CN119264149A - Condensed polycyclic aromatic compound, photoelectric conversion element material, organic thin film, and organic photoelectric conversion element - Google Patents
Condensed polycyclic aromatic compound, photoelectric conversion element material, organic thin film, and organic photoelectric conversion element Download PDFInfo
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- CN119264149A CN119264149A CN202410881632.7A CN202410881632A CN119264149A CN 119264149 A CN119264149 A CN 119264149A CN 202410881632 A CN202410881632 A CN 202410881632A CN 119264149 A CN119264149 A CN 119264149A
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 104
- 239000000463 material Substances 0.000 title claims abstract description 71
- -1 polycyclic aromatic compound Chemical class 0.000 title claims abstract description 48
- 239000010409 thin film Substances 0.000 title claims description 18
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims abstract description 38
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 claims abstract description 8
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 58
- 230000004044 response Effects 0.000 abstract description 8
- 150000002894 organic compounds Chemical class 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
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- BMQDAIUNAGXSKR-UHFFFAOYSA-N (3-hydroxy-2,3-dimethylbutan-2-yl)oxyboronic acid Chemical class CC(C)(O)C(C)(C)OB(O)O BMQDAIUNAGXSKR-UHFFFAOYSA-N 0.000 description 20
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Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/60—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation in which radiation controls flow of current through the devices, e.g. photoresistors
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/04—Ortho-condensed systems
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
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Abstract
本发明提供一种作为响应速度优异的有机光电转换元件的材料的有机化合物、及包含所述有机化合物的有机薄膜、以及包含所述有机薄膜的有机光电转换元件。提供一种缩合多环芳香族化合物所述化合物的光电转换元件用材料，所述化合物由下述式(1)表示(式中，R1表示取代或未取代的芳香族烃基、取代或未取代的苯并噻吩基、或者取代或未取代的苯并呋喃基，R2表示取代或未取代的芳香族烃基或单键，R3及R4分别独立地表示取代或未取代的芳香族烃基或单键)。[化1]
The present invention provides an organic compound as a material for an organic photoelectric conversion element having excellent response speed, an organic film containing the organic compound, and an organic photoelectric conversion element containing the organic film. Provided is a photoelectric conversion element material of a condensed polycyclic aromatic compound, wherein the compound is represented by the following formula (1) (wherein R1 represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted benzothiophenyl group, or a substituted or unsubstituted benzofuranyl group, R2 represents a substituted or unsubstituted aromatic hydrocarbon group or a single bond, and R3 and R4 each independently represent a substituted or unsubstituted aromatic hydrocarbon group or a single bond). [Chemical 1]
Description
Technical Field
The present invention relates to a novel condensed polycyclic aromatic compound and its use. More specifically, the present invention relates to a condensed polycyclic aromatic compound which is a benzothieno [3,2-b ] [1] benzothiophene (benzothieno [3,2-b ] [1] benzothiophene) (hereinafter abbreviated as "BTBT") derivative, a material for a photoelectric conversion element containing the compound, an organic thin film, and an organic photoelectric conversion element containing the organic thin film.
Background
Organic electronic devices can be stably supplied without containing rare metals or the like in raw materials, and have flexibility not available in inorganic materials, and can be manufactured by a wet film forming method, and thus, research and development have been actively conducted in recent years. Specific examples of the organic electronic device include an organic Electroluminescence (EL) device, an organic solar cell device, an organic photoelectric conversion device, and an organic transistor device, and various applications have been studied to effectively utilize the characteristics of an organic compound, as well as to improve the device performance.
In the above-mentioned device, for example, an organic photoelectric conversion element is used for a photosensor or the like, and a case of being used for an image pickup element is studied (patent document 1), but a response speed for capturing a moving object is required for the image pickup element (patent document 2).
In order to meet the above requirements, a BTBT compound known to exhibit high mobility as an organic semiconductor material is being studied for use in a photoelectric conversion element (patent document 3).
[ Prior Art literature ]
[ Patent literature ]
[ Patent document 1] WO2022/114065
[ Patent document 2] Japanese patent laid-open publication No. 2013-012535
[ Patent document 3] WO2016/185858
[ Patent document 4] WO2018/016465
Disclosure of Invention
[ Problem to be solved by the invention ]
However, in the photoelectric conversion element using the BTBT compound reported so far, a practically sufficient response speed cannot be obtained. Patent document 4 reports a BTBT compound having excellent light-to-dark ratio for use in a photoelectric conversion element, but the inventors of the present invention have not described the responsiveness and have found that a practically sufficient response speed cannot be obtained as a result of evaluation.
In view of the above-described circumstances, an object of the present invention is to provide a condensed polycyclic aromatic compound as a material of an organic photoelectric conversion element excellent in response speed, an organic thin film containing the condensed polycyclic aromatic compound, and an organic photoelectric conversion element containing the organic thin film.
[ Means of solving the problems ]
As a result of diligent studies, the present inventors have found that the above problems can be solved by using a novel condensed polycyclic aromatic compound having a specific structure, and have completed the present invention.
Namely, the present invention relates to the following [1] to [6].
[1] A condensed polycyclic aromatic compound represented by the following formula (1),
(Wherein R 1 represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted benzothienyl group, or a substituted or unsubstituted benzofuranyl group, R 2 represents a substituted or unsubstituted aromatic hydrocarbon group or a single bond, and R 3 and R 4 each independently represent a substituted or unsubstituted aromatic hydrocarbon group or a single bond).
[2] The condensed polycyclic aromatic compound according to [1], wherein R 1 represents a substituted or unsubstituted aromatic hydrocarbon group, R 2 represents a substituted or unsubstituted aromatic hydrocarbon group or a single bond, and R 3 and R 4 each independently represent a substituted or unsubstituted aromatic hydrocarbon group or a single bond.
[3] The condensed polycyclic aromatic compound according to [1], wherein R 1 represents a substituted or unsubstituted benzothienyl group, or a substituted or unsubstituted benzofuranyl group, R 2 represents a substituted or unsubstituted aromatic hydrocarbon group, and R 3 and R 4 each independently represent a substituted or unsubstituted aromatic hydrocarbon group or a single bond.
[4] A material for a photoelectric conversion element, which contains the condensed polycyclic aromatic compound according to any one of [1] to [3 ].
[5] An organic thin film comprising the material for a photoelectric conversion element according to [4 ].
[6] An organic photoelectric conversion element comprising the material for a photoelectric conversion element according to [4] or the organic thin film according to [5 ].
[ Effect of the invention ]
The present invention provides a condensed polycyclic aromatic compound as a material of an organic photoelectric conversion element having excellent response speed, an organic thin film containing the condensed polycyclic aromatic compound, and an organic photoelectric conversion element containing the organic thin film. In the present specification, the condensed polycyclic aromatic compound of the present invention is sometimes referred to as "the compound of the present invention".
Drawings
Fig. 1 is a schematic cross-sectional view showing an embodiment of an organic photoelectric conversion element.
[ Description of symbols ]
1 Substrate
2 First electrode
3 Electron blocking layer
4 Photoelectric conversion layer
5 Hole blocking layer
6 Second electrode
7 Organic photoelectric conversion element
Detailed Description
The following describes the present invention in detail. The explanation of the constituent elements described herein is based on the representative embodiments or specific examples of the present invention, but the present invention is not limited to such embodiments or specific examples.
[ Condensed polycyclic aromatic Compounds ]
The compound of the present invention is represented by the following formula (1). In the present specification, the condensed polycyclic aromatic ring to which R 2 and R 3 are bonded is sometimes referred to as a BTBT ring.
(Wherein R 1 represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted benzothienyl group, or a substituted or unsubstituted benzofuranyl group, R 2 represents a substituted or unsubstituted aromatic hydrocarbon group or a single bond, and R 3 and R 4 each independently represent a substituted or unsubstituted aromatic hydrocarbon group or a single bond)
Specific examples of the aromatic hydrocarbon group represented by R 1 in the formula (1) include phenyl, biphenyl, indenyl, naphthyl, anthracenyl, fluorenyl, phenanthryl and the like, preferably phenyl, biphenyl, and naphthyl, more preferably phenyl and biphenyl.
In formula (1), R 1 may also represent a substituted or unsubstituted benzothienyl or benzofuranyl group, and may be represented by formula (2) below. In formula (2), X represents an oxygen atom or a sulfur atom, preferably a sulfur atom. A bond is formed with R 2 in one of the substitution positions selected from a to f. The substitution positions forming a bond with R 2 are preferably b, c, and f, more preferably c and f, and still more preferably c.
In the case where a benzothienyl group or a benzofuranyl group has a substituent, examples of the substituent include an aromatic hydrocarbon group, and phenyl and naphthyl groups are preferable.
R 2 represents a substituted or unsubstituted divalent aromatic hydrocarbon group or a single bond. The divalent aromatic hydrocarbon group is a divalent linking group obtained by removing two hydrogen atoms from an aromatic ring of an aromatic hydrocarbon compound. When the divalent aromatic hydrocarbon group has a substituent, the substituent is preferably an aromatic hydrocarbon group, and the substitution position is not particularly limited. Examples of the substituent include phenyl and naphthyl. The case where R 2 is a single bond means that R 1 is directly bonded to the BTBT ring.
Specific examples of the divalent aromatic hydrocarbon group represented by R 2 include a linking group obtained by removing two hydrogen atoms from an aromatic organic compound selected from benzene, biphenyl, indene, naphthalene, anthracene, fluoran, and phil, and are preferably benzene, biphenyl, and naphthalene, and more preferably benzene and biphenyl. Benzene, biphenyl, and naphthalene are preferably bonded to the R 1 or BTBT ring at the substitution positions indicated by the wavy lines described below. The divalent aromatic hydrocarbon group is preferably a linking group obtained by removing two hydrogen atoms from an aromatic organic compound selected from benzene, biphenyl, and naphthalene, and these linking groups are preferably bonds formed at substitution positions represented by the following formula (3).
In the case where both R 1 and R 2 are aromatic hydrocarbon groups, specific examples of the combination of R 1 and R 2 include combinations represented by the following formulas (1A-1) to (1A-2), formulas (1B-1) to (1B-4), and formulas (1C-1) to (1C-4). The formula (I) represents a site bonded to a BTBT ring. Among them, the combination represented by any one of the formulas (1A-1) to (1A-2) and (1B-1) to (1B-4) is preferable, and the combination represented by the formulas (1A-1) to (1A-2) is more preferable.
* Indicates the junction with the BTBT ring.
R 3 and R 4 are substituted or unsubstituted divalent aromatic hydrocarbon groups or single bonds. The divalent aromatic hydrocarbon group is a divalent linking group obtained by removing two hydrogen atoms from an aromatic ring of an aromatic hydrocarbon compound. When the divalent aromatic hydrocarbon group has a substituent, the substituent is preferably an aromatic hydrocarbon group, and the substitution position is not particularly limited. The case where R 3 is a single bond and R 4 is a substituted or unsubstituted divalent aromatic hydrocarbon group means that R 4 is directly bonded to the BTBT ring. In addition, the case where R 3 is a substituted or unsubstituted divalent aromatic hydrocarbon group and R 4 is a single bond means that a thiophene ring is directly bonded to R 3. The case where R 3 and R 4 are single bonds means that the thiophene ring is directly bonded to the BTBT ring.
Specific examples of the divalent aromatic hydrocarbon group represented by R 3 and R 4 include a linking group obtained by removing two hydrogen atoms from an aromatic organic compound selected from benzene, biphenyl, indene, naphthalene, anthracene, fluoran, and phil, and are preferably benzene, biphenyl, and naphthalene, and more preferably benzene and biphenyl. Benzene, biphenyl, and naphthalene are preferably bonded to a thiophene ring, R 3、R4, or BTBT ring at substitution positions indicated by wavy lines as described below.
Specific examples of the combination of R 3、R4 and a thiophene ring include combinations represented by the following formulas (2A-1) to (2A-2), formulas (2B-1) to (2B-2) and formulas (2C-1) to (2C-3), and the like. The formula (I) represents a site bonded to a BTBT ring. Among them, the combination represented by any one of the formulas (2A-1) to (2A-2) and (2B-1) to (2B-2) is preferable, and the combination represented by the formulas (2A-1) to (2A-2) is more preferable.
* Indicates the junction with the BTBT ring.
In the thiophene ring at the end on the side where R 3 and R 4 exist in formula (1) (i.e., the thiophene ring at the right end in formula (1)), three carbon atoms that are not bonded may have substituents, but preferably do not have substituents. The thiophene ring does not have more condensed ring structures.
The compound of the present invention can be obtained by subjecting a dihalogenated BTBT (2, 7-dihalobenzo [ B ] benzo [4,5] thieno [2,3-B ] thiophene) represented by the following formula (A) synthesized by a known method to a coupling reaction with a borate derivative represented by the following formulas (B) and (C), and then removing the target compound by purification by sublimation, for example.
X in the formula (A) represents a halogen atom. R 1、R2、R3 and R 4 in the formula (B) and the formula (C) are the same as R 1、R2、R3 and R 4 in the formula (1), respectively.
The method for purifying the compound of the present invention is not particularly limited, and known methods such as recrystallization, column chromatography, and vacuum sublimation purification can be employed. In addition, these methods may be combined as necessary.
Specific examples of the compounds of the present invention are shown below, but are not limited to these specific examples.
[ Material for photoelectric conversion element ]
The material for photoelectric conversion elements contains the compound of the present invention. The material for a photoelectric conversion element may contain a component other than the condensed polycyclic aromatic compound represented by the formula (1) within a range that does not impair the effect of the present invention, but preferably contains only the compound of the present invention. The content of the compound of the present invention in the material for a photoelectric conversion element is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, particularly preferably 98% by mass or more, and most preferably 99% by mass or more. Other components that can be used in combination with the compound of the present invention are not particularly limited.
In addition, one or more condensed polycyclic aromatic compounds represented by formula (1) may be used in the material for photoelectric conversion elements.
The material for a photoelectric conversion element containing the compound of the present invention can realize a photoelectric conversion element having excellent response speed by being used as a hole transporting material for a photoelectric conversion element.
[ Organic film ]
The organic thin film of the present invention includes the material for a photoelectric conversion element of the present invention. The film thickness of the organic thin film may be selected according to the application, but is usually 1nm to 1. Mu.m, preferably 5nm to 500nm, more preferably 10nm to 500nm. Examples of the method for forming the organic thin film include a dry process such as a vapor deposition method (a method in which a material for a photoelectric conversion element is directly used) and various solution processes (a method in which a solution obtained by dissolving and/or dispersing a material for a photoelectric conversion element in an organic solvent or the like is used). Examples of the solution process include spin coating, drop casting, dip coating, spray, flexography and other relief printing methods, offset printing, dry offset printing, pad printing and other lithographic printing methods, gravure printing and other intaglio printing methods, screen printing, mimeography, stencil printing and other stencil printing methods, inkjet printing and microcontact printing methods, and combinations of these methods. In the case of forming a film by a solution process, it is preferable to form a thin film by evaporating a solvent after the coating or printing is performed.
[ Organic photoelectric conversion element ]
The organic photoelectric conversion element is an element including an organic semiconductor material, an electrode, and the like, and is an element that converts light into electricity. Fig. 1 shows an example of an organic photoelectric conversion element. The organic photoelectric conversion element 7 includes, in order, a substrate 1, a first electrode 2, an electron blocking layer 3, a photoelectric conversion layer 4, a hole blocking layer 5, and a second electrode 6. The organic photoelectric conversion element 7 is characterized in that one or both of the electron blocking layer 3 and the photoelectric conversion layer 4 has an organic thin film including the material for a photoelectric conversion element of the present invention as a hole transporting material. The organic photoelectric conversion element of the present invention is not limited to the structure of fig. 1, and layers may be added or omitted as necessary. The organic photoelectric conversion element shown in fig. 1 can be used as an organic photoelectric conversion element for image pickup, for example.
Substrate 1-
The substrate 1 is a member for supporting the organic photoelectric conversion element 7. The material of the substrate 1 is not particularly limited, and for example, a material including glass, transparent plastic, quartz, or the like can be used. In addition, in the case where light is incident from the second electrode 6 side in fig. 1, the substrate 1 may not necessarily have transparency. Here, "transparent" means that the transmittance of light of a specific wavelength to be converted into a current is excellent. Further, a substrate may be further disposed outside the second electrode 6, but at least one of the substrate 1 and the substrate outside the second electrode 6 needs to have transparency.
First electrode 2, second electrode 6-
The first electrode 2 and the second electrode 6 have a function of capturing holes and electrons generated in the photoelectric conversion layer 4. Since a function of making light incident on the photoelectric conversion layer 4 is also required, at least one of the first electrode 2 and the second electrode 6 needs to have transparency. The material of the first electrode 2 and the second electrode 6 is not particularly limited as long as it is a material having conductivity, and examples thereof include conductive transparent materials such as Indium Tin Oxide (ITO), indium Zinc Oxide (Indium Zinc Oxide, IZO), snO 2, ATO (Antimony-doped Tin Oxide), znO, AZO (Aluminum-doped Zinc Oxide), GZO (Gallium-doped Zinc Oxide), tiO 2, and Fluorine-doped Tin Oxide (FTO), inorganic conductive materials such as gold, silver, platinum, chromium, aluminum, iron, cobalt, nickel, and tungsten, inorganic conductive materials such as copper iodide and copper sulfide, and conductive polymers such as polythiophene, polypyrrole, and polyaniline. The first electrode 2 and the second electrode 6 may contain a plurality of mixtures of these materials as needed, or may be formed by laminating two or more layers.
Electron blocking layer 3-
The electron blocking layer 3 is provided for suppressing dark current generated by injection of electrons from one of the electrodes to the photoelectric conversion layer 4 when a bias voltage is applied between the two electrodes. In addition, the photoelectric conversion layer 4 also functions as a hole transport layer for transporting holes generated by charge separation to an electrode. The electron blocking layer 3 may be configured with a single layer or multiple layers as needed.
The electron blocking layer 3 may include a P-type organic semiconductor material as a hole transporting material. The P-type organic semiconductor material is preferably a material for a photoelectric conversion element containing the condensed polycyclic aromatic compound represented by the formula (1), but may be another P-type organic semiconductor material.
As the other P-type organic semiconductor material, for example, naphthalene, anthracene, phenanthrene, pyrene, and the like can be used,Compounds having condensed polycyclic aromatic groups such as tetracene, triphenylene, perylene, fluoranthene, fluorene, indene, etc., cyclopentadiene derivatives, furan derivatives, thiophene derivatives, pyrrole derivatives, benzofuran derivatives, benzothiophene derivatives, dinaphthathiophene derivatives, indole derivatives, pyrazoline derivatives, dibenzofuran derivatives, dibenzothiophene derivatives, carbazole derivatives, etc., compounds having pi electron excess aromatic groups, etc., and aromatic amine derivatives, styrylamine derivatives, benzidine derivatives, porphyrin derivatives, phthalocyanine derivatives, and quinacridone derivatives.
Photoelectric conversion layer 4-
The photoelectric conversion layer 4 is a layer that generates holes and electrons by charge separation of excitons generated by incident light. The photoelectric conversion layer 4 may be formed of only a photoelectric conversion material, or may be formed in combination with a P-type organic semiconductor material as a hole transporting material or an N-type organic semiconductor material as an electron transporting material. In addition, two or more P-type organic semiconductor materials may be used, or two or more N-type organic semiconductor materials may be used. One or more of the photoelectric conversion material, the P-type organic semiconductor material, and the N-type organic semiconductor material contained in the photoelectric conversion layer 4 desirably contains a dye material having a function of absorbing light of a desired wavelength in the visible region. A preferred embodiment is to use a material for a photoelectric conversion element containing the compound of the present invention as a P-type organic semiconductor material for a hole transporting material.
The photoelectric conversion material may be any material that generates excitons by incident light, and examples thereof include naphthalene, anthracene, phenanthrene, pyrene, and the like,Compounds having condensed polycyclic aromatic groups such as tetracene, triphenylene, perylene, fluoranthene, fluorene, indene, etc., compounds having pi electron excess aromatic groups such as cyclopentadiene derivatives, furan derivatives, thiophene derivatives, pyrrole derivatives, benzofuran derivatives, benzothiophene derivatives, dinaphthiophene derivatives, indole derivatives, pyrazoline derivatives, dibenzofuran derivatives, dibenzothiophene derivatives, carbazole derivatives, indolocarbazole derivatives, etc., aromatic amine derivatives, styrylamine derivatives, benzidine derivatives, porphyrin derivatives, phthalocyanine derivatives, quinacridone derivatives, etc. In view of the utilization efficiency of incident light, a material having a high light absorption coefficient is preferable, and for example, a pyrrole methylene derivative, a porphyrin derivative, a phthalocyanine derivative, a quinacridone derivative, a pyrrolopyrrole derivative, a coumarin derivative, a perylene derivative, an aromatic amine derivative, and the like can be used.
When the material for a photoelectric conversion element is used as a P-type organic semiconductor material, the material may be used in combination with other P-type organic semiconductor materials, or two or more kinds of the materials for a photoelectric conversion element may be used.
As the other P-type organic semiconductor material, for example, naphthalene, anthracene, phenanthrene, pyrene, and the like can be used,Compounds having condensed polycyclic aromatic groups such as tetracene, triphenylene, perylene, fluoranthene, fluorene, indene, etc., compounds having pi electron excess aromatic groups such as cyclopentadiene derivatives, furan derivatives, thiophene derivatives, pyrrole derivatives, benzofuran derivatives, benzothiophene derivatives, dinaphthiophene derivatives, indole derivatives, pyrazoline derivatives, dibenzofuran derivatives, dibenzothiophene derivatives, carbazole derivatives, indolocarbazole derivatives, etc., aromatic amine derivatives, styrylamine derivatives, benzidine derivatives, porphyrin derivatives, phthalocyanine derivatives, and quinacridone derivatives.
Examples of the polymer P-type organic semiconductor material include polystyrene derivatives, polyparaphenylene derivatives, polyfluorene derivatives, polyvinylcarbazole derivatives, and polythiophene derivatives. The material for a photoelectric conversion element or the non-polymer P-type organic semiconductor material of the present invention may be mixed with a polymer P-type organic semiconductor material, or two or more polymer P-type organic semiconductor materials may be mixed and used.
Examples of the N-type organic semiconductor material include naphthalene tetracarboxylic acid diimide, perylene tetracarboxylic acid diimide, fullerene, imidazole, thiazole, thiadiazole, oxazole, oxadiazole, triazole and other azole derivatives, and a single kind or a combination of two or more kinds selected from these N-type organic semiconductor materials may be used.
Hole blocking layer 5-
The hole blocking layer 5 is provided for suppressing dark current generated by injection of holes from one of the electrodes to the photoelectric conversion layer 4 when a bias voltage is applied between the two electrodes. In addition, the hole blocking layer 5 also has a function as an electron transport layer that transports electrons generated by charge separation in the photoelectric conversion layer 4 to the electrode. The hole blocking layer 5 may have a single layer or multiple layers as needed. An N-type organic semiconductor material having electron-transporting property may be used in the hole blocking layer 5.
Examples of the N-type organic semiconductor material include polycyclic aromatic polycarboxylic acid anhydrides such as naphthalene tetracarboxylic acid diimide and perylene tetracarboxylic acid diimide and imide compounds thereof, fullerenes such as C 60 and C 70, azole derivatives such as imidazole, thiazole, thiadiazole, oxazole, oxadiazole and triazole, tris (8-hydroxyquinoline) aluminum (III) derivatives, phosphine oxide derivatives, nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimide, fluorenylidene methane derivatives, anthraquinone dimethane and anthrone derivatives, bipyridine derivatives, quinoline derivatives, indolocarbazole derivatives, and the like, and one or a combination of two or more selected from these N-type organic semiconductor materials may be used.
The organic photoelectric conversion element 7 can be used for a solar cell, a photosensor, an imaging element, a photon counter, a laser radar (LIDAR), and the like.
Examples
The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the examples, "parts" means parts by mass and "%" means% by mass.
[ Synthesis of condensed polycyclic aromatic Compound No.10 ]
To dimethylformamide (dimethylformamide, DMF) (200 parts), diiodoBTBT (4.9 parts) synthesized by the method described in Japanese patent No. 4945757, a compound (2.8 parts) represented by the following formula (A-1) synthesized by a known method as pinacol borate derivative A, a compound (3.6 parts) represented by the following formula (B-1) synthesized by a known method as pinacol borate derivative B, tripotassium phosphate (6.3 parts) and tetrakis (triphenylphosphine) palladium (0.58 parts) were added, and the mixture was stirred under nitrogen at 80℃for five hours. The resulting reaction solution was cooled to room temperature, water was then added thereto, and the resultant solid was separated by filtration. The obtained solid was washed with acetone, dried and purified by sublimation, whereby the condensed polycyclic aromatic compound represented by specific example No.10 was obtained as a yellow solid (1.2 parts, yield 19%).
[ Synthesis of condensed polycyclic aromatic Compound No.16 ]
A condensed polycyclic aromatic compound (1.5 parts, 24% yield) represented by example No.16 was obtained in the same manner as in example 1 except that the pinacol borate derivative A was changed to a compound (3.6 parts) represented by the formula (A-2) synthesized by a known method, and the pinacol borate derivative B was changed to a compound (2.9 parts) represented by the following formula (B-2) synthesized by a known method.
[ Synthesis of condensed polycyclic aromatic Compound No.45 ]
A condensed polycyclic aromatic compound (1.8 parts, yield 27%) was obtained by the same procedure as in example 1 except that the pinacol borate derivative A was changed to a compound represented by the formula (A-3) synthesized by a known method (3.3 parts), and the pinacol borate derivative B was changed to a compound represented by the following formula (B-1) synthesized by a known method (3.6 parts).
[ Synthesis of condensed polycyclic aromatic Compound No.19 ]
A condensed polycyclic aromatic compound represented by example No.19 (2.7 parts, yield 39%) was obtained by the same procedure as in example 1 except that the pinacol borate derivative A was changed to a compound represented by the formula (A-2) synthesized by a known method (3.6 parts), and the pinacol borate derivative B was changed to a compound represented by the following formula (B-3) synthesized by a known method (3.4 parts).
[ Synthesis of condensed polycyclic aromatic Compound No.57 ]
A condensed polycyclic aromatic compound (1.0 part, 17% yield) represented by example No.57 was obtained in the same manner as in example 1 except that the pinacol borate derivative A was changed to a compound (3.4 parts) represented by the formula (A-4) synthesized by a known method, and the pinacol borate derivative B was changed to a compound (3.2 parts) represented by the following formula (B-2) synthesized by a known method.
[ Synthesis of condensed polycyclic aromatic Compound No.58 ]
A condensed polycyclic aromatic compound (1.2 parts, 24% yield) represented by example No.58 was obtained in the same manner as in example 1 except that the pinacol borate derivative A was changed to a compound (3.2 parts) represented by the formula (A-4) synthesized by a known method and the pinacol borate derivative B was changed to a compound (3.7 parts) represented by the following formula (B-1) synthesized by a known method.
[ Synthesis of condensed polycyclic aromatic Compound No.65 ]
A condensed polycyclic aromatic compound (1.2 parts, 18% yield) represented by example No.65 was obtained in the same manner as in example 1 except that the pinacol borate derivative A was changed to a compound (3.4 parts) represented by the formula (A-5) synthesized by a known method, and the pinacol borate derivative B was changed to a compound (3.4 parts) represented by the following formula (B-3) synthesized by a known method.
Example 8 production of photoelectric conversion element A
On a glass substrate on which an electrode containing ITO having a film thickness of 70nm was formed, czBDF (manufactured by Tokyo chemical Co., ltd.) was formed as an electron blocking layer at a substrate temperature of room temperature under a vacuum of 4.0X10 -5 Pa to a thickness of 10 nm. Next, as a photoelectric conversion layer, the compound of specific example No.10 obtained in example 1, cl 6 -SubPc-OPh (manufactured by lumiteck (Lumitec)) and fullerene (C 60, manufactured by tokyo chemical Co.) were co-deposited at a deposition rate ratio of 4:4:2 to form an organic thin film having a thickness of 230 nm. Next, a hole blocking layer was formed by performing 10nm vapor deposition on a conventionally available dpy-NDI (manufactured by tokyo chemical industry Co., ltd.). Finally, aluminum was formed into a film having a thickness of 100nm as an electrode, and a photoelectric conversion element a was fabricated.
Example 9 production of photoelectric conversion element B
The photoelectric conversion element B was produced in the same manner as in example 8 except that the compound of No.16 obtained in example 2 was used instead of the compound of specific example No.10 obtained in example 1.
Example 10 production of photoelectric conversion element C
A photoelectric conversion element C was produced in the same manner as in example 8 except that the compound of No.45 obtained in example 3 was used instead of the compound of specific example No.10 obtained in example 1.
Example 11 production of photoelectric conversion element D
A photoelectric conversion element D was produced in the same manner as in example 8 except that the compound of No.19 obtained in example 4 was used instead of the compound of specific example No.10 obtained in example 1.
Example 12 production of photoelectric conversion element E
A photoelectric conversion element E was produced in the same manner as in example 8 except that the compound of No.57 obtained in example 5 was used instead of the compound of specific example No.10 obtained in example 1.
Example 13 production of photoelectric conversion element F
A photoelectric conversion element F was produced in the same manner as in example 8 except that the compound of No.58 obtained in example 6 was used instead of the compound of specific example No.10 obtained in example 1.
Example 14 production of photoelectric conversion element G
A photoelectric conversion element G was produced in the same manner as in example 8 except that the compound of No.65 obtained in example 7 was used instead of the compound of specific example No.10 obtained in example 1.
Comparative example 1 production of photoelectric conversion element X
The compound (3.0 parts, 61%) represented by the formula (X) was obtained by the same procedure as in example 1, except that the pinacol borate derivative (6.6 parts) represented by the formula (B-2) was used instead of the pinacol borate derivative (2.8 parts) represented by the formula (A-1) and the pinacol borate derivative (3.6 parts) represented by the formula (B-1).
A photoelectric conversion element X was produced in the same manner as in example 8 except that the compound represented by the formula (X) was used instead of the compound represented by specific example No.10 obtained in example 1.
Comparative example 2 production of photoelectric conversion element Y
The photoelectric conversion element Y was produced by the same operation as that of example 8, except that the compound represented by the following formula (Y) synthesized by a known method was used instead of the compound represented by specific example No.10 obtained in example 1.
Comparative example 3 production of photoelectric conversion element Z
The compound (3.3 parts, 67%) represented by the formula (Z) was obtained by the same procedure as in example 1, except that the pinacol borate derivative (6.6 parts) represented by the formula (A-4) was used instead of the pinacol borate derivative (3.4 parts) represented by the formula (A-1) and the pinacol borate derivative (3.2 parts) represented by the formula (B-1).
A photoelectric conversion element Z was produced in the same manner as in example 8 except that the compound represented by the formula (Z) was used instead of the compound represented by specific example No.10 obtained in example 1.
(Evaluation of organic photoelectric conversion element)
(A) External quantum efficiency (External Quantum Efficiency, EQE) evaluation
The evaluation of EQE was performed based on the examples of WO 2018/105269. Using the obtained photoelectric conversion elements a to B, X, and Y, the following operation confirmation evaluation was performed.
Specifically, a voltage was applied to the photoelectric conversion element so as to have an intensity of 2.0X10 5 V/cm, and the external quantum efficiency of photoelectric conversion at 550nm (efficiency of converting an incident photon into an output electron, hereinafter also referred to as "photoelectric conversion efficiency") was measured.
As a result, the obtained photoelectric conversion elements all showed EQEs of 70% or more, and it was confirmed that the photoelectric conversion elements fully function.
(B) Evaluation of responsiveness
The examples based on WO2018/105269 conducted an evaluation of responsiveness.
Specifically, a voltage was applied to the obtained photoelectric conversion element so as to have a strength of 2.0X10 5 V/cm. Then, an LED (LIGHT EMITTING diode) was turned on instantaneously to irradiate light from a lower electrode on the transparent conductive film side, and the photocurrent at this time was measured by an oscilloscope, and the rise time of the signal intensity from 0 to 97% was measured. Then, the relative value was obtained when the rise time of comparative example 1 was set to 10. The results are shown in Table 1.
In comparative example 3, the relative value of the rise time was "a" when the rise time was 5 or less, "B" when the rise time was more than 5 and 8 or less, "C" when the rise time was more than 8 and less than 10, and "D" when the rise time was 10 or more.
In practice, the photoelectric conversion element preferably has a fast light response speed, and therefore "a" is optimal and "D" is worst.
TABLE 1
As shown in table 1, the photoelectric conversion elements of examples 8 to 14 showed evaluation of response speed superior to those of comparative examples 1 to 3.
[ Industrial applicability ]
By using the condensed polycyclic aromatic compound represented by the formula (1), an organic semiconductor device (for example, a photoelectric conversion element, a photosensor, or the like) excellent in responsiveness can be provided.
Claims (6)
1.A condensed polycyclic aromatic compound represented by the following formula (1),
Wherein R 1 represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted benzothienyl group, or a substituted or unsubstituted benzofuranyl group, R 2 represents a substituted or unsubstituted aromatic hydrocarbon group or a single bond, and R 3 and R 4 each independently represent a substituted or unsubstituted aromatic hydrocarbon group or a single bond.
2. The condensed polycyclic aromatic compound according to claim 1, wherein R 1 represents a substituted or unsubstituted aromatic hydrocarbon group, R 2 represents a substituted or unsubstituted aromatic hydrocarbon group or a single bond, and R 3 and R 4 each independently represent a substituted or unsubstituted aromatic hydrocarbon group or a single bond.
3. The condensed polycyclic aromatic compound according to claim 1, wherein R 1 represents a substituted or unsubstituted benzothienyl group, or a substituted or unsubstituted benzofuranyl group, R 2 represents a substituted or unsubstituted aromatic hydrocarbon group, and R 3 and R 4 each independently represent a substituted or unsubstituted aromatic hydrocarbon group or a single bond.
4. A material for photoelectric conversion elements, comprising the condensed polycyclic aromatic compound according to any one of claims 1 to 3.
5. An organic thin film comprising the material for a photoelectric conversion element according to claim 4.
6. An organic photoelectric conversion element comprising the material for a photoelectric conversion element according to claim 4 or the organic thin film according to claim 5.
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| US11374044B2 (en) | 2016-07-19 | 2022-06-28 | Nippon Kayaku Kabushiki Kaisha | Material for photoelectric conversion element for use in imaging element, and photoelectric conversion element including same |
| TW202222800A (en) | 2020-11-27 | 2022-06-16 | 日商日鐵化學材料股份有限公司 | Material of photoelectric conversion element for imaging, and photoelectric conversion element |
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