-oxadiazolyl) phenylene (OXD-7) and other oxadiazole derivatives, anthraquinodimethane derivatives, and diphenylquinone derivatives. , Bathocuproine, bathophenanthroline, and derivatives thereof, triazole compounds, tris (8-hydroxyquinolinato) aluminum complexes, bis (4-methyl-8-quinolinato) aluminum complexes, distyrylarylene derivatives, silole compounds, etc. Can do. Moreover, even if it is not an electron-accepting organic material, it can be used if it is a material which has sufficient electron transport property. A porphyrin-based compound or a styryl-based compound such as DCM (4-dicyanomethylene-2-methyl-6- (4- (dimethylaminostyryl))-4H pyran) or a 4H pyran-based compound can be used.
Specifically, the following compounds are preferable. In the following specific examples, Ea represents the electron affinity (eV) of the material, and Ip represents the ionization potential (eV) of the material.

The charge blocking layer can be formed by vapor deposition. The vapor deposition may be either physical vapor deposition (PVD) or chemical vapor deposition (CVD), but physical vapor deposition such as vacuum vapor deposition is preferred. In the case of forming a film by vacuum vapor deposition, production conditions such as the degree of vacuum and vapor deposition temperature can be set in accordance with a conventional method.
The thickness of the charge blocking layer is preferably 10 nm or more and 300 nm or less, more preferably 30 nm or more and 150 nm or less, and particularly preferably 50 nm or more and 100 nm or less. When the thickness is 10 nm or more, a suitable dark current suppressing effect is obtained, and when the thickness is 300 nm or less, a suitable photoelectric conversion efficiency is obtained.
Note that a plurality of charge blocking layers may be formed.

(Photoelectric conversion layer)
In the present invention, the organic material constituting the photoelectric conversion layer (12 in FIG. 1) preferably includes at least one of a p-type organic semiconductor and an n-type organic semiconductor, and more preferably includes an n-type organic semiconductor. preferable. The effect of the present invention is particularly significant when the photoelectric conversion layer contains a material having an electron affinity (Ea) of 4.0 eV or more. Examples of the material having an electron affinity (Ea) of 4.0 eV or more include an n-type organic semiconductor described later.

[P-type organic semiconductor]
A p-type organic semiconductor (compound) is a donor-type organic semiconductor (compound), which is mainly represented by a hole-transporting organic compound and refers to an organic compound having a property of easily donating electrons. More specifically, an organic compound having a smaller ionization potential when two organic materials are used in contact with each other. Therefore, any organic compound can be used as the donor organic compound as long as it is an electron-donating organic compound. For example, triarylamine compound, benzidine compound, pyrazoline compound, styrylamine compound, hydrazone compound, triphenylmethane compound, carbazole compound, polysilane compound, thiophene compound, phthalocyanine compound, cyanine compound, merocyanine compound, oxonol compound, polyamine compound, indole Compounds, pyrrole compounds, pyrazole compounds, polyarylene compounds, condensed aromatic carbocyclic compounds (naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, fluoranthene derivatives), nitrogen-containing heterocyclic compounds The metal complex etc. which it has as can be used. Not limited to this, as described above, any organic compound having an ionization potential smaller than that of the organic compound used as the n-type (acceptor property) compound may be used as the donor organic semiconductor.

Among the above, a triarylamine compound is preferable.
Among these, triarylamine compounds represented by the following general formula (I) are more preferable.

In the formula, Z ₁ represents an atomic group necessary for forming a 5- or 6-membered ring. L ₁ , L ₂ and L ₃ each represents an unsubstituted methine group or a substituted methine group. D ₁ represents an atomic group. n ₁ represents an integer of 0 or more.
In the general formula (I), Z ₁ represents an atomic group necessary for forming a 5- or 6-membered ring. L ₁ , L ₂ and L ₃ each represents an unsubstituted methine group or a substituted methine group. D ₁ represents an atomic group. n ₁ represents an integer of 0 or more.

Z ₁ represents an atomic group necessary for forming a 5- or 6-membered ring, and the ring formed is preferably one that is usually used as an acidic nucleus in a merocyanine dye, and specific examples thereof include the following: Can be mentioned.

(A) 1,3-dicarbonyl nucleus: For example, 1,3-indandione nucleus, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione, 1,3-dioxane-4,6- Zeon etc. (B) pyrazolinone nucleus: for example 1-phenyl-2-pyrazolin-5-one, 3-methyl-1-phenyl-2-pyrazolin-5-one, 1- (2-benzothiazoyl) -3-methyl-2 -Pyrazolin-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) Oxindole nucleus: For example, 1-alkyl-2,3-dihydro-2-oxindole and the like. (E) 2,4,6-triketohexahydropyrimidine nucleus: for example, barbituric acid or 2-thiobarbituric acid and its derivatives. Examples of the derivatives include 1-alkyl compounds such as 1-methyl and 1-ethyl, 1,3-dialkyl compounds such as 1,3-dimethyl, 1,3-diethyl and 1,3-dibutyl, 1,3-diphenyl, 1,3-diaryl compounds such as 1,3-di (p-chlorophenyl) and 1,3-di (p-ethoxycarbonylphenyl), 1-alkyl-1-aryl compounds such as 1-ethyl-3-phenyl, Examples include 1,3-di (2-pyridyl) 1,3-diheterocyclic substituents and the like. (F) 2-thio-2,4-thiazolidinedione nucleus: for example, rhodanine and derivatives thereof. Examples of the derivatives include 3-alkylrhodanine such as 3-methylrhodanine, 3-ethylrhodanine and 3-allylrhodanine, 3-arylrhodanine such as 3-phenylrhodanine, and 3- (2-pyridyl) rhodanine. And the like.

(G) 2-thio-2,4-oxazolidinedione (2-thio-2,4- (3H, 5H) -oxazoledione nucleus: for example, 3-ethyl-2-thio-2,4-oxazolidinedione and the like. h) thianaphthenone nucleus: eg 3 (2H) -thianaphthenone-1,1-dioxide etc. (i) 2-thio-2,5-thiazolidinedione nucleus: eg 3-ethyl-2-thio-2,5-thiazolidine (J) 2,4-thiazolidinedione nucleus: for example 2,4-thiazolidinedione, 3-ethyl-2,4-thiazolidinedione, 3-phenyl-2,4-thiazolidinedione, etc. (k) thiazoline- 4-one nucleus: for example 4-thiazolinone, 2-ethyl-4-thiazolinone, etc. (l) 2,4-imidazolidinedione (hydantoin) nucleus: for example 2,4-imidazoli N-dione, 3-ethyl-2,4-imidazolidinedione, etc. (m) 2-thio-2,4-imidazolidinedione (2-thiohydantoin) nucleus: for example 2-thio-2,4-imidazolidinedione, 3-ethyl-2-thio-2,4-imidazolidinedione, etc. (n) imidazolin-5-one nucleus: for example, 2-propylmercapto-2-imidazolin-5-one, etc. (o) 3,5-pyra Zolidinedione nucleus: for example 1,2-diphenyl-3,5-pyrazolidinedione, 1,2-dimethyl-3,5-pyrazolidinedione, etc. (p) Benzothiophen-3-one nucleus: for example benzo Thiophen-3-one, oxobenzothiophen-3-one, dioxobenzothiophen-3-one, etc. (q) Indanone nucleus: for example 1-indanone, 3-phenyl-1-inda Down, 3-methyl-1-indanone, 3,3-diphenyl-1-indanone, 3,3-dimethyl-1-indanone and the like.

The ring formed by Z ₁ is preferably a 1,3-dicarbonyl nucleus, a pyrazolinone nucleus, a 2,4,6-triketohexahydropyrimidine nucleus (including a thioketone body, for example, a barbituric acid nucleus, 2-thiobarbitur tool) Acid nucleus), 2-thio-2,4-thiazolidinedione nucleus, 2-thio-2,4-oxazolidinedione nucleus, 2-thio-2,5-thiazolidinedione nucleus, 2,4-thiazolidinedione nucleus, 2, In 4-imidazolidinedione nucleus, 2-thio-2,4-imidazolidinedione nucleus, 2-imidazolin-5-one nucleus, 3,5-pyrazolidinedione nucleus, benzothiophen-3-one nucleus, indanone nucleus More preferably 1,3-dicarbonyl nucleus, 2,4,6-triketohexahydropyrimidine nucleus (including thioketone, for example, barbituric acid nucleus, 2-thiovale nucleus, Bituric acid nucleus), 3,5-pyrazolidinedione nucleus, benzothiophen-3-one nucleus, indanone nucleus, more preferably 1,3-dicarbonyl nucleus, 2,4,6-triketohexahydropyrimidine Nuclei (including thioketone bodies, such as barbituric acid nuclei, 2-thiobarbituric acid nuclei), particularly preferably 1,3-indandione nuclei, barbituric acid nuclei, 2-thiobarbituric acid nuclei and their derivatives. is there.

What is preferable as a ring formed by Z ₁ is represented by the following formula.

Z ³ represents an atomic group necessary for forming a 5- to 6-membered ring. Z ³ can be selected from the ring formed by Z ₁ above, preferably 1,3-dicarbonyl nucleus, 2,4,6-triketohexahydropyrimidine nucleus (including thioketone body), Particularly preferred are a 1,3-indandione nucleus, a barbituric acid nucleus, a 2-thiobarbituric acid nucleus and derivatives thereof.

By controlling the interaction between acceptor parts, when used as a co-deposited film and C _60, we have found that it is possible to express a high hole-transport property. It is possible to control the interaction by introducing an acceptor moiety structure and a steric hindrance substituent. In the barbituric acid nucleus and 2-thiobarbituric acid nucleus, it is possible to control the intermolecular interaction preferably by substituting two hydrogen atoms at two N positions with substituents. Includes a substituent W described later, more preferably an alkyl group, still more preferably a methyl group, an ethyl group, a propyl group, or a butyl group.
When the ring formed by Z ₁ is a 1,3-indandione nucleus, it is preferably a group represented by the following general formula (IV) or a group represented by the following general formula (V).
Formula (IV)

R _{41 to} R ₄₄ each independently represents a hydrogen atom or a substituent.
General formula (V)

R ₄₁ , R ₄₄ and R _{45 to} R ₄₈ each independently represent a hydrogen atom or a substituent.

In the case of the group represented by the general formula (IV), R _{41 to} R ₄₄ each independently represents a hydrogen atom or a substituent. As the substituent, those exemplified as the substituent W can be applied. Further, R _{41 to} R ₄₄ that are adjacent to each other can be bonded to form a ring, and R ₄₂ and R ₄₃ are bonded to form a ring (for example, a benzene ring, a pyridine ring, or a pyrazine ring). The case is preferred. R _{41 to} R ₄₄ are preferably all hydrogen atoms.
The case where the group represented by the general formula (IV) is a group represented by the general formula (V) is preferable. In the case of the group represented by the general formula (V), R ₄₁ , R ₄₄ , and R _{45 to} R ₄₈ each independently represent a hydrogen atom or a substituent. As the substituent, those exemplified as the substituent W can be applied. R ₄₁ , R ₄₄ , and R _{45 to} R ₄₈ are preferably all hydrogen atoms.

When the ring formed by Z ₁ is a 2,4,6-triketohexahydropyrimidine nucleus (including a thioketone body), it is preferably a group represented by the following general formula (VI).
Formula (VI)

R ₈₁ and R ₈₂ each independently represents a hydrogen atom or a substituent. R ₈₃ represents an oxygen atom, a sulfur atom or a substituent.

In the case of the group represented by the general formula (VI), R ₈₁ and R ₈₂ each independently represents a hydrogen atom or a substituent. As the substituent, those exemplified as the substituent W can be applied. R ₈₁ and R ₈₂ are each independently preferably an alkyl group, an aryl group, or a heterocyclic group (such as 2-pyridyl), and an alkyl group having 1 to 6 carbon atoms (for example, methyl, ethyl, n-propyl, t-butyl). ) Is more preferable.
R ₈₃ represents an oxygen atom, a sulfur atom or a substituent, and R ₈₃ preferably represents an oxygen atom or a sulfur atom. As the substituent, those in which the bond part is a nitrogen atom and those having a carbon atom are preferable. In the case of a nitrogen atom, an alkyl group (1 to 12 carbon atoms) or an aryl group (6 to 12 carbon atoms) is preferable. Specific examples include a methylamino group, an ethylamino group, a butylamino group, a hexylamino group, a phenylamino group, and a naphthylamino group. In the case of a carbon atom, it is sufficient that at least one electron-withdrawing group is substituted. Examples of the electron-withdrawing group include a carbonyl group, a cyano group, a sulfoxide group, a sulfonyl group, or a phosphoryl group. It is good to have. Examples of this substituent include W. R ₈₃ is preferably one that forms a 5-membered or 6-membered ring containing the carbon atom, and specifically includes those having the following structures.

Ph in the above group represents a phenyl group.
L ₁ , L ₂ and L ₃ each independently represents an unsubstituted methine group or a substituted methine group. Substituted methine groups may combine to form a ring (eg, a 6-membered ring such as a benzene ring). Although the substituent of the substituted methine group includes the substituent W, it is preferable that all of L ₁ , L ₂ and L ₃ are unsubstituted methine groups.

n ₁ represents an integer of 0 or more, preferably 0 or more and 3 or less, and more preferably 0. If increased n _1, it can be absorbed wavelength region to a long wavelength, the thermal decomposition temperature becomes low. N ₁ = 0 is preferable in that it has appropriate absorption in the visible region and suppresses thermal decomposition during vapor deposition.

D ₁ represents an atomic group. The D ₁ is preferably a group containing —NR ^a (R ^b ), and the D ₁ is an aryl group substituted with —NR ^a (R ^b ) (preferably a phenyl group or A naphthyl group) is preferred. R ^a and R ^b each independently represents a hydrogen atom or a substituent, and examples of the substituent represented by R ^a and R ^b include the substituent W, preferably an aliphatic hydrocarbon group (preferably An alkyl group which may be substituted, an alkenyl group), an aryl group (preferably a phenyl group which may be substituted), or a heterocyclic group. The heterocycle is preferably a 5-membered ring such as furan, thiophene, pyrrole or oxadiazole.
When R ^a and R ^b are a substituent (preferably an alkyl group or an alkenyl group), the substituent is an aromatic ring (preferably benzene ring) skeleton of an aryl group substituted by —NR ^a (R ^b ). It may combine with a hydrogen atom or a substituent to form a ring (preferably a 6-membered ring). In this case, the case represented by the following general formula (VIII), (IX) or (X) is preferable.
R ^a and R ^b may be bonded to each other to form a ring (preferably a 5-membered or 6-membered ring, more preferably a 6-membered ring), and each of R ^a and R ^b is L A ring (preferably a 5-membered or 6-membered ring, more preferably a 6-membered ring) may be formed by combining with a substituent in (represents any one of L ₁ , L ₂ and L ₃ ).
D ₁ is preferably an aryl group substituted with an amino group at the para position (preferably a phenyl group). In this case, it is preferably represented by the following general formula (II). The amino group may be substituted. Examples of the substituent of the amino group include a substituent W, an aliphatic hydrocarbon group (preferably an alkyl group which may be substituted), an aryl group (preferably an optionally substituted phenyl group), or a heterocyclic group. Is preferred. The amino group is preferably a so-called diaryl group-substituted amino group in which two aryl groups are substituted. In this case, the amino group is preferably represented by the following general formula (III). Further, the substituent of the amino group (preferably an alkyl group or alkenyl group which may be substituted) is bonded to a hydrogen atom of the aromatic ring (preferably benzene ring) skeleton of the aryl group or a ring (preferably 6-membered). Ring) may be formed.
Formula (II)

In the formula, R _{1 to} R ₆ each independently represent a hydrogen atom or a substituent. R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆ , R ₂ and R ₅ , and R ₄ and R ₆ may be bonded to each other to form a ring.
Formula (III)

In the formula, R _{811 to} R ₈₁₄ , R _{820 to} R ₈₂₄ , and R _{830 to} R ₈₃₄ each independently represent a hydrogen atom or a substituent. R _{811 to} R ₈₁₄ , R _{820 to} R ₈₂₄ , and R _{830 to} R ₈₃₄ may be bonded to each other to form a ring.

When R ^a and R ^b are an aliphatic hydrocarbon group, an aryl group or a heterocyclic group, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, Aryloxycarbonyl group, acylamino group, sulfonylamino group, sulfonyl group, silyl group, aromatic heterocyclic group, more preferably alkyl group, alkenyl group, aryl group, alkoxy group, aryloxy group, silyl group, aromatic A heterocyclic group, more preferably an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a silyl group, and an aromatic heterocyclic group. As specific examples, those exemplified for the substituent W can be applied.

R ^a and R ^b are preferably an alkyl group, an aryl group, or an aromatic heterocyclic group. R ^a and R ^b are particularly preferably an alkyl group, an alkylene group linked to L to form a ring, or an aryl group, and more preferably an alkyl group having 1 to 8 carbon atoms, linked to L to 5 to 6 An alkylene group forming a member ring, or a substituted or unsubstituted phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted phenyl group.

It is also preferable that D ₁ is represented by the following general formula (VII).
Formula (VII)

In the formula, R _{91 to} R ₉₈ each independently represent a hydrogen atom or a substituent. m represents an integer of 0 or more. m is preferably 0 or 1. Rx and Ry each independently represent a hydrogen atom or a substituent. When m is 2 or more, Rx and Ry bonded to each 6-membered ring may be different substituents. R ₉₁ and R ₉₂ , R ₉₂ and Rx, Rx and R ₉₄ , R ₉₄ and R ₉₇ , R ₉₃ and Ry, Ry and R ₉₅ , R ₉₅ and R ₉₆ , R ₉₇ and R ₉₈ are independent of each other. Thus, a ring may be formed. In addition, the bonding portion with L ₃ (L ₁ when n ₁ is 0) may be the position of R ₉₁ , R ₉₂ , R ₉₃ , and in that case, the bonding portion with L ₃ in the general formula (VII) A substituent or a hydrogen atom corresponding to R ₉₁ , R ₉₂ , or R ₉₃ may be bonded to the site represented as, and adjacent Rs may be bonded to form a ring. Here, “adjacent Rs may be bonded to form a ring” means, for example, when R ₉₁ is a bonding part with L ₃ (L ₁ when n ₁ is 0), If R ₉₀ is bonded to the bonding part of the general formula (VII), R ₉₀ and R ₉₃ may be bonded to form a ring, and R ₉₂ is L ₃ (when n ₁ is 0). Is a bond to L ₁ ), and R ₉₀ is bonded to the bond of general formula (VII), R ₉₀ and R ₉₁ , and R ₉₀ and R ₉₃ are bonded to form a ring. In addition, when R ₉₃ is a bonding portion with L ₃ (L ₁ when n ₁ is 0), it is assumed that R ₉₀ is bonded to the bonding portion of the general formula (VII). R ₉₀ and R ₉₁ , R ₉₁ and R ₉₂ may be bonded to each other to form a ring.
The above ring is preferably a benzene ring.
The substituent of R _{91 to} R ₉₈ , Rx, and Ry includes the substituent W.
R _{91 to} R ₉₆ are preferably all hydrogen atoms, and Rx and Ry are preferably both hydrogen atoms. R _{91 to} R ₉₆ are preferably hydrogen atoms, and Rx and Ry are also preferably hydrogen atoms.
R ₉₇ and R ₉₈ each independently preferably represent a phenyl group which may be substituted, and examples of the substituent include the substituent W, preferably an unsubstituted phenyl group.
m represents an integer of 0 or more, but 0 or 1 is preferable.

It is also preferred that D ₁ is a group represented by the general formula (VIII), (IX) or (X).
Formula (VIII)

In the formula, R _{51 to} R ₅₄ each independently represent hydrogen or a substituent. Substituent W is mentioned as this substituent. R ₅₂ and R ₅₃ , or R ₅₁ and R ₅₂ may be linked to form a ring.
Formula (IX)

In the formula, R _{61 to} R ₆₄ each independently represent hydrogen or a substituent. Substituent W is mentioned as this substituent. R ₆₂ and R ₆₃ , or R ₆₁ and R ₆₂ may be linked to form a ring.
Formula (X)

_Wherein, R 71 _{to R 73} each independently represents hydrogen or a substituent. Substituent W is mentioned as this substituent. R ₇₂ and R ₇₃ may be linked to form a ring.

The group represented by the general formula (II) or (III) is more preferably used as the D ₁ .
In general formula (II), R < ₁ > -R < ₆ > represents a hydrogen atom or a substituent each independently. R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆ , R ₂ and R ₅ , and R ₄ and R ₆ may be bonded to each other to form a ring.
Examples of the substituent in R _{1 to} R ₄ include the substituent W, preferably R _{1 to} R ₄ are a hydrogen atom, or R ₂ and R ₅ or R ₄ and R ₆ form a 5-membered ring. More preferably, R _{1 to} R ₄ are all hydrogen atoms.
The substituent in R ₅ and R ₆ includes the substituent W, and among the substituents, a substituted or unsubstituted aryl group is preferable, and the substituent of the substituted aryl group is an alkyl group (for example, a methyl group, an ethyl group, or the like). Group) and an aryl group (for example, phenyl group, naphthylene group, phenanthryl group, anthryl group) are preferable. R ₅ and R ₆ are preferably a phenyl group, an alkyl-substituted phenyl group, a phenyl-substituted phenyl group, a naphthyl group, a phenanthryl group, an anthryl group, or a fluorenyl group (preferably a 9,9′-dimethyl-2-fluorenyl group).
In general formula (III), R < ₁₁ > -R < ₁₄ >, R < ₂₀ > -R < ₂₄ >, R < ₃₀ > -R < ₃₄ > represents a hydrogen atom or a substituent each independently. R _{11 to} R ₁₄ , R _{20 to} R ₂₄ , and R _{30 to} R ₃₄ may be bonded to each other to form a ring. As an example of the ring formation, R ₁₁ and R ₁₂ , R ₁₃ and R ₁₄ are bonded to form a benzene ring, and two adjacent R _{20 to} R ₂₄ (R ₂₄ and R ₂₃ , R ₂₃ and R ₂₀ , R ₂₀ and R ₂₁ , R ₂₁ and R ₂₂ ) are bonded to form two benzene rings adjacent to R _{30 to} R ₃₄ (R ₃₄ and R ₃₃ , R ₃₃ and R ₃₀ , R ₃₀ and R ₃₁ , R ₃₁ and R ₃₂ ) are combined to form a benzene ring, and R ₂₂ and R ₃₄ are combined to form a 5-membered ring with an N atom.
Examples of the substituent represented by R _{11 to} R ₁₄ , R _{20 to} R ₂₄ , and R _{30 to} R ₃₄ include the substituent W, but preferably an alkyl group (for example, a methyl group or an ethyl group) or an aryl group (for example, , Phenyl group, naphthyl group), and these groups may be further substituted with a substituent W (preferably an aryl group). Among _them, preferred is a case R _{20, R 30} is a substituent, and the other _{R 11 ~R 14, R 21 ~R} 24, R 31 ~R 34 is more preferably be a hydrogen atom.

The compound represented by the general formula (I) is preferably a compound represented by the following general formula (pI).
Formula (pI)

In the formula, Z ₁ represents a ring containing two carbon atoms and represents a 5-membered ring, a 6-membered ring, or a condensed ring containing at least one of a 5-membered ring and a 6-membered ring. L ₁ , L ₂ and L ₃ each independently represents an unsubstituted methine group or a substituted methine group. n ₁ represents an integer of 0 or more. _{Rp 1, Rp 2, Rp 3} , Rp 4, Rp 5, Rp 6 independently represents a hydrogen atom or a substituent. Rp ₁ and Rp ₂ , Rp ₂ and Rp ₃ , Rp ₄ and Rp ₅ , Rp ₅ and Rp ₆ may be bonded to each other to form a ring. Rp ₂₁ and Rp ₂₂ each independently represent a substituted aryl group, an unsubstituted aryl group, a substituted heteroaryl group, or an unsubstituted heteroaryl group.

As a photoelectric conversion material, a compound having a naphthylene group as a connecting part of a donor part (site of —NRp ₂₁ Rp ₂₂ ) / acceptor part (site bonded to a naphthylene group via L _{1 to} L ₃ ) as described above. By using it together with fullerenes, a photoelectric conversion element having excellent heat resistance and high-speed response can be obtained. This is considered that the interaction with the fullerenes is improved and the response speed is improved by using a naphthylene group as the connecting part of the donor part / acceptor part. Moreover, the said compound has sufficient sensitivity.

In the general formula (pI), L ₁ , L ₂ and L ₃ each independently represent an unsubstituted methine group or a substituted methine group. The substituents in the substituted methine group may be bonded to form a ring. A 6-membered ring (for example, benzene ring etc.) is mentioned as a ring. Examples of the substituent of the substituted methine group include the substituent W described later. L ₁ , L ₂ and L ₃ are preferably all unsubstituted methine groups.

n ₁ represents an integer of 0 or more, preferably 0 or more and 3 or less, and more preferably 0. If increased n _1, can be absorbed wavelength region to a long wavelength, the thermal decomposition temperature becomes low. N ₁ = 0 is preferable in that it has appropriate absorption in the visible region and suppresses thermal decomposition during vapor deposition.

Rp _{1 to} Rp ₆ each independently represent a hydrogen atom or a substituent. If Rp ₁ to Rp ₆ represents a _substituent, but examples of a substituent Rp 1 to Rp ₆ represents include the substituent W described below, in particular a halogen atom, an alkyl group, an aryl group, a heterocyclic group, hydroxy group, A nitro group, alkoxy group, aryloxy group, heterocyclic oxy group, amino group, alkylthio group, arylthio group, alkenyl group, and cyano group heterocyclic thio group are preferred.
Rp _{1 to} Rp ₆ are each independently a hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, hydroxy group, nitro group, alkoxy group, aryloxy group, heterocyclic oxy group, amino group, alkylthio group , An arylthio group, an alkenyl group, a cyano group or a heterocyclic thio group, more preferably a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a carbon number. A 6-20 aryl group and a C4-C16 heterocyclic group are more preferable, a hydrogen atom, a C1-C12 alkyl group, and a C6-C14 aryl group are still more preferable, a hydrogen atom, carbon number 1 -6 alkyl groups and C6-C10 aryl groups are more preferred, and hydrogen atoms are particularly preferred. In the case of an alkyl group, there may be a branch. _Also, if Rp 1 to Rp ₆ is a substituent, it may have further substituents. Examples of the further substituent include the substituent W described later.
Preferable specific examples of Rp _{1 to} Rp ₆ include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, a phenyl group, and a naphthyl group.

Rp ₁ and Rp ₂ , Rp ₂ and Rp ₃ , Rp ₄ and Rp ₅ , Rp ₅ and Rp ₆ may be bonded to each other to form a ring. Examples of the ring formed include ring R described later. Preferred are a benzene ring, a naphthalene ring, an anthracene ring, a pyridine ring, a pyrimidine ring and the like.

Rp ₂₁ and Rp ₂₂ each independently represent a substituted aryl group, an unsubstituted aryl group, a substituted heteroaryl group, or an unsubstituted heteroaryl group.
It is preferable that both Rp ₂₁ and Rp ₂₂ are not unsubstituted phenyl groups.
The aryl group Rp _{21, Rp 22} represents preferably an aryl group having 6 to 30 carbon atoms, more preferably an aryl group having 6 to 20 carbon atoms. Specific examples of the aryl group include a phenyl group, a naphthyl group, a biphenylyl group, a terphenyl group, an anthryl group, and a fluorenyl group.
Examples of the substituent of the substituted aryl group in Rp ₂₁ and Rp ₂₂ include an alkyl group (eg, methyl group, ethyl group, t-butyl group), an alkoxy group (eg, methoxy group, ethoxy group, isopropoxy group), and aryl group (For example, phenyl group, naphthyl group, phenanthryl group, anthryl group) and heteroaryl groups (for example, thienyl group, furanyl group, pyridyl group, carbazolyl group) are preferable.

The aryl group or substituted aryl group represented by Rp ₂₁ or Rp ₂₂ is preferably a phenyl group, a substituted phenyl group, a biphenyl group, a naphthyl group, a phenanthryl group, an anthryl group, a fluorenyl group, or a substituted fluorenyl group (preferably 9,9 ′ -Dialkyl-2-fluorenyl group).

When Rp ₂₁ and Rp ₂₂ are heteroaryl groups, the heteroaryl group is preferably a heteroaryl group consisting of a 5-membered, 6-membered or 7-membered ring or a condensed ring thereof. 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, an imidazoline ring, and an imidazolidine. Ring, pyrazole ring, pyrazoline ring, pyrazolidine ring, triazole ring, furazane ring, tetrazole ring, pyran ring, thiine ring, pyridine ring, piperidine ring, oxazine ring, morpholine ring, thiazine ring, pyridazine ring, pyrimidine ring, pyrazine ring, Examples include a piperazine ring and a triazine ring.
As the condensed ring, benzofuran ring, isobenzofuran ring, benzothiophene ring, indole ring, indoline ring, isoindole ring, benzoxazole ring, benzothiazole ring, indazole ring, benzimidazole ring, quinoline ring, isoquinoline ring, cinnoline ring, Phthalazine ring, quinazoline ring, quinoxaline ring, dibenzofuran ring, carbazole ring, xanthene ring, acridine ring, phenanthridine ring, phenanthroline ring, phenazine ring, phenoxazine ring, thianthrene ring, thienothiophene ring, indolizine ring, quinolidine ring, A quinuclidine ring, a naphthyridine ring, a purine ring, a pteridine ring, etc. are mentioned.

Examples of the substituent of the substituted heteroaryl group in Rp ₂₁ and Rp ₂₂ include an alkyl group (for example, methyl group, ethyl group, t-butyl group), an alkoxy group (for example, methoxy group, ethoxy group, isopropoxy group), aryl A group (for example, phenyl group, naphthyl group, phenanthryl group, anthryl group) or a heteroaryl group (for example, thienyl group, furanyl group, pyridyl group, carbazolyl group) is preferable.
The ring constituting the heteroaryl group or substituted heteroaryl group represented by Rp ₂₁ and Rp ₂₂ is preferably a thiophene ring, a substituted thiophene ring, a furan ring, a substituted furan ring, a thienothiophene ring, a substituted thienothiophene ring, or a carbazolyl group. It is.

Rp ₂₁ and Rp ₂₂ are each independently preferably a phenyl group, a naphthyl group, a fluorenyl group, a biphenyl group, an anthracenyl group, or a phenanthrenyl group, and more preferably a phenyl group, a naphthyl group, or a fluorenyl group. The preferred substituents in the case of Rp _21, Rp ₂₂ has a substituent, an alkyl group, a halogenated alkyl group, an alkoxy group, an aryl group or a heteroaryl group, more preferably a methyl group, an isopropyl group, t- butyl Group, trifluoromethyl group, phenyl group, or carbazolyl group.

When Z ₁ is a group represented by the general formula (VI) or a group represented by the general formula (VII), the compound represented by the general formula (pI) is represented by the following general formula (pII), respectively. Or a compound represented by the following general formula (pIII).
The compound represented by the general formula (pI) is preferably a compound represented by the following general formula (pII) or a compound represented by the following general formula (pIII).

  General formula (pII)

In the formula, L ₁ , L ₂ , L ₃ , n ₁ , Rp ₁ , Rp ₂ , Rp ₃ , Rp ₄ , Rp ₅ , Rp ₆ , Rp ₂₁ , Rp ₂₂ are synonymous with the general formula (pI), The preferable range is also the same. Rp ₄₁ , Rp ₄₂ , Rp ₄₃ , Rp ₄₄ are synonymous with R ₄₁ , R ₄₂ , R ₄₃ , R ₄₄ in general formula (IV), and preferred ranges are also the same.

  General formula (pIII)

In the formula, L ₁ , L ₂ , L ₃ , n ₁ , Rp ₁ , Rp ₂ , Rp ₃ , Rp ₄ , Rp ₅ , Rp ₆ , Rp ₂₁ , Rp ₂₂ are synonymous with the general formula (pI), The preferable range is also the same. Rp ₅₁ , Rp ₅₂ , Rp ₅₃ , Rp ₅₄ , Rp ₅₅ , Rp ₅₆ are synonymous with R ₄₁ , R ₄₄ , R ₄₅ , R ₄₆ , R ₄₇ , R ₄₈ in the general formula (V), and preferred ranges are also the same. It is.

The compound represented by the general formula (pI) is preferably a compound represented by the following general formula (pIV).
General formula (pIV)

In the formula, Z ₁ , L ₁ , L ₂ , L ₃ , n ₁ , Rp ₁ , Rp ₂ , Rp ₃ , Rp ₄ , Rp ₅ , Rp ₆ are synonymous with the general formula (pI), and preferred ranges are also included. It is the same.
Rp _{7 to} Rp ₁₁ and Rp _{12 to} Rp ₁₆ each independently represent a hydrogen atom or a substituent. However, the case where all of Rp _{7 to} Rp ₁₁ and Rp _{12 to} Rp ₁₆ are hydrogen atoms is excluded. Further, adjacent ones of Rp _{7 to} Rp ₁₁ and Rp _{12 to} Rp ₁₆ may be bonded to each other to form a ring. Further, Rp ₃ and Rp ₇ , Rp ₆ and Rp ₁₆ may be connected to each other.

In General Formula (pIV), Rp _{7 to} Rp ₁₁ and Rp _{12 to} Rp ₁₆ each independently represent a hydrogen atom or a substituent. However, all of Rp _{7 to} Rp ₁₁ and Rp _{12 to} Rp ₁₆ do not become hydrogen atoms. In the case where Rp ₃ and Rp _7, or Rp ₆ and _{Rp 16} are linked, the other of _{Rp 8 ~Rp 11, Rp 12 ~Rp} 15 may be all a hydrogen atom.
When Rp _{7 to} Rp ₁₁ , Rp _{12 to} Rp ₁₆ represent a substituent, examples of the substituent represented by Rp _{7 to} Rp ₁₁ , Rp _{12 to} Rp ₁₆ include the substituent W described below. Group, aryl group, heterocyclic group, hydroxy group, nitro group, alkoxy group, aryloxy group, heterocyclic oxy group, amino group, alkylthio group, arylthio group, alkenyl group, cyano group and heterocyclic thio group are preferred.
Rp _{7 to} Rp ₁₁ and Rp _{12 to} Rp ₁₆ are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxy group, a nitro group, an alkoxy group, an aryloxy group, or a heterocyclic oxy group. , An amino group, an alkylthio group, an arylthio group, an alkenyl group, a cyano group or a heterocyclic thio group, and more preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, or a heterocyclic group. Preferably, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms A heterocyclic group consisting of a 5-membered, 6-membered or 7-membered ring or a condensed ring thereof is more preferred, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms. An alkenyl group having 2 to 12 carbon atoms, an alkyloxy group having 1 to 12 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a 5-membered or 6-membered ring, or a condensed ring thereof. The heterocyclic group is more preferable.
In the case of an alkyl group, it may be linear or branched. Examples of the hetero atom contained in the heterocyclic group include an oxygen atom, a sulfur atom, and a nitrogen atom.
Specific examples of the alkyl group, alkenyl group, aryl group and the like include groups exemplified by the alkyl group, alkenyl group, and aryl group of the substituent W described later.

Further, adjacent ones of Rp _{7 to} Rp ₁₁ and Rp _{12 to} Rp ₁₆ may be bonded to each other to form a ring. Examples of the ring formed include ring R described later. The ring to be formed is preferably a benzene ring, a naphthalene ring, an anthracene ring, a pyridine ring, a pyrimidine ring or the like.
Further, Rp ₃ and Rp ₇ , Rp ₆ and Rp ₁₆ may be connected to each other. When Rp ₃ and Rp ₇ or Rp ₆ and Rp ₁₆ are connected, it becomes a condensed ring of 4 or more rings containing a naphthylene group and a phenyl group. The linkage between Rp ₃ and Rp ₇ or Rp ₆ and Rp ₁₆ may be a single bond.

The compound represented by the general formula (I) is a compound described in JP 2000-297068 A, and a compound not described in the above publication can also be produced according to the synthesis method described in the above publication. .
Specific examples of the compound represented by the general formula (I) are shown below, but the present invention is not limited thereto.

In the above exemplary compounds, R ₁₀₁ and R ₁₀₂ each independently represent a hydrogen atom or a substituent. Although the substituent W is mentioned as a substituent, An alkyl group or an aryl group is preferable.

  Moreover, the compound represented by the said general formula (I) is compoundable according to the following reaction, for example.

In the above formula, Rp ₁ , Rp ₂ , Rp ₃ , Rp ₄ , Rp ₅ , Rp ₆ , Rp ₂₁ , Rp ₂₂ are as defined above.
In the above synthesis examples, the case where Z ₁ is a 1,3-benzoindandione nucleus among the compounds represented by the general formula (I) has been described, but the case where Z ₁ has another structure is also described above. It can be synthesized in the same manner as described above by changing 3-benzoindandione to a compound that becomes an acidic nucleus in another merocyanine dye.

[N-type organic semiconductor]
An n-type organic semiconductor (compound) is an acceptor organic semiconductor (compound), which is represented by mainly an electron-transporting organic compound and refers to an organic compound having a property of easily accepting electrons. More specifically, the organic compound having the higher electron affinity when two organic compounds are used in contact with each other.
Therefore, as the acceptor organic compound, any organic compound can be used as long as it is an electron-accepting organic compound. For example, condensed aromatic carbocyclic compounds (naphthalene, anthracene, fullerene, phenanthrene, tetracene, pyrene, perylene, fluoranthene, or derivatives thereof), 5- to 7-membered heterocyclic compounds containing a nitrogen atom, an oxygen atom, or a sulfur atom (E.g. pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, pteridine, acridine, phenazine, phenanthroline, tetrazole, pyrazole, imidazole, thiazole, oxazole, indazole, benzimidazole, benzotriazole, Benzoxazole, benzothiazole, carbazole, purine, triazolopyridazine, triazolopyrimidine, tetrazaindene, oxadiazo , Imidazopyridine, pyralidine, pyrrolopyridine, thiadiazolopyridine, dibenzazepine, tribenzazepine, etc.), polyarylene compounds, fluorene compounds, cyclopentadiene compounds, silyl compounds, nitrogen-containing heterocyclic compounds as ligands Etc. Note that the present invention is not limited thereto, and as described above, any organic compound having an electron affinity higher than that of the organic compound used as the donor organic compound may be used as the acceptor organic semiconductor.

  As the n-type organic semiconductor, fullerene or fullerene derivatives are preferably used.

Fullerene C ₆₀ , fullerene C ₇₀ , fullerene C ₇₆ , fullerene C ₇₈ , fullerene C ₈₀ , fullerene C ₈₂ , fullerene C ₈₄ , fullerene C ₉₀ , fullerene C ₉₆ , fullerene C ₂₄₀ , fullerene ₅₄₀ , mixed fullerene Represents a fullerene nanotube, and a fullerene derivative represents a compound having a substituent added thereto. As the substituent, an alkyl group, an aryl group, or a heterocyclic group is preferable.
As the fullerene derivative, the following compounds are preferable.

In addition, as for fullerene and fullerene derivatives, there are quarterly chemical reviews No. 43 (1999), JP-A-10-167994, JP-A-11-255508, JP-A-11-255509, JP-A-2002-241323, JP-A-2003-19681, and the like. It can also be used.
The content of fullerene and fullerene derivative is preferably 50% or more (molar ratio) of the amount of the material forming the mixed film in the mixed layer with the p-type material, and more than 200% The amount (molar ratio) is more preferable, and the amount (molar ratio) of 300% or more is particularly preferable.

The photoelectric conversion layer can be formed by vapor deposition. The vapor deposition may be either physical vapor deposition (PVD) or chemical vapor deposition (CVD), but physical vapor deposition such as vacuum vapor deposition is preferred. In the case of forming a film by vacuum vapor deposition, production conditions such as the degree of vacuum and vapor deposition temperature can be set in accordance with a conventional method.
The thickness of the photoelectric conversion layer is preferably from 10 nm to 1000 nm, more preferably from 50 nm to 800 nm, and particularly preferably from 100 nm to 500 nm. By setting it to 10 nm or more, a suitable dark current suppressing effect is obtained, and by setting it to 1000 nm or less, suitable photoelectric conversion efficiency is obtained.
The present invention also relates to a method for producing a photoelectric conversion element including a step of forming a photoelectric conversion layer and an electron blocking layer by vacuum heating deposition (vacuum deposition).

[Film density]
The photoelectric conversion layer of the present invention is preferably formed in a state where fullerene or a fullerene derivative and at least one other material are mixed or laminated. The film density of the photoelectric conversion layer of the present invention is more preferably 1.40 g / cm ³ or more 2.00 g / cm ³ or less is preferably 1.50 g / cm ³ or more 1.70 g / cm ³ or less.

[Optical sensor]
Photoelectric conversion elements can be broadly classified into photovoltaic cells and optical sensors, but the photoelectric conversion elements of the present invention are suitable for optical sensors. As an optical sensor, the photoelectric conversion element used alone may be used, or a line sensor in which the photoelectric conversion elements are arranged linearly or a two-dimensional sensor arranged on a plane can be used. The photoelectric conversion element of the present invention converts optical image information into an electrical signal using an optical system and a drive unit like a scanner in a line sensor, and optically converts optical image information like an imaging module in a two-dimensional sensor. The system functions as an image sensor by forming an image on a sensor and converting it into an electrical signal.
Since the photovoltaic cell is a power generation device, the efficiency of converting light energy into electrical energy is an important performance, but the dark current that is a current in a dark place is not a functional problem. Furthermore, a subsequent heating step is not necessary for installing the color filter. Since it is important to convert light and dark signals into electrical signals with high accuracy, the efficiency of converting light intensity into current is also important for optical sensors. Low dark current is required. In addition, resistance to subsequent processes is also important.

[Image sensor]
Next, a configuration example of an image sensor including a photoelectric conversion element will be described. In the configuration examples described below, members having the same configuration / action as those already described are denoted by the same or corresponding reference numerals in the drawings, and the description thereof is simplified or omitted.
An image sensor is an element that converts optical information of an image into an electric signal. A plurality of photoelectric conversion elements are arranged on a matrix in the same plane, and an optical signal is converted into an electric signal in each photoelectric conversion element (pixel). That can be output to the outside of the imaging device for each pixel sequentially. Therefore, one pixel is composed of one photoelectric conversion element and one or more transistors.

FIG. 2 is a schematic cross-sectional view showing a schematic configuration of an image sensor for explaining an embodiment of the present invention. This imaging device is used by being mounted on an imaging device such as a digital camera or a digital video camera, an imaging module such as an electronic endoscope or a mobile phone, or the like.
This imaging element has a plurality of photoelectric conversion elements configured as shown in FIG. 1 and a circuit board on which a readout circuit for reading a signal corresponding to the charge generated in the photoelectric conversion film of each photoelectric conversion element is formed. A plurality of photoelectric conversion elements are arranged one-dimensionally or two-dimensionally on the same surface above the circuit board.

  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, buffer layer 109, sealing layer 110, color filter (CF) 111, partition 112, light shielding layer 113, protective layer 114, counter electrode voltage supply 115, and readout circuit 116.

  The pixel electrode 104 has the same function as the electrode 11 of the photoelectric conversion element 10a shown in FIG. The counter electrode 108 has the same function as the electrode 15 of the photoelectric conversion element 10a shown in FIG. The photoelectric conversion film 107 has the same configuration as the layer provided between the electrode 11 and the electrode 15 of the photoelectric conversion element 10a illustrated in FIG.

  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 the photoelectric conversion elements provided on the plurality of pixel electrodes 104 so as to cover them.

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

  The connection part 106 is embedded in the insulating layer 102 and is a plug or the like for electrically connecting the connection electrode 103 and the counter electrode voltage supply part 115. The counter electrode voltage supply unit 115 is formed on the substrate 101 and applies a predetermined voltage to the counter electrode 108 via the connection unit 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 power supply voltage is boosted by a booster circuit such as a charge pump to supply the predetermined voltage.

  The readout circuit 116 is provided on the substrate 101 corresponding to each of the plurality of pixel electrodes 104, and reads out a signal corresponding to the charge collected by the corresponding pixel electrode 104. The reading circuit 116 is configured by, for example, a CCD, a CMOS circuit, a TFT circuit, or the like, and is shielded from light by a light shielding layer (not shown) disposed in the insulating layer 102. The readout circuit 116 is electrically connected to the corresponding pixel electrode 104 via the connection unit 105.

  The buffer layer 109 is formed on the counter electrode 108 so as to cover the counter electrode 108. The sealing layer 110 is formed on the buffer layer 109 so as to cover the buffer layer 109. The color filter 111 is formed at a position facing each pixel electrode 104 on the sealing layer 110. The partition wall 112 is provided between the color filters 111 and is for improving the light transmission efficiency of the color filter 111.

  The light shielding layer 113 is formed in a region other than the region where the color filter 111 and the partition 112 on the sealing layer 110 are provided, 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 partition 112, and the light shielding layer 113, and protects the entire image sensor 100.

  In the imaging device 100 configured as described above, when light is incident, the light is incident on the photoelectric conversion film 107, and charges are generated here. Holes in the generated charges are collected by the pixel electrode 104, and a voltage signal corresponding to the amount is output to the outside of the image sensor 100 by the readout circuit 116.

  The manufacturing method of the image sensor 100 is as follows.

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

  Next, the photoelectric conversion film 107 is formed on the plurality of pixel electrodes 104 by, for example, a vacuum heating deposition method. Next, the counter electrode 108 is formed on the photoelectric conversion film 107 under vacuum 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, a vacuum heating deposition method. Next, after forming the color filter 111, the partition 112, and the light shielding layer 113, the protective layer 114 is formed, and the imaging element 100 is completed.

  Also in the method of manufacturing the image sensor 100, a step of placing the image sensor 100 being manufactured under non-vacuum is added between the process of forming the photoelectric conversion layer included in the photoelectric conversion film 107 and the process of forming the sealing layer 110. Even so, performance degradation of the plurality of photoelectric conversion elements can be prevented. By adding this step, it is possible to suppress the manufacturing cost while preventing the performance degradation of the image sensor 100.

Below, the detail of the sealing layer 110 of the component of the image pick-up element 100 mentioned above is demonstrated.
[Sealing layer]
The following conditions are required for the sealing layer 110.
First, it is possible to protect the photoelectric conversion layer by preventing intrusion of factors that degrade the organic photoelectric conversion material contained in the solution, plasma, and the like in each manufacturing process of the device.
Secondly, after the device is manufactured, the intrusion of factors such as water molecules that degrade the organic photoelectric conversion material is prevented, and the deterioration of the photoelectric conversion film 107 is prevented over a long period of storage / use.
Third, when the sealing layer 110 is formed, the already formed photoelectric conversion layer is not deteriorated.
Fourth, since incident light reaches the photoelectric conversion film 107 through the sealing layer 110, the sealing layer 110 must be transparent to light having a wavelength detected by the photoelectric conversion film 107.

  The sealing layer 110 can be composed of a thin film made of a single material. However, by providing a multi-layered structure and providing each layer with a different function, stress relaxation of the entire sealing layer 110 and generation of dust during the manufacturing process are possible. Such effects as the suppression of defects such as cracks and pinholes caused by the above, and the optimization of material development can be expected. For example, the sealing layer 110 is formed by laminating a “sealing auxiliary layer” having a function that is difficult to achieve on the layer that serves the original purpose of preventing the penetration of deterioration factors such as water molecules. A two-layer structure can be formed. Although it is possible to have three or more layers, it is preferable that the number of layers is as small as possible in consideration of manufacturing costs.

[Formation of sealing layer 110 by atomic layer deposition (ALD)]
The performance of the photoelectric conversion material is significantly deteriorated due to the presence of deterioration factors such as water molecules. Therefore, it is necessary to cover and seal the entire photoelectric conversion film with ceramics such as dense metal oxide / metal nitride / metal nitride oxide, diamond-like carbon (DLC), etc. that do not allow water molecules to permeate. Conventionally, aluminum oxide, silicon oxide, silicon nitride, silicon nitride oxide, a laminated structure thereof, a laminated structure of them and an organic polymer, or the like is used as a sealing layer to form various vacuum film forming techniques. However, since these conventional sealing layers are difficult to grow in a step due to structures on the substrate surface, minute defects on the substrate surface, particles adhering to the substrate surface, etc. (because the step becomes a shadow), In comparison, the film thickness is significantly reduced. For this reason, the step portion becomes a path through which the deterioration factor penetrates. In order to completely cover this step with the sealing layer, it is preferable to form the film so as to have a film thickness of 1 μm or more in the flat portion, thereby increasing the thickness of the entire sealing layer.

  In the image sensor 100 having a pixel size of less than 2 μm, particularly about 1 μm, if the distance between the color filter 111 and the photoelectric conversion layer, that is, the film thickness of the sealing layer 110 is large, incident light is diffracted / diverged in the sealing layer 110. As a result, color mixing occurs. For this reason, the imaging element 100 having a pixel size of about 1 μm is preferably a sealing layer material / manufacturing method that does not deteriorate the element performance even when the film thickness of the entire sealing layer 110 is reduced.

  The atomic layer deposition (ALD) method is a kind of CVD method, and adsorption / reaction of organometallic compound molecules, metal halide molecules, and metal hydride molecules, which are thin film materials, onto the substrate surface and unreacted groups contained therein. Is a technique for forming a thin film by alternately repeating decomposition. When the thin film material reaches the substrate surface, it is in the above-mentioned low molecular state, so that the thin film can be grown in a very small space where the low molecule can enter. For this reason, the step portion, which was difficult with the conventional thin film formation method, is completely covered (the thickness of the thin film grown on the step portion is the same as the thickness of the thin film grown on the flat portion), that is, the step coverage is very high. Excellent. For this reason, steps due to structures on the substrate surface, minute defects on the substrate surface, particles adhering to the substrate surface, and the like can be completely covered, and such a step portion does not become an intrusion path for a deterioration factor of the photoelectric conversion material. When the sealing layer 110 is formed by the atomic layer deposition method, the required sealing layer thickness can be reduced more effectively than in the prior art.

  In the case where the sealing layer 110 is formed by the atomic layer deposition method, a material corresponding to ceramics preferable for the sealing layer 110 described above can be appropriately selected. However, since the photoelectric conversion film of the present invention uses a photoelectric conversion material, it is limited to a material capable of growing a thin film at a relatively low temperature so that the photoelectric conversion material does not deteriorate. According to the atomic layer deposition method using alkyl aluminum or aluminum halide as a material, a dense aluminum oxide thin film can be formed at less than 200 ° C. at which the photoelectric conversion material does not deteriorate. In particular, when trimethylaluminum is used, an aluminum oxide thin film can be formed even at about 100 ° C. Silicon oxide and titanium oxide are also preferable because a dense thin film can be formed at less than 200 ° C., similarly to aluminum oxide, by appropriately selecting materials.

In the above description, the photoelectric conversion layer that absorbs B light can, for example, absorb light of at least 400 to 500 nm, and preferably has a peak wavelength absorptance of 50% or more in that wavelength region. It means something. The photoelectric conversion layer that absorbs G light means, for example, that it can absorb light of at least 500 to 600 nm, and preferably has a peak wavelength absorptance of 50% or more in that wavelength region. . The photoelectric conversion layer that absorbs R light means, for example, that it can absorb light of at least 600 to 700 nm, and preferably has a peak wavelength absorptance of 50% or more in that wavelength region. .
[Driving method]
Furthermore, the present invention is a method for driving a photoelectric conversion element, an optical sensor, and an imaging element according to the present invention, wherein a voltage is applied with the electrode in contact with the electron blocking layer as a cathode and the other electrode as an anode. Also related to the driving method.

[Substituent W]
The substituent W is described.
As the substituent W, a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, an aryl group, and a heterocyclic group (May be referred to as a heterocyclic group), cyano group, hydroxy group, nitro group, carboxy group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, Aryloxycarbonyloxy group, amino group (including anilino group), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group Mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and hetero Ring azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, phosphono group, silyl group, hydrazino group, ureido group, boronic acid group (-B (OH) ₂ ), phosphato Examples include a group (—OPO (OH) ₂ ), a sulfato group (—OSO ₃ H), and other known substituents.

More specifically, W represents the following (1) to (48).
(1) Halogen atom For example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom (2) an alkyl group represents a linear, branched, or cyclic substituted or unsubstituted alkyl group. They also include (2-a) to (2-e).
(2-a) alkyl group Preferably an alkyl group having 1 to 30 carbon atoms (for example, methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl) )

(2-b) a cycloalkyl group, preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms (eg, cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl) (2-c) a bicycloalkyl group, preferably C5-C30 substituted or unsubstituted bicycloalkyl group (eg, bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-yl)

(2-d) Tricycloalkyl group Preferably, it is a substituted or unsubstituted tricycloalkyl group having 7 to 30 carbon atoms (for example, 1-adamantyl).

(2-e) A polycyclic cycloalkyl group having a larger ring structure In addition, an alkyl group (for example, an alkyl group of an alkylthio group) in a substituent described below represents an alkyl group of such a concept, Group and alkynyl group.

(3) Alkenyl group represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group. They include (3-a) to (3-c).

(3-a) Alkenyl group Preferably it is a C2-C30 substituted or unsubstituted alkenyl group (for example, vinyl, allyl, prenyl, geranyl, oleyl).

(3-b) Cycloalkenyl group Preferably, the substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms (for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl)

(3-c) Bicycloalkenyl group A substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms (for example, bicyclo [2,2,1] hept-2-ene -1-yl, bicyclo [2,2,2] oct-2-en-4-yl)

(4) Alkynyl group Preferably, the substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms (for example, ethynyl, propargyl, trimethylsilylethynyl group)

(5) Aryl group Preferably, it is a C6-C30 substituted or unsubstituted aryl group (for example, phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl, ferrocenyl).

(6) Heterocyclic group Preferably, it is a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, more preferably carbon. It is a 5- or 6-membered aromatic heterocyclic group of 2 to 50. (For example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl, 2-carbazolyl, 3-carbazolyl, 9-carbazolyl. In addition, like 1-methyl-2-pyridinio and 1-methyl-2-quinolinio May be a cationic heterocyclic group)

(7) Cyano group

(8) Hydroxy group

(9) Nitro group

(10) Carboxy group

(11) Alkoxy group Preferably, the substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms (for example, methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy)

(12) Aryloxy group Preferably, it is a C6-C30 substituted or unsubstituted aryloxy group (for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoyl) Aminophenoxy)

(13) Silyloxy group Preferably, the silyloxy group having 3 to 20 carbon atoms (for example, trimethylsilyloxy, t-butyldimethylsilyloxy)

(14) Heterocyclic oxy group Preferably, the substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms (for example, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy)

(15) Acyloxy group, preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms (for example, formyloxy, acetyloxy , Pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy)

(16) Carbamoyloxy group Preferably, the substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms (for example, N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N- Di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy)

(17) Alkoxycarbonyloxy group Preferably, the substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms (for example, methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy)

(18) Aryloxycarbonyloxy group Preferably, the substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms (for example, phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyl) Oxy)

(19) Amino group Preferably, an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms (for example, amino, methylamino, dimethylamino, Anilino, N-methyl-anilino, diphenylamino)

(20) Ammonio group Preferably, an ammonio group, an ammonio group substituted with 1 to 30 carbon atoms, substituted or unsubstituted alkyl, aryl, or heterocyclic ring (for example, trimethylammonio, triethylammonio, diphenylmethylammonio)

(21) Acylamino group Preferably, a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms (for example, formylamino, acetyl) Amino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino)

(22) Aminocarbonylamino group Preferably, the substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms (for example, carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino) )

(23) Alkoxycarbonylamino group Preferably, the substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms (for example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N- Methyl-methoxycarbonylamino)

(24) Aryloxycarbonylamino group Preferably, the substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms (for example, phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino) )

(25) Sulfamoylamino group Preferably, the substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms (for example, sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylamino) Sulfonylamino)

(26) Alkyl or arylsulfonylamino group Preferably, the substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, or the substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms (for example, methylsulfonylamino, butylsulfonyl) Amino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino)

(27) Mercapto group

(28) Alkylthio group Preferably, it is a C1-C30 substituted or unsubstituted alkylthio group (for example, methylthio, ethylthio, n-hexadecylthio).

(29) Arylthio group Preferably, the substituted or unsubstituted arylthio having 6 to 30 carbon atoms (for example, phenylthio, p-chlorophenylthio, m-methoxyphenylthio)

(30) Heterocyclic thio group Preferably, the substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms (for example, 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio)

(31) Sulfamoyl group Preferably, the substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms (for example, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl) N-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N′-phenylcarbamoyl) sulfamoyl)

(32) Sulfo group

(33) an alkyl or arylsulfinyl group, preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms (for example, methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl)

(34) an alkyl or arylsulfonyl group, preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, such as methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl)

(35) Acyl group Preferably, it is a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, a substituted or unsubstituted group having 4 to 30 carbon atoms. Heterocyclic carbonyl groups bonded to carbonyl groups at substituted carbon atoms (eg, acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl )

(36) Aryloxycarbonyl group Preferably, the substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms (for example, phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl) )

(37) Alkoxycarbonyl group Preferably, the substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms (for example, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl)

(38) Carbamoyl group Preferably, the substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms (for example, carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (Methylsulfonyl) carbamoyl)

(39) Aryl and heterocyclic azo group Preferably, the substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, or the substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms (for example, phenylazo, p-chlorophenylazo , 5-ethylthio-1,3,4-thiadiazol-2-ylazo)

(40) Imido group, preferably N-succinimide, N-phthalimide

(41) Phosphino group Preferably, the substituted or unsubstituted phosphino group having 2 to 30 carbon atoms (for example, dimethylphosphino, diphenylphosphino, methylphenoxyphosphino)

(42) Phosphinyl group Preferably, the substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms (for example, phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl).

(43) Phosphinyloxy group Preferably, the substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms (for example, diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy)

(44) Phosphinylamino group Preferably, the substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms (for example, dimethoxyphosphinylamino, dimethylaminophosphinylamino)

(45) Phosphor group

(46) Silyl group, preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms (for example, trimethylsilyl, triethylsilyl, triisopropylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl) (47) hydrazino group, preferably A substituted or unsubstituted hydrazino group having 0 to 30 carbon atoms (for example, trimethylhydrazino)
(48) Ureido group Preferably a substituted or unsubstituted ureido group having 0 to 30 carbon atoms (for example, N, N-dimethylureido).

Among the above-described substituents W, those having a hydrogen atom may be substituted with the above groups by removing this. Examples of such substituents include a —CONHSO ₂ — group (sulfonylcarbamoyl group, carbonylsulfamoyl group), —CONHCO— group (carbonylcarbamoyl group), —SO ₂ NHSO ₂ — group (sulfonylsulfamoyl group). ). More specifically, alkylcarbonylaminosulfonyl group (for example, acetylaminosulfonyl), arylcarbonylaminosulfonyl group (for example, benzoylaminosulfonyl group), alkylsulfonylaminocarbonyl group (for example, methylsulfonylaminocarbonyl), arylsulfonylamino A carbonyl group (for example, p-methylphenylsulfonylaminocarbonyl) is mentioned.

[Ring R]
Examples of the ring R include an aromatic or non-aromatic hydrocarbon ring, a heterocyclic ring, and a polycyclic fused ring formed by further combining these. For example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, Pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenant Examples include a lysine ring, an acridine ring, a phenanthroline ring, a thianthrene ring, a chromene ring, a xanthene ring, a phenoxathiin ring, a phenothiazine ring, and a phenazine ring.

(Synthesis of Exemplary Compound a-2 (A-1))
Exemplary compound a-2 of the compound represented by formula (F-1) can be produced by the following reaction formula.

2-Bromofluorene (89.0 g, 0.363 mol) is dissolved in 1.3 l of THF, cooled to 5 ° C., and potassium tert-butoxide (102 g, 0.908 mol) is added. Methyl iodide (565 ml, 0.908 mol) is added dropwise at 5 ° C. After dropping, the mixture was stirred at room temperature for 5 hours to obtain 2-bromo-9,9-dimethyl-fluorene in a yield of 87%. Magnesium powder (3.51 g, 0.144 mol) is added to 50 ml of THF in a nitrogen atmosphere, the mixture is refluxed at the boiling point, and a solution of 2-bromo-9,9-dimethyl-fluorene (75.0 g, 0.275 mol) in THF 250 ml is added dropwise. Stir for 1 hour. Thereafter, tetrakis (triphenylphosphine) palladium (1.59 g, 1.38 mmol) was added, and the mixture was refluxed at the boiling point for 2 hours to obtain Compound 1 in a yield of 82%. Bromine (39.8 g, 0.249 mol) was added dropwise to a 500 ml chloroform solution of compound 1 (43.8 g, 0.113 mol), and the mixture was stirred for 3 hours to synthesize compound 2 in a yield of 78%. Compound 2 (1.10 g, 2.02 mmol), palladium acetate (22.7 mg, 0.101 mmol), tri (t-butyl) phosphine (61.3 mg, 0.303 mmol), cesium carbonate (2.63 g, 8. 08 mmol) and compound 3 (991 mg, 4.44 mmol) were dissolved in 11 ml of xylene and reacted at reflux at boiling point for 4 hours under a nitrogen atmosphere. Ethyl acetate and water are added to the reaction mixture, and the organic phase is separated. The organic phase is washed with water and saturated brine and then concentrated under reduced pressure. The resulting reaction mixture is purified by recrystallization and sublimation purification. Compound a-2 was obtained with a yield of 66%. In addition, compound A-1 used in the Example corresponds to this exemplified compound a-2.
¹ H-NMR (400 MHz, in CDCl ₃ ): δ (ppm) = 1.50 (s, 18H), 1.65 (s, 12H), 7.28-7.32 (m, 2H), 7 40-7.46 (m, 4H), 7.49 (d, J = 8.2, 2H), 7.53 (dd, J = 8.7, 1.9 Hz, 2H), 7.57 ( dd, J = 8.0, 1.8 Hz, 2H), 7.66 (d, J = 1.8 Hz, 2H), 7.74 (dd, J = 7.9, 1.6 Hz, 2H), 7 .77 (s, 2H), 7.89 (d, J = 7.8 Hz, 2H), 7.96 (d, J = 8.0 Hz, 2H), 8.18-8.18 (m, 6H) .
According to HPLC, the purity of the compound was 98.3%. In ICP emission analysis, the content of Br and Br ions is 80 ppm, the content of Cl and Cl ions is 30 ppm, the content of F and F ions is 5 ppm, the content of Pd and Pd ions is 6 ppm, the content of Cu and Cu ions The rate was below the detection limit (<1 ppm).

(Synthesis of Exemplary Compound a-3 (A-2))
Exemplary compound a-3 of the compound represented by formula (F-1) can be produced by the following reaction formula.

Compound 2 (1.10 g, 2.02 mmol), palladium acetate (22.7 mg, 0.101 mmol), tri (t-butyl) phosphine (61.3 mg, 0.303 mmol), cesium carbonate (2.63 g, 8. 08 mmol) and compound 4 (1.24 g, 4.44 mmol) were dissolved in 11 ml of xylene, and reacted at boiling point reflux for 4 hours under a nitrogen atmosphere. Ethyl acetate and water are added to the reaction mixture, and the organic phase is separated. The organic phase is washed with water and saturated brine and then concentrated under reduced pressure. The resulting reaction mixture is purified by recrystallization and sublimation purification. Compound a-3 was obtained with a yield of 61%. In addition, the compound A-2 used in the Example corresponds to this exemplified compound a-3.
¹ H-NMR (400 MHz, in CDCl ₃ ): δ (ppm) = 1.49 (s, 36H), 7.44 (d, J = 7.6 Hz, 4H), 7.51 (dd, J = 8.4, 1.9 Hz, 4H), 7.56 (dd, J = 8.0, 1.9 Hz, 2H), 7.65 (d, J = 1.4 Hz, 2H), 7.73 (dd , J = 7.8, 1.8 Hz, 2H), 7.77 (d, J = 1.2 Hz, 2H), 7.88 (d, J = 7.8 Hz, 2H), 7.95 (d, J = 8.0 Hz, 2H), 8.17 (d, J = 1.6 Hz, 4H)
According to HPLC, the purity of the compound was 99.5%. In the ICP emission analysis, the content of Br and Br ions was 55 ppm, the content of Cl and Cl ions was 29 ppm, and the content of Pd and Pd ions was 30 ppm or less.

  Exemplified compound a-3 can also be produced by the following reaction formula.

Compound 2 (5.00 g, 9.19 mmol), copper (I) iodide (1.75 g, 9.19 mmol), tri (t-butyl) phosphine (61.3 mg, 0.303 mmol), cesium carbonate (5. 09 g, 15.6 mmol) and compound 4 (5.90 g, 21.1 mmol) were dissolved in 20 ml of N-ethylpyrrolidone and reacted at boiling point reflux for 10 hours under a nitrogen atmosphere. The reaction mixture was dissolved in 100 ml of THF, filtered through celite, concentrated under reduced pressure, purified by recrystallization and sublimation purification, and exemplary compound a-3 was obtained in a yield of 43%.
According to HPLC, the purity of the compound was 99.3%. In the ICP emission analysis, the content of Br and Br ions is 120 ppm, the content of Cl and Cl ions is 30 ppm, the content of F and F ions is 10 ppm, the content of Pd and Pd ions is 10 ppm, the content of Cu and Cu ions The rate was 90 ppm or less.

(Synthesis of Exemplary Compound a-5 (A-4))
Exemplary compound a-5 of the compound represented by the general formula (F-1) can be produced by the following reaction formula.

Compound 2 (1.10 g, 2.02 mmol), palladium acetate (22.7 mg, 0.101 mmol), tri (t-butyl) phosphine (61.3 mg, 0.303 mmol), cesium carbonate (2.63 g, 8. 08 mmol) and compound 6 (1.13 g, 4.24 mmol) were dissolved in 10 ml of xylene, and reacted at boiling point reflux for 4 hours under a nitrogen atmosphere. Ethyl acetate and water are added to the reaction mixture, and the organic phase is separated. The organic phase is washed with water and saturated brine and then concentrated under reduced pressure. The resulting reaction mixture is purified by recrystallization, sublimation purification, etc. Compound a-5 was obtained with a yield of 44%. In addition, the compound A-4 used in the Example corresponds to this exemplified compound a-5.
¹ H-NMR (400 MHz, in CDCl ₃ ): δ (ppm) = 1.32 (s, 18H), 1.61 (s, 12H), 1.73 (s, 12H), 6.31-6 37 (m, 4H), 6.91-6.99 (m, 4H), 7.02 (dd, J = 8.6, 2.1 Hz, 2H), 7.32 (dd, J = 7. 9, 1.6 Hz, 2H), 7.42 (d, J = 1.5 Hz, 2H), 7.47 (d, J = 8.5 Hz, 2H), 7.51 (d, J = 2.1 Hz) , 2H), 7.73 (d, J = 7.8 Hz, 2H), 7.77 (s, 2H), 7.88 (d, J = 7.8 Hz, 2H), 7.99 (d, J = 7.9Hz, 2H)
According to HPLC, the purity of the compound was 99.9%. In the ICP emission analysis, the content of Br and Br ions is 8 ppm, the content of Cl and Cl ions is 4 ppm, the content of F and F ions is below the detection limit (<1 ppm), the content of Pd and Pd ions is 4 ppm, The content of Cu and Cu ions was below the detection limit (<1 ppm).

(Synthesis of Exemplified Compound a-6 (A-5))
Exemplary compound a-6 of the compound represented by the general formula (F-1) can be produced by the following reaction formula.

Compound 2 (1.10 g, 2.02 mmol), palladium acetate (22.7 mg, 0.101 mmol), tri (t-butyl) phosphine (61.3 mg, 0.303 mmol), cesium carbonate (2.63 g, 8. 08 mmol) and compound 7 (1.36 g, 4.24 mmol) were dissolved in 10 ml of xylene and reacted at boiling point reflux for 4 hours under a nitrogen atmosphere. Ethyl acetate and water are added to the reaction mixture, and the organic phase is separated. The organic phase is washed with water and saturated brine and then concentrated under reduced pressure. The resulting reaction mixture is purified by recrystallization, sublimation purification, etc. Compound a-6 was obtained with a yield of 35%. In addition, the compound A-5 used in the Example corresponds to this exemplified compound a-6.
¹ H-NMR (400 MHz, in CDCl ₃ ): δ (ppm) = 1.32 (s, 18H), 1.60 (s, 12H), 1.76 (s, 12H), 6.29 (d , J = 8.6 Hz, 4H), 7.00 (dd, J = 8.6, 2.2 Hz, 4H), 7.31 (dd, J = 7.9, 1.8 Hz, 2H), 7. 43 (d, J = 1.6 Hz, 2H), 7.50 (d, J = 2.2 Hz, 4H), 7.73 (d, J = 7.9, 1.5 Hz, 2H), 7.77 (S, 2H), 7.88 (d, J = 7.8 Hz, 2H), 7.97 (d, J = 7.9 Hz, 2H)
According to HPLC, the purity of the compound was 97.8%. In the ICP emission analysis, the content of Br and Br ions is 40 ppm, the content of Cl and Cl ions is 20 ppm, the content of F and F ions is 2 ppm, the content of Pd and Pd ions is 4 ppm, and the content of Cu and Cu ions The rate was below the detection limit (<1 ppm).

(Synthesis of Exemplified Compound e-5 (A-13))
Illustrative compound e-5 of the compound represented by general formula (F-1) can be produced by the following reaction formula.

1,4-Dibromo-2-nitrobenzene (23.2 g, 0.0825 mol) and copper powder (15.6 g, 0.248 mol) were added to 4-iodoanisole (25.1 g, 0.107 mol) at 175 ° C. The mixture was stirred for 3 hours to obtain Compound 10 in a yield of 44%. Compound 10 (11.1 g, 36.0 mmol) and triphenylphosphine (23.6 g, 90.0 mmol) were dissolved in 70 ml of o-dichlorobenzene and reacted at boiling point reflux for 5 hours under a nitrogen atmosphere to recover compound 11. Obtained at 89% rate. Compound 11 (4.4 g, 0.15.9 mmol), palladium acetate (89.4 mg, 0.398 mmol), tri (t-butyl) phosphine (241 mg, 119 mmol), cesium carbonate (15.5 g, 47.7 mmol) , And iodotoluene (16.2 g, 79.5 mmol) were dissolved in 86 ml of xylene and reacted at boiling point reflux for 3 hours under a nitrogen atmosphere to synthesize Compound 12 (yield 52%).
Magnesium (103 mg, 4.24 mmol) was added to 2 ml of THF under a nitrogen atmosphere and refluxed at the boiling point, and a solution of compound 12 (2.90 g, 8.23 mmol) in 8 ml of THF was added dropwise and stirred for 1 hour. Thereafter, tetrakis (triphenylphosphine) palladium (47.6 mg, 0.0412 mmol) was added, and the mixture was refluxed at the boiling point for 2 hours to obtain Compound 13 in a yield of 52%. Compound 13 (1.20 g, 2.20 mmol) was dissolved in 50 ml of methylene chloride, 5.5 ml of 1 mol / l BBr ₃ methylene chloride solution was added dropwise at 0 ° C. in a nitrogen atmosphere, and the mixture was reacted at room temperature for 3 hours.
After quenching the reaction, ethyl acetate and water were added to the reaction mixture to separate the organic phase. The organic phase was washed with water and saturated brine, and then concentrated under reduced pressure. The concentrated reaction mixture was dissolved in 30 ml of a mixed solvent of methylene chloride and N, N′-dimethylformamide (1: 1). Perfluorobutanesulfonyl fluoride (1.16 ml, 6.60 mmol) was added dropwise at 5 ° C. under a nitrogen atmosphere and reacted at room temperature for 3 hours to obtain Compound 15 in a yield of 46%. Palladium acetate (11.3 mg, 0.0463 mmol) with compound 15 (1.00 g, 0.925 mmol), tri (t-butyl) phosphine (28.1 mg, 0.139 mmol), cesium carbonate (1.21 g, 3 .70 mmol) and compound 6 (540 mg, 2.03 mmol) were dissolved in 9 ml of xylene, and reacted at boiling point reflux for 4 hours under a nitrogen atmosphere.
Ethyl acetate and water are added to the reaction mixture, and the organic phase is separated. The organic phase is washed with water and saturated brine and then concentrated under reduced pressure. The resulting reaction mixture is purified by recrystallization and sublimation purification. Compound e-5 was obtained with a yield of 39%. In addition, the compound A-13 used in the Example corresponds to this exemplified compound e-5.
¹ H-NMR (400 MHz, in CDCl ₃ ): δ (ppm) = 1.30 (s, 18H), 1.72 (s, 12H), 6.25 (d, J = 8.6 Hz, 2H) 6.30 (dd, J = 8.3, 1.4 Hz, 2H), 6.86-6.94 (m, 4H), 6.97 (dd, J = 8.9, 2.0 Hz, 2H) ), 7.23 (dd, J = 6.4, 1.8 Hz, 2H), 7.38 (d, J = 1.8 Hz, 2H), 7.43-7.49 (m, 6H), 7 .57-7.59 (m, 8H), 7.65 (dd, J = 8.5, 1.6 Hz, 2H), 7.72 (s, 2H), 8.24 (d, J = 8. 1 Hz, 2H), 8.37 (d, J = 8.2 Hz, 2H)
According to HPLC, the purity of the compound was 98.8%. In the ICP emission analysis, the content of Br and Br ions is 40 ppm, the content of Cl and Cl ions is 20 ppm, the content of F and F ions is 5 ppm, the content of Pd and Pd ions is below the detection limit (<1 ppm), The content of Cu and Cu ions was below the detection limit (<1 ppm).

  Other compounds used in the examples can be synthesized in the same manner.

[Example 1]
A photoelectric conversion element having the form shown in FIG. That is, an amorphous ITO film of 30 nm was formed on a glass substrate by a sputtering method, and then a lower electrode was formed. A compound (A-1) of 100 nm was formed by a vacuum heating vapor deposition method to form an electron blocking layer. Further, a layer in which the compound (70) and fullerene (C ₆₀ ) are co-deposited so as to be 100 nm and 300 nm in terms of a single layer, respectively, is formed in a state where the substrate temperature is controlled to 25 ° C. by vacuum heating deposition. Thus, a photoelectric conversion layer was formed. Note that the vacuum evaporation of the photoelectric conversion layer was performed at a vacuum degree of 4 × 10 ⁻⁴ Pa or less.
Further thereon, an amorphous ITO film having a thickness of 10 nm was formed as an upper electrode by sputtering to form a transparent conductive film, thereby producing a photoelectric conversion element.

[Examples 2, 22, and 23]
A photoelectric conversion element was produced in the same manner as in Example 1 except that the compound (70) used in the photoelectric conversion layer was changed as shown in Table 1.

[Examples 3 to 21, Comparative Examples 1 to 8]
A photoelectric conversion element was produced in the same manner as in Example 1 except that the compound (A-1) used in the electron blocking layer was changed as shown in Table 1.

[Evaluation]
Each of the obtained elements was confirmed to function as a photoelectric conversion element. When a voltage was applied to the lower electrode and the upper electrode of each of the obtained devices so that the electric field strength was 2.5 × 10 ⁵ V / cm, each device had a dark current of 100 nA / cm ² or less in the dark. However, in a bright place, a current of 10 μA / cm ² or more was shown, and it was confirmed that the photoelectric conversion element functions.
Table 1 shows the dark current value (relative value based on Example 1) of each device obtained, and each device was held in an environment of 200 ° C. and 210 ° C. for 30 minutes and returned to room temperature. The increase rate with respect to the dark current before the heating of dark current is shown. In addition, Ip of each material was calculated | required by measuring each single layer film | membrane which formed each material each by AC-2 by Riken Keiki, and Ea was calculated | required by subtracting the energy for an energy gap from Ip. As the energy corresponding to the energy gap, a value obtained by converting the wavelength of the long wave end of the spectral absorption spectrum of the single layer film into energy was used.

  The compounds used in Examples and Comparative Examples are shown below.

  It turns out that Examples 1-23 have a small increase amount of the dark current after a heating compared with Comparative Examples 1-8, and heat resistance is high. Compared with Comparative Examples 2, 5, 6 and 8, the relative value of dark current is small.

  Further, an image sensor similar to the embodiment shown in FIG. 2 was produced. That is, after depositing amorphous ITO 30 nm on a CMOS substrate by sputtering, patterning is performed so that one pixel exists on each photodiode (PD) on the CMOS substrate by photolithography to form a lower electrode. The film forming of the electron blocking material was made in the same manner as in Examples 1 to 23 and Comparative Examples 1 to 8. The evaluation was carried out in the same manner, and the same results as in Table 1 were obtained. In the image pickup device, the device based on the example of the present invention showed a low dark current after heating and high heat resistance.

10a, 10b Photoelectric conversion element 11 Lower electrode (conductive film)
12 Photoelectric conversion layer (photoelectric conversion film)
15 Upper electrode (transparent conductive film)
16A Electron blocking layer 16B Hole blocking layer 100 Image sensor 101 Substrate 102 Insulating layer 103 Connection electrode 104 Pixel electrode (lower electrode)
105 connecting portion 106 connecting portion 107 photoelectric conversion film 108 counter electrode (upper electrode)
109 Buffer layer 110 Sealing layer 111 Color filter (CF)
112 partition wall 113 light shielding layer 114 protective layer 115 counter electrode voltage supply unit 116 readout circuit

Claims (17)

A photoelectric conversion element having a transparent conductive film, a photoelectric conversion film, and a conductive film in this order,
The photoelectric conversion film includes a photoelectric conversion layer and an electron blocking layer,
The photoelectric conversion element in which the said electron blocking layer contains the compound represented by the following general formula (F-1).

(In General Formula (F-1), R _{11 to} R ₁₈ , R ′ _{11 to} R ′ ₁₈ are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxyl group, an amino group, or It represents a mercapto group, which may further have a substituent. _However, any one in R 15 _{to R 18} is coupled with any one in R _'15 ~R' _18, single bond A ₁₁ and A ₁₂ each independently represent a substituent represented by the following general formula (A-1), any one of R _{11 to} R ₁₄ , and R ′ _{11 to} R ′ _14. And each Y is independently a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, or a silicon atom, which may further have a substituent.

(In General Formula (A-1), Ra _{1 to} Ra ₈ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, and these may further have a substituent. At least two members out of Ra _{1 to} Ra ₈ may be bonded to each other to form a ring, and * represents a substituent represented by the general formula (A-1) as R ₁₁ in the general formula (F-1). any one in to R _14, and .Xa representing the binding position when substituted as any one of R _'11 to R' of ₁₄ represents a single bond, an oxygen atom, a sulfur atom, an alkylene group, a silylene group, alkenylene group, cycloalkylene group, cycloalkenylene group, an arylene group, a divalent heterocyclic group or an imino group, which may further have a substituent .S ₁₁ each independently represent the following substituents (S ₁₁ ) and Ra _{1 to} R a is substituted as any one of _8. Each n independently represents an integer of 1 to 4.)

(R _{1 to} R ₃ each independently represents a hydrogen atom or an alkyl group. At least two of R _{1 to} R ₃ may be bonded to each other to form a ring.) The photoelectric conversion element according to claim 1, wherein the compound represented by the general formula (F-1) is a compound represented by the following general formula (F-2).

(In General Formula (F-2), R _{11 to} R ₁₆ , R ₁₈ , R ′ _{11 to} R ′ ₁₆ and R ′ ₁₈ are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. , A hydroxyl group, an amino group, or a mercapto group, which may further have a substituent, A ₁₁ and A ₁₂ each independently represent a substituent represented by the general formula (A-1); Substitute as any one of R _{11 to} R ₁₄ and any one of R ′ _{11 to} R ′ _14. Y is independently a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, or silicon. Represents an atom, which may further have a substituent.) The general formula (F-1) or the general formula (F-2), wherein the substituent represented by the general formula (A-1) is independently substituted with R ₁₂ and R ′ _12. The photoelectric conversion element as described in 2.   The photoelectric conversion element of any one of Claims 1-3 in which n in the said general formula (A-1) represents 1 or 2. The photoelectric conversion element according to claim 1, wherein at least one of Ra ₃ and Ra ₆ in the general formula (A-1) independently represents the substituent (S ₁₁ ). . The formula (F-1) or Y in Formula (F-2) is -N _{(R 20)} - represents, said _{R 20} represents an alkyl group, an aryl group, or a heterocyclic group, claim 1 The photoelectric conversion element according to any one of 5. Y in the general formula (F-1) or the general formula (F-2) represents —C (R ₂₁ ) (R ₂₂ ) —, and each of R ₂₁ and R ₂₂ independently represents an alkyl group, an aryl group, or The photoelectric conversion element according to claim 1, which represents a heterocyclic group.   The ionization potential (Ip) of the compound represented by the general formulas (F-1) and (F-2) is 4.9 eV or more and 5.8 eV or less, according to any one of claims 1 to 7. Photoelectric conversion element.   The photoelectric conversion element of any one of Claims 1-8 whose molecular weight of the compound represented by the said general formula (F-1) and (F-2) is 500-2000.   The photoelectric conversion element of any one of Claims 1-9 in which the said photoelectric converting layer contains an n-type organic semiconductor.   The photoelectric conversion element according to claim 10, wherein the n-type organic semiconductor is fullerene or a fullerene derivative. The photoelectric conversion element of any one of Claims 1-11 in which the said photoelectric conversion film contains the compound of the following general formula (I).
Formula (I)

(In the formula, Z ₁ represents an atomic group necessary for forming a 5- or 6-membered ring. L ₁ , L ₂ , and L ₃ each independently represent an unsubstituted methine group or a substituted methine group. D ₁ represents an atomic group, and n ₁ represents an integer of 0 or more.)   The photoelectric conversion element of any one of Claims 1-12 in which the electroconductive film, the electron blocking layer, the photoelectric converting layer, and the transparent conductive film were laminated | stacked in this order.   It is a manufacturing method of the photoelectric conversion element of any one of Claims 1-13, Comprising: The manufacturing method including the process of forming into a film the said photoelectric converting layer and the said electronic blocking layer by vacuum heating vapor deposition, respectively.   The optical sensor containing the photoelectric conversion element of any one of Claims 1-13.   The image pick-up element containing the photoelectric conversion element of any one of Claims 1-13. The photoelectric conversion element according to claim 1, the optical sensor according to claim 15, or the image sensor driving method according to claim 16, wherein the electrode is in contact with the electron blocking layer. A driving method in which a voltage is applied with the other electrode as an anode and the other electrode as an anode .

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