WO2016186186A1 - Composé aromatique polycyclique condensé - Google Patents

Composé aromatique polycyclique condensé Download PDF

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WO2016186186A1
WO2016186186A1 PCT/JP2016/064945 JP2016064945W WO2016186186A1 WO 2016186186 A1 WO2016186186 A1 WO 2016186186A1 JP 2016064945 W JP2016064945 W JP 2016064945W WO 2016186186 A1 WO2016186186 A1 WO 2016186186A1
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photoelectric conversion
layer
compound represented
polycyclic aromatic
condensed polycyclic
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PCT/JP2016/064945
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Japanese (ja)
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一樹 新見
秀典 薬師寺
俊文 井内
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日本化薬株式会社
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Priority to JP2017519406A priority Critical patent/JP6619806B2/ja
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    • 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
    • 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
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a novel condensed polycyclic aromatic compound that can be used for a photoelectric conversion element, an imaging element, an optical sensor, an organic semiconductor device, and the like.
  • the characteristics of the organic electronic device include flexibility, a large area, and enabling an inexpensive and high-speed printing method in the electronic device manufacturing process.
  • Typical examples of the organic electronic device include an organic EL element, an organic solar cell element, an organic photoelectric conversion element, and an organic transistor element.
  • the organic EL element is expected as a main target for next-generation flat panel display applications, and is applied to mobile phone displays, TVs, and the like, and development aimed at further enhancement of functionality is continued.
  • Organic solar cell elements and the like are used as flexible and inexpensive energy sources, and organic transistor elements and the like are used as flexible displays and inexpensive IC components.
  • organic photoelectric conversion elements are expected to be developed into next-generation imaging elements, and reports have been made by several groups.
  • a quinacridone derivative or a quinazoline derivative is used for a photoelectric conversion element (Patent Document 4)
  • a diketopyrrolopyrrole derivative There is a report of an example (Patent Document 6).
  • an image pickup device achieves higher contrast and lower power consumption by reducing dark current. Therefore, a method of inserting a hole block layer or an electron block layer between the photoelectric conversion unit and the electrode unit is used for the purpose of reducing the leakage current from the photoelectric conversion unit in the dark.
  • the hole blocking layer and the electron blocking layer are generally widely used in the field of organic electronic devices, and in each of the constituent films of the device, there are electrodes or conductive films and other films. It is arranged at the interface and controls reverse movement of holes or electrons. Further, the hole blocking layer and the electron blocking layer are for adjusting unnecessary leakage of holes or electrons. Depending on the application of the device, considering properties such as heat resistance, transmission wavelength, and film forming method, these are appropriately selected and used. However, since the required performance of materials for photoelectric conversion elements is particularly high, the conventional hole blocking layer or electron blocking layer has sufficient performance in terms of leakage current prevention characteristics and heat resistance to process temperature. It cannot be said that it has been used commercially.
  • the present invention has been made in view of such a situation, including a photoelectric conversion element excellent in hole or electron leakage prevention characteristics and heat resistance against process temperature, an organic transistor excellent in heat resistance, and the like.
  • An object of the present invention is to provide a novel condensed polycyclic aromatic compound that can be used in various electronic devices.
  • the present inventors have found that the above problems can be solved by using a compound represented by the following formula (1), and have completed the present invention. That is, the present invention is as follows.
  • a condensed polycyclic aromatic compound represented by: [2] A method for producing a condensed polycyclic aromatic compound represented by the formula (1) according to the above [1], wherein the following formula (4) And a compound represented by the following formula (5) (In the formula (5), X represents a halogen atom), a method for producing a condensed polycyclic aromatic compound, comprising reacting a compound represented by the formula: [3]
  • An imaging device having (A) a first electrode film, (B) a second electrode film, and (C) a photoelectric conversion unit disposed between the first electrode film and the second electrode film.
  • the organic thin film layer other than the photoelectric conversion layer contains the condensed polycyclic aromatic compound according to the above [1], and the method includes the step (c-2) of depositing an organic thin film layer other than the photoelectric conversion layer by a vapor deposition method.
  • Forming a photoelectric conversion element for an image pickup device comprising: [5] (c-2) The photoelectric conversion element for an image sensor according to [4], wherein the organic thin film layer other than the photoelectric conversion layer is an electron block layer, a hole block layer, an electron transport layer, or a hole transport layer And [6] (c-2) The method for producing a photoelectric conversion element for an image sensor according to [5] above, wherein the organic thin film layer other than the photoelectric conversion layer is an electron block layer or a hole block layer.
  • a photoelectric conversion element for an image sensor excellent in required characteristics such as hole or electron leakage prevention and heat resistance, an organic transistor excellent in heat resistance, and the like.
  • FIG. 1 is a cross-sectional view illustrating an embodiment of a photoelectric conversion element for an image sensor according to the present invention.
  • the condensed polycyclic aromatic compound represented by the formula (1) of the present invention is, for example, 4-halogeno-1,1 ′: 4 ′, 1 ′′ -terphenyl (a compound represented by the following formula (2) 2-([1,1 ′: 4 ′, 1 ′′ -terphenyl]-) obtained by reacting bis (pinacolato) diboron (a compound represented by the following formula (3)) with a halogen atom in 4-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (a compound represented by the following formula (4)) and 2,7-dihalogeno [1] benzothieno [3,2 -B] [1] It can be synthesized by a reaction with benzothiophene (a compound represented by the following formula (5)).
  • X in formula (2) and formula (5) independently represents a halogen atom.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • the purification method of the compound represented by the above formula (1) is not particularly limited, and known methods such as recrystallization, column chromatography, and vacuum sublimation purification can be employed. These methods can be combined as necessary.
  • the photoelectric conversion element for an image sensor obtained by the production method of the present invention is (A) the first electrode film and (B) the second.
  • (C) is an element in which a photoelectric conversion unit is disposed between two electrode films, and (A) the first electrode film or (B) light is photoelectrically converted from above the second electrode film. It is incident on the part.
  • the photoelectric conversion unit generates electrons and holes according to the amount of incident light, and is a device in which a signal corresponding to the electric charge is read out by a semiconductor and indicates the amount of incident light according to the absorption wavelength of the photoelectric conversion unit. .
  • a reading transistor is connected to the electrode film on which light is not incident.
  • the photoelectric conversion element is an imaging element because it indicates incident position information in addition to the incident light quantity. If the photoelectric conversion element arranged closer to the light source does not shield (transmit) the absorption wavelength of the photoelectric conversion element arranged behind the light source when viewed from the light source side, a plurality of photoelectric conversion elements are stacked. It may be used. By stacking a plurality of photoelectric conversion elements each having a different absorption wavelength in the visible light region, it can be used as a multicolor imaging element (full color photodiode array).
  • the condensed polycyclic aromatic compound represented by the formula (1) of the present invention is used as a material constituting the (C) photoelectric conversion part.
  • the photoelectric conversion part is (c-1) from the group consisting of a photoelectric conversion layer, an electron transport layer, a hole transport layer, an electron block layer, a hole block layer, a crystallization prevention layer, an interlayer contact improvement layer, and the like.
  • One or a plurality of selected (c-2) organic thin film layers other than the photoelectric conversion layer may be included.
  • the photoelectric conversion element material for an image sensor of the present invention can be used for both (c-1) a photoelectric conversion layer and (c-2) an organic thin film layer other than the photoelectric conversion layer. It is preferable to use for organic thin film layers other than the layer.
  • the (A) first electrode film and (B) second electrode film included in the photoelectric conversion element of the present invention are included in (C) the photoelectric conversion unit described later.
  • C-1) The photoelectric conversion layer transports holes.
  • c-2) an organic thin film layer other than the photoelectric conversion layer (hereinafter, the organic thin film layer other than the photoelectric conversion layer is simply referred to as “(c-2)) an organic thin film layer”).
  • a hole transport layer having a hole transport property plays a role of collecting and collecting holes from the (c-1) photoelectric conversion layer and the (c-2) organic thin film layer, and ( C)
  • the (c-1) photoelectric conversion layer included in the photoelectric conversion portion has an electron transporting property
  • the organic thin film layer is an electron transporting layer having an electron transporting property
  • the (c -1) Takes out electrons from the photoelectric conversion layer and (c-2) the organic thin film layer and discharges them.
  • the material that can be used as (A) the first electrode film and (B) the second electrode film is not particularly limited as long as it has a certain degree of conductivity, but the adjacent (c-1) photoelectric conversion layer (C-2) It is preferable to select in consideration of adhesion to the organic thin film layer, electron affinity, ionization potential, stability and the like.
  • Examples of materials that can be used for (A) the first electrode film and (B) the second electrode film include tin oxide (NESA), indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO).
  • Conductive metal oxide metals such as gold, silver, platinum, chromium, aluminum, iron, cobalt, nickel and tungsten; inorganic conductive materials such as copper iodide and copper sulfide; conductive polymers such as polythiophene, polypyrrole and polyaniline Carbon etc. are mentioned. When a plurality of these materials are used, they may be used in combination, or two or more layers containing each material may be stacked and used.
  • the conductivity of the material used for (A) the first electrode film and (B) the second electrode film is not particularly limited as long as it does not obstruct the light reception of the photoelectric conversion element more than necessary, but the signal intensity and consumption of the photoelectric conversion element It is preferable that it is as high as possible from the viewpoint of electric power.
  • an ITO film having a sheet resistance value of 300 ⁇ / ⁇ or less functions well as (A) the first electrode film and (B) the second electrode film, but has a conductivity of several ⁇ / ⁇ . Since a commercial product of a substrate provided with an ITO film having the above is also available, it is desirable to use a substrate having such high conductivity.
  • the thickness of the ITO film can be arbitrarily selected in consideration of conductivity, but is usually about 5 to 500 nm, preferably about 10 to 300 nm.
  • Examples of a method for forming a film such as ITO include conventionally known vapor deposition methods, electron beam methods, sputtering methods, chemical reaction methods, and coating methods.
  • the ITO film provided on the substrate may be subjected to UV-ozone treatment, plasma treatment or the like as necessary.
  • the transmittance of light incident through the transparent electrode film at the absorption peak wavelength of the photoelectric conversion layer is preferably 60% or more, more preferably 80% or more, and 95% or more. It is particularly preferred.
  • the electrode films used between the respective photoelectric conversion layers (this is other than (A) the first electrode film and (B) the second electrode film) It is necessary to transmit light having a wavelength other than the light detected by each photoelectric conversion layer, and the electrode film is preferably made of a material that transmits 90% or more of incident light. It is more preferable to use a material that transmits at least% of light.
  • the electrode film is preferably made plasma-free.
  • plasma-free means that no plasma is generated when the electrode film is formed, or 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, and reaches the substrate. It means a state where plasma is reduced.
  • Examples of an apparatus that does not generate plasma when forming an electrode film include an electron beam vapor deposition apparatus (EB vapor deposition apparatus) and a pulse laser vapor deposition apparatus.
  • EB vapor deposition apparatus electron beam vapor deposition apparatus
  • pulse laser vapor deposition apparatus a method of forming a transparent electrode film using an EB vapor deposition apparatus is referred to as an EB vapor deposition method
  • 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.
  • a plasma-free film formation apparatus As an apparatus capable of realizing a state in which plasma can be reduced during film formation (hereinafter referred to as a plasma-free film formation apparatus), for example, an opposed target sputtering apparatus, an arc plasma deposition apparatus, or the like can be considered.
  • the transparent conductive film is an electrode film (for example, the first conductive film)
  • a DC short circuit or an increase in leakage current may occur.
  • One of the causes is that fine cracks generated in the photoelectric conversion layer are covered with a dense film such as TCO (Transparent Conductive Oxide), and the opposite electrode film (second conductive film) from the transparent conductive film This is thought to be due to the increased conduction between the two. For this reason, when a material such as Al that is inferior in film quality is used for the electrode, an increase in leakage current is unlikely to occur.
  • TCO Transparent Conductive Oxide
  • the resistance value increases rapidly.
  • the sheet resistance of the conductive film in the photoelectric conversion element for an image sensor according to the present embodiment is usually 100 to 10,000 ⁇ / ⁇ , and the degree of freedom in film thickness is large.
  • the thinner the transparent conductive film the smaller the amount of light that is absorbed and the higher the light transmittance. High light transmittance is very preferable because light absorbed by the photoelectric conversion layer is increased and the photoelectric conversion performance is improved.
  • the (C) photoelectric conversion part of the photoelectric conversion element of the present invention includes at least (c-1) a photoelectric conversion layer and (c-2) an organic thin film layer other than the photoelectric conversion layer.
  • the organic semiconductor film is generally used for the photoelectric conversion layer constituting the photoelectric conversion part.
  • the organic semiconductor film may be a single layer or a plurality of layers.
  • a P-type organic semiconductor film, an N-type organic semiconductor film, or a mixed film thereof (bulk heterostructure) is used.
  • a plurality of layers it is about 2 to 10 layers, and has a structure in which any one of a P-type organic semiconductor film, an N-type organic semiconductor film, or a mixed film (bulk heterostructure) is laminated, A buffer layer may be inserted between the layers.
  • the organic semiconductor film of the photoelectric conversion layer has a triarylamine compound, a benzidine compound, a pyrazoline compound, a styrylamine compound, a hydrazone compound, a triphenylmethane compound, a carbazole compound, a polysilane compound depending on the wavelength band to be absorbed.
  • the organic thin film layer constituting the photoelectric conversion portion is (c-1) a layer other than the photoelectric conversion layer, for example, an electron transport layer, a hole transport layer, It is also used as an electron blocking layer, a hole blocking layer, a crystallization preventing layer, an interlayer contact improving layer, or the like.
  • a thin film layer selected from the group consisting of an electron transport layer, a hole transport layer, an electron block layer and a hole block layer an element capable of efficiently converting into an electric signal even with weak light energy can be obtained. Therefore, it is preferable.
  • the electron transport layer has (c-1) a role of transporting electrons generated in the photoelectric conversion layer to (A) the first electrode film or (B) the second electrode film, and (c) -1) Plays the role of blocking the movement of holes to the photoelectric conversion layer.
  • the hole transport layer has the role of transporting the generated holes from (c-1) the photoelectric conversion layer to (A) the first electrode film or (B) the second electrode film, and the hole transport destination electrode film (C-1) serves to block the movement of electrons to the photoelectric conversion layer.
  • the electron blocking layer prevents movement of electrons from (A) the first electrode film or (B) second electrode film to (c-1) the photoelectric conversion layer, and (c-1) It serves to prevent recombination and reduce dark current.
  • the hole blocking layer prevents the movement of holes from (A) the first electrode film or (B) the second electrode film to (c-1) the photoelectric conversion layer, and (c-1) It has a function of preventing recombination at the time and reducing dark current.
  • a film containing a hole blocking substance may be used alone, or two or more kinds of films may be laminated. Alternatively, it may be formed by mixing a plurality of hole blocking substances.
  • the hole blocking substance is not particularly limited as long as it is a compound that can prevent holes from flowing out of the element from the electrode.
  • the (c-2) organic thin film layer containing the compound represented by the general formula (1) can be suitably used as a hole blocking layer, but other compounds such as bathophenanthroline and bathocuproin Can be used in combination with phenanthroline derivatives, silole derivatives, quinolinol derivative metal complexes, oxadiazole derivatives, oxazole derivatives, quinoline derivatives, and the like.
  • the hole blocking layer should be thick, but from the standpoint of obtaining a sufficient amount of current when reading the signal at the time of light incidence, the thickness should be as thin as possible. .
  • the film thickness of the (C-1) photoelectric conversion portion including the (c-1) photoelectric conversion layer and (c-2) the organic thin film layer is generally about 5 to 500 nm. Is preferred.
  • the hole blocking layer and the electron blocking layer preferably have a high absorption wavelength transmittance in the (c-1) photoelectric conversion layer in order not to disturb the light absorption of the (c-1) photoelectric conversion layer. It is preferable to use it in a thin film.
  • FIG. 1 illustrates in detail a typical element structure of a photoelectric conversion element for an image sensor according to the present invention, but the present invention is not limited to these structures.
  • 1 is an insulating part
  • 2 is one electrode film (first electrode film or second electrode film)
  • 3 is an electron block layer
  • 4 is a photoelectric conversion layer
  • 5 is a hole block.
  • a layer, 6 represents the other electrode film (second electrode film or first electrode film)
  • 7 represents an insulating base material, or a stacked photoelectric conversion element.
  • the readout transistor (not shown in the drawing) only needs to be connected to either the electrode film 2 or 6, for example, if the photoelectric conversion layer 4 is transparent, the side opposite to the light incident side It may be formed on the outer side of the electrode film (the upper side of the electrode 2 or the lower side of the electrode 6). If the thin film layer (electron block layer, hole block layer, etc.) other than the photoelectric conversion layer constituting the photoelectric conversion element does not extremely shield the absorption wavelength of the photoelectric conversion layer, the direction in which light is incident is the upper side (Fig. 1 or the lower portion (the insulating substrate or the other photoelectric conversion element 7 side in FIG. 1). The electron block layer 3 and the hole block layer 5 may be interchanged.
  • the method for forming the (c-1) photoelectric conversion layer and the (c-2) organic thin film layer in the photoelectric conversion element of the present invention is generally a vacuum process such as resistance heating vapor deposition, electron beam vapor deposition, sputtering, molecular lamination.
  • Coating methods such as casting, solution process casting, spin coating, dip coating, blade coating, wire bar coating, spray coating, etc., printing methods such as inkjet printing, screen printing, offset printing, letterpress printing, micro contact printing method, etc.
  • the method of soft lithography, etc., and further a method combining a plurality of these methods can be employed.
  • each layer depends on the resistance value and charge mobility of each substance and cannot be limited, but is usually in the range of 0.5 to 5000 nm, preferably in the range of 1 to 1000 nm, more preferably 5 It is the range of thru
  • the condensed polycyclic aromatic compound represented by the formula (1) of the present invention is also suitably used as a material for organic thin films of organic electronic devices such as organic EL devices, organic solar cell devices, and organic transistor devices.
  • An organic transistor element has two electrodes (source electrode and drain electrode) in contact with an organic semiconductor, and controls the current flowing between the electrodes with a voltage applied to another electrode called a gate electrode.
  • the organic thin film containing the condensed polycyclic aromatic compound of the present invention is particularly preferably used as a semiconductor layer of an organic transistor element.
  • Examples of a method for forming an organic thin film in an organic electronic device such as an organic transistor element include a dry process such as a vapor deposition method and various solution processes, but a solution process is preferable.
  • Examples of the solution process include spin coating, drop casting, dip coating, spraying, flexographic printing, relief printing such as relief printing, flat printing such as offset printing, dry offset printing, and pad printing. , Intaglio printing methods such as gravure printing methods, screen printing methods, stencil printing methods, stencil printing methods such as lingraph printing methods, ink jet printing methods, micro contact printing methods, etc., and also a combination of these methods .
  • the block layer described in the examples may be either a hole block layer or an electron block layer.
  • Production of the photoelectric conversion elements of Comparative Examples 1 to 3 and 9 was performed with a vapor deposition machine, and application measurement of current voltage was performed in the atmosphere.
  • the photoelectric conversion elements of Example 2 and Comparative Examples 4 to 8 were produced by a vapor deposition machine integrated with a glove box, and the produced photoelectric conversion elements were sealed in a glove box in a nitrogen atmosphere in a sealed bottle-type measurement chamber (AELS).
  • AELS sealed bottle-type measurement chamber
  • a photoelectric conversion element was installed in (Technology Co., Ltd.), and current voltage application measurement was performed. Current voltage application measurements were performed using a semiconductor parameter analyzer 4200-SCS (Keithley Instruments) unless otherwise specified.
  • Irradiation of incident light was performed using PVL-3300 (manufactured by Asahi Spectroscope) at an irradiation light wavelength of 550 nm and an irradiation light half width of 20 nm unless otherwise specified.
  • the light / dark ratio in the examples indicates a value obtained by dividing the current value in the case of light irradiation by the current value in a dark place.
  • the phase change point was measured using a thermal analyzer TGA / DSC 1 (METTLER TOLEDO) at a heating rate of 10 ° C./min.
  • Example 1 (Synthesis of the condensed polycyclic aromatic compound of the present invention represented by the formula (1)) (Process 1) 200 parts of toluene, 5 parts of 4-bromo-1,1 ′: 4 ′, 1 ′′ -terphenyl, 5 parts of bis (pinacolato) diboron, 3 parts of potassium acetate and [1,1′-bis (diphenylphosphino) ) Ferrocene] palladium (II) dichloride 0.5 part of dichloromethane adduct was mixed and stirred at reflux temperature for 4 hours under nitrogen atmosphere. After cooling the obtained reaction liquid to room temperature, 20 parts of silica gel was added and stirred for 5 minutes.
  • Process 1 200 parts of toluene, 5 parts of 4-bromo-1,1 ′: 4 ′, 1 ′′ -terphenyl, 5 parts of bis (pinacolato) diboron, 3 parts of potassium acetate and [1,1′-bis (diphenylphosphino
  • 120 parts of DMF is represented by the following formula (6) and is generally available ([1,1 ′: 4 ′, 1 ′′ -terphenyl] -4-yl) 2.6 parts of boronic acid, 2,7
  • a mixture of 2.0 parts of diiodo [1] benzothieno [3,2-b] [1] benzothiophene, 14 parts of tripotassium phosphate and 0.2 part of tetrakis (triphenylphosphine) palladium (0) The mixture was stirred at 90 ° C. for 6 hours. After cooling the obtained reaction liquid to room temperature, 120 parts of water was added, and solid content was separated by filtration.
  • Example 2 (Production and Evaluation of Photoelectric Conversion Device Using Condensed Polycyclic Aromatic Compound Represented by Formula (1)) 2,7-bis (1,1 ′: 4 ′, 1 ′′ -terphenyl-4-yl) obtained in Example 1 on an ITO transparent conductive glass (manufactured by Geomat Co., Ltd., ITO film thickness 150 nm) -[1] benzothieno [3,2-b] [1] benzothiophene was deposited as a blocking layer to a thickness of 50 nm by resistance heating vacuum deposition. Next, quinacridone was formed into a 100 nm vacuum film as a photoelectric conversion layer on the block layer.
  • Comparative Example 1 (Preparation of photoelectric conversion element using comparative compound and its evaluation) A photoelectric conversion element for a comparative imaging device according to the description of Example 2 except that the compound represented by the following formula (11) was used instead of the condensed polycyclic aromatic compound represented by the formula (1).
  • the light / dark ratio was 600 when a voltage of 5 V was applied to the transparent conductive glass side using ITO and aluminum as electrodes.
  • the phase change point of the compound represented by the following formula (11) was 366 ° C.
  • Comparative Example 2 (Production and Evaluation of Photoelectric Conversion Element Using Comparative Compound)
  • the light / dark ratio was 3500 when a voltage of 5 V was applied to the transparent conductive glass side using ITO and aluminum as electrodes.
  • the phase change point of the compound represented by the following formula (12) was 269 ° C.
  • Comparative Example 3 (Production and Evaluation of Photoelectric Conversion Element Using Comparative Compound)
  • the light / dark ratio was 3900 when a voltage of 5 V was applied to the transparent conductive glass side using ITO and aluminum as electrodes.
  • the phase change point of the compound represented by the following formula (13) was 260 ° C.
  • Comparative Example 4 (Production of photoelectric conversion element using comparative compound and its evaluation) A photoelectric conversion element for a comparative imaging device according to the description of Example 2 except that the compound represented by the following formula (14) was used instead of the condensed polycyclic aromatic compound represented by the formula (1). Was made.
  • the light / dark ratio was 15000 when a voltage of 5 V was applied to the transparent conductive glass side using ITO and aluminum as electrodes.
  • the phase change point of the compound represented by the following formula (14) was 422 ° C.
  • Comparative Example 5 (Preparation of photoelectric conversion element using comparative compound and its evaluation) A photoelectric conversion element for a comparative imaging device according to the description of Example 2 except that the compound represented by the following formula (15) was used instead of the condensed polycyclic aromatic compound represented by the formula (1). Was made.
  • the contrast ratio was 1800 when a voltage of 5 V was applied to the transparent conductive glass side using ITO and aluminum as electrodes.
  • the phase change point of the compound represented by the following formula (15) was 314 ° C.
  • Comparative Example 6 (Preparation of photoelectric conversion element using comparative compound and its evaluation) A photoelectric conversion element for a comparative imaging device according to the description of Example 2 except that the compound represented by the following formula (16) was used instead of the condensed polycyclic aromatic compound represented by the formula (1). Was made. The light / dark ratio was 690 when a voltage of 5 V was applied to the transparent conductive glass side using ITO and aluminum as electrodes. The phase change point of the compound represented by the following formula (16) was 379 ° C.
  • Comparative Example 7 (Production of photoelectric conversion element using comparative compound and its evaluation) A photoelectric conversion element for a comparative imaging device according to the description of Example 2 except that the compound represented by the following formula (17) was used instead of the condensed polycyclic aromatic compound represented by the formula (1). Was made.
  • the light / dark ratio was 240 when a voltage of 5 V was applied to the transparent conductive glass side using ITO and aluminum as electrodes.
  • the phase change point of the compound represented by the following formula (17) was 316 ° C.
  • Comparative Example 8 (Production of photoelectric conversion element using comparative compound and its evaluation) A photoelectric conversion element for a comparative imaging device according to the description of Example 2 except that the compound represented by the following formula (18) was used instead of the condensed polycyclic aromatic compound represented by the formula (1). Was made. The contrast ratio was 47 when a voltage of 5 V was applied to the transparent conductive glass side using ITO and aluminum as electrodes. The phase change point of the compound represented by the following formula (18) was 371 ° C.
  • Comparative Example 9 (Production and Evaluation of Photoelectric Conversion Element Using Comparative Compound) A comparative photoelectric conversion element for an image sensor was prepared according to the description of Example 2 except that tris (8-quinolinolato) aluminum was used instead of the condensed polycyclic aromatic compound represented by the formula (1). .
  • the contrast ratio was 31 when a voltage of 5 V was applied to the transparent conductive glass side using ITO and aluminum as electrodes.
  • the compound represented by the formula (1) of the present invention has high heat resistance, and the photoelectric conversion element for the image sensor of Example 1 using the compound is the image sensor of Comparative Examples 1 to 9. It is clear that it has characteristics superior to those of photoelectric conversion elements for use.
  • the condensed polycyclic aromatic compound represented by the formula (1) of the present invention has excellent performance in organic photoelectric conversion characteristics, and an organic imaging device having high resolution and high response is
  • organic electronics devices such as organic EL elements, organic solar cell elements and organic transistor elements, optical sensors, infrared sensors, ultraviolet sensors, devices such as X-ray sensors and photon counters, and cameras, video cameras, and infrared cameras using them. Application to such fields is expected.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Light Receiving Elements (AREA)
  • Solid State Image Pick-Up Elements (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Abstract

La présente invention concerne le composé aromatique polycyclique condensé représenté par la formule (1) ; un procédé de production du composé aromatique polycyclique condensé ; et un procédé de production d'un élément de conversion photoélectrique mettant en œuvre le composé aromatique polycyclique condensé. Grâce à l'utilisation du composé représenté par la formule (1), il est possible de produire un élément de conversion photoélectrique présentant d'excellentes caractéristiques de prévention de fuite de trou et de fuite d'électrons et une excellente résistance à la chaleur à des températures de traitement, et de produire une variété de dispositifs électroniques, tels que des transistors organiques, présentant une excellente résistance à la chaleur.
PCT/JP2016/064945 2015-05-20 2016-05-19 Composé aromatique polycyclique condensé WO2016186186A1 (fr)

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CN110301052B (zh) * 2017-02-07 2023-12-12 佳能株式会社 光电转换元件、和使用其的光学区域传感器、图像拾取元件和图像拾取设备
JPWO2021172185A1 (fr) * 2020-02-28 2021-09-02

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