WO2016186186A1 - Condensed polycyclic aromatic compound - Google Patents

Condensed polycyclic aromatic compound

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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
method
polycyclic aromatic
electrode
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PCT/JP2016/064945
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French (fr)
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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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D495/00Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02Heterocyclic 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
    • C07D495/04Ortho-condensed systems
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L51/00Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof
    • H01L51/05Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof specially adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential- jump barrier or surface barrier multistep processes for their manufacture
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L51/00Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof
    • H01L51/42Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof specially adapted for sensing infra-red radiation, light, electro-magnetic radiation of shorter wavelength or corpuscular radiation and adapted for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation using organic materials as the active part, or using a combination of organic materials with other material as the active part; Multistep processes for their manufacture
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/54Material technologies
    • Y02E10/549Material technologies organic PV cells

Abstract

The present invention provides the condensed polycyclic aromatic compound represented by formula (1); a method for producing the condensed polycyclic aromatic compound; and a method for producing a photoelectric conversion element by using the condensed polycyclic aromatic compound. By using the compound represented by formula (1), it is possible to produce a photoelectric conversion element having excellent hole leakage and electron leakage prevention characteristics and excellent heat resistance to processing temperatures, and to produce a variety of electronic devices, such as organic transistors, having excellent heat resistance.

Description

Condensed polycyclic aromatic compound

The present invention is a photoelectric conversion element, an imaging device, a novel condensed polycyclic aromatic compound which may be used in an optical sensor and an organic semiconductor device or the like.

In recent years, there has been a growing interest in organic electronics device. It The characteristics of the organic electronic device is flexible, it can have a large area, even, and the like allow for inexpensive high-speed printing method in electronics device manufacturing processes. Representative examples of the organic electronic devices organic EL device, an organic solar cell device, an organic photoelectric conversion element, and an organic transistor device. The organic EL element is expected as a main target of the next generation flat panel display applications are applications such as cell phone displays and TV, it is continuously developed, further aiming at high performance. The organic solar cell element, as an inexpensive source of energy in a flexible, also an organic transistor element is to be utilized as a component of flexible displays and inexpensive IC, research and development have been made.

The development of organic electronic devices, development of a material constituting the device is very important. Therefore it has been studied a number of materials, not be said to have sufficient performance, development of materials useful for various devices still have been vigorously conducted. Among them, a compound a benzothienopyridine benzothiophene as a base skeleton have also been developed as an organic electronic material (Patent Document 1-3). Alkyl derivatives of benzothienopyridine benzothiophene, although having sufficient solvent solubility to form a semiconductor thin film in the printing process prone to phase transition at low temperature by the number of condensed rings is relatively small with respect to the alkyl chain length, it organic electronics devices using, there is a problem that the heat resistance will be inferior.

Further, in recent organic electronic devices, organic photoelectric conversion device, development of the next generation of the image pickup device has been expected, the report from several groups have been made. Use for example, quinacridone derivatives, or example a quinazoline derivative used in the photoelectric conversion element (Patent Document 4), an example of applying the photoelectric conversion element using the quinacridone derivatives to the imaging element (Patent Document 5), a diketopyrrolopyrrole derivative it has been reported, such as stomach example (Patent Document 6). Generally, the imaging device, the reduction of dark current, high contrast, believed to power saving. Therefore, for the purpose of reducing leakage current from the photoelectric conversion portion of the dark, between the photoelectric conversion portion and the electrode portion, a hole blocking layer, or a method of inserting an electron blocking layer is used.

Hole blocking layer, and an electron blocking layer, in the field of organic electronics devices have generally widely used, respectively, in the configuration membrane of the device, the membrane having an electrode or conductive, and the other film it is disposed at the interface, and controls the reverse movement of holes or electrons. Further, a hole blocking layer, and electron blocking layer is also intended to adjust the leakage of unwanted holes or electrons. The application of the device, the heat resistance, the transmission wavelength, in consideration of properties such as film forming method, these materials are selected appropriately. However, in particular for required performance of the material of the photoelectric conversion element application high, a hole blocking layer so far, or the electron blocking layer, leakage current prevention properties, in terms of heat resistance to the process temperatures, have sufficient performance it can not be said to be, not yet to be commercially exploited.

JP 2008-258592 JP International Publication No. WO 2008/047896 International Publication No. WO 2010/098372 Patent No. 4945146 Patent No. 5022573 Patent No. 2008-290963 Publication

The present invention has been made in view of such circumstances, holes or electrons leak prevention characteristics, and or a photoelectric conversion device excellent in heat resistance, etc. to the process temperature, the organic transistor or the like having excellent heat resistance Introduction and to provide a novel condensed polycyclic aromatic compound which may be used in various electronic devices that.

The present inventors, in order to solve the above problems, intensive studies and as a result, found that the solution to the challenges by using a compound represented by the following formula (1), and completed the present invention.
That is, the present invention is as follows.

[1] the following formula (1)

Figure JPOXMLDOC01-appb-C000006
In condensed polycyclic aromatic compound represented by,
[2] A production method of the condensed polycyclic aromatic compound represented by the formula (1) according to [1], the following formula (4)
Figure JPOXMLDOC01-appb-C000007
A compound represented in the following formula (5)
Figure JPOXMLDOC01-appb-C000008
(Equation (5), X represents. A halogen atom) comprising reacting a compound represented by a method for producing a condensed polycyclic aromatic compound,
[3] A production method of the condensed polycyclic aromatic compound represented by the formula (1) according to [1], the following formula (6)
Figure JPOXMLDOC01-appb-C000009
A compound represented in the following formula (5)
Figure JPOXMLDOC01-appb-C000010
(Equation (5), X represents. A halogen atom) comprising reacting a compound represented by a method for producing a condensed polycyclic aromatic compound,
[4] (A) a first electrode film, (B) a second electrode layer and disposed between said first electrode film and said second electrode layer (C) an imaging device having a photoelectric conversion unit a method of manufacturing a use photoelectric conversion element, wherein the (C) photoelectric conversion unit of at least (c-1) a photoelectric conversion layer and (c-2) organic thin film layer other than the photoelectric conversion layer, wherein the (c-2 ) organic thin film layer other than the photoelectric conversion layer, the include fused polycyclic aromatic compound according to [1], the method comprising the (c-2) organic thin film layer other than the photoelectric conversion layer, the vapor deposition method and forming method of manufacturing a photoelectric conversion element for image pickup element,
[5] (c-2) organic thin film layer is an electron blocking layer other than the photoelectric conversion layer, a hole blocking layer, an electron transport layer or a hole transport layer, a photoelectric conversion element for image pickup device according to [4] production process, and [6] (c-2) organic thin film layer other than the photoelectric conversion layer is an electron blocking layer or a hole blocking layer, a method for manufacturing a photoelectric conversion element for image pickup device according to [5].

The present invention, excellent and photoelectric conversion element for image pickup element to the required characteristics such as leakage preventing properties and heat resistance of the holes or electrons, it is possible to provide an organic transistor or the like having excellent heat resistance.

Figure 1 illustrates an exemplary cross-sectional view an embodiment of a photoelectric conversion element for image pickup device of the present invention.

Will be described in detail the contents of the present invention. Description of constituent features described below, but is based on the exemplary embodiments and specific examples of the present invention, the present invention is not limited to such embodiments or examples.

Condensed polycyclic aromatic compound represented by the formula (1) of the present invention, for example, 4-halogeno-1,1 ': 4', 1 '' - compounds represented by terphenyl (formula (2) ) bis halogen atoms in (pinacolato) diboron (the following formula (3) obtained compound) by reacting represented by 2 - ([1,1 ': 4', 1 '' - terphenyl] - 4-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane compound represented by (formula (4)), 2,7-dihalogeno [1] benzothieno [3,2 -b] [1] can be synthesized by reaction of a benzothiophene (a compound represented by the following formula (5)).

Figure JPOXMLDOC01-appb-C000011

In the above reaction formula, X in formula (2) and (5) represents a halogen atom independently. Specific examples of the halogen atom, fluorine atom, a chlorine atom, a bromine atom, an iodine atom.

Further, the following formula (6) instead of the compound represented by the formula (4) ([1,1 ': 4', 1 '' - terphenyl] -4-yl) with boronic acid Te, the equation (5) by the reaction with a compound represented by it is possible to obtain a condensed polycyclic aromatic compound represented by the formula (1).

Figure JPOXMLDOC01-appb-C000012

Method for purifying the compound represented by the above formula (1) is not particularly limited, recrystallization, column Gros Mato chromatography, and a known method such as vacuum sublimation purification can be employed. You can combine these methods depending also required.

Imaging device for a photoelectric conversion device obtained by the production method of the present invention (hereinafter, sometimes simply referred to as "photoelectric conversion element of the present invention".) Is opposed to (A) a first electrode film (B) Second between two electrode films and electrode films, (C) a device where the photoelectric conversion unit is disposed, (a) the first electrode film or (B) above from light photoelectric conversion of the second electrode film it is intended to be incident on the part. The photoelectric conversion unit is intended for generating electrons and holes in response to the amount of incident signal corresponding to the charges are read out by the semiconductor, is a device that indicates the amount of incident light corresponding to the absorption wavelength of the photoelectric conversion portion . On the side of the electrode film no light is incident is also when the transistor for reading is connected. The photoelectric conversion element, if it is arranged in large numbers in an array, to indicate also the incident position information added to the amount of incident light, the image pickup device. The photoelectric conversion elements which are disposed more close to the light source does not shield the absorption wavelength of arranged photoelectric elements behind as viewed from the light source side (transmitting) If, by laminating a plurality of photoelectric conversion elements it may be used. By stacking a plurality of photoelectric conversion elements having different absorption wavelengths in the visible light region it can be used as a multi-color imaging element (full-color photodiode array).

Condensed polycyclic aromatic compound represented by the formula (1) of the present invention is used as a material for constituting the (C) photoelectric conversion unit.
(C) The photoelectric conversion unit, and (c-1) a photoelectric conversion layer, an electron transport layer, a hole transport layer, an electron blocking layer, a hole blocking layer, from the group consisting of anti-crystallization layer and the interlayer contact improvement layer, etc. can include a one or more of (c-2) organic thin film layer other than the photoelectric conversion layer is selected. The photoelectric conversion element material for an imaging device of the present invention can be used in any of (c-1) a photoelectric conversion layer and (c-2) the photoelectric conversion layer other than the organic thin film layer, (c-2) photoelectric conversion it is preferable to use the organic thin film layer other than the layer.

(A) the first electrode layer and (B) a second electrode film photoelectric conversion element has the present invention will be described later (C) contained in the photoelectric conversion unit (c-1) the photoelectric conversion layer is a hole transport If you have sex, (c-2) organic thin film layer other than the photoelectric conversion layer (hereinafter, an organic thin film layer other than the photoelectric conversion layer, simply referred to as "(c-2)) the organic thin film layer") positive when a hole transporting layer having a hole transporting property, serve to collect this removed the holes from the (c-1) a photoelectric conversion layer and the (c-2) organic thin film layer, ( C) and when included in the photoelectric conversion unit (c-1) the photoelectric conversion layer has an electron transporting property, when (c-2) organic thin film layer is an electron transporting layer having an electron transporting property, the (c -1) the photoelectric conversion layer and the (c-2) plays a role of discharging it takes out the electrons from the organic thin film layer. Therefore, (A) material can be used as the first electrode layer and (B) the second electrode film is not particularly limited as long as it has a certain degree of conductivity, the adjacent (c-1) a photoelectric conversion layer and (c-2) adhesion and electron affinity of the organic thin film layer, ionization potential, it is preferable to select in consideration of stability. (A) A material that can be used as the first electrode layer and (B) a second electrode film, for example, tin oxide (NESA), indium oxide, indium tin oxide (ITO) and indium zinc oxide (IZO), such as conductive metal oxides; gold, silver, platinum, chromium, aluminum, iron, cobalt, metals such as nickel and tungsten; copper iodide and inorganic conductive materials copper sulfide and the like; polythiophene, electrically conductive polymers such as polypyrrole and polyaniline ; and carbon and the like. In the case of using a plurality of these materials may be used as a mixture, it may be used a layer containing each material by laminating two or more layers. (A) but unless not particularly limited hinder unnecessarily the reception of the first electrode layer and (B) a second electrically conductive material used for the electrode film and the photoelectric conversion element, and the signal intensity of the photoelectric conversion element, consumption it is preferable high as possible from the point of view of power. For example, the sheet resistance is sufficiently functions as a 300 [Omega / □ less if ITO film having conductivity (A) the first electrode layer and (B) a second electrode layer, the number Omega / □ degree of conductivity since the commercial products of the substrate having the ITO film are also made available with, it is desirable to use a substrate having such high conductivity. The thickness of the ITO film (electrode film) can be arbitrarily selected in consideration of conductivity, generally 5 to 500 nm, preferably from 10 to 300nm approximately. As a method for forming a film such as ITO is known deposition method, electron beam method, a sputtering method, chemical reaction method and coating method. The ITO film provided on the substrate may be subjected to corresponding UV- ozone treatment or plasma treatment or the like as required.

(A) of the first electrode layer and (B) a second electrode film, as the material of the transparent electrode film used on either side of at least the light is incident, ITO, IZO, SnO 2, ATO ( antimony-doped tin oxide), ZnO, AZO (Al-doped zinc oxide), GZO (gallium-doped zinc oxide), TiO 2, FTO (fluorine-doped tin oxide) and the like. (C-1) the transmittance of light incident through the transparent electrode film in the absorption peak wavelength of the photoelectric conversion layer is preferably 60% or more, more preferably 80% or more, 95% or more there it is particularly preferred.

In the case of stacking a plurality of photoelectric conversion layers having different wavelengths to be detected, the electrode film used between each of the photoelectric conversion layer (which is (A) other than the first electrode layer and (B) a second electrode film an electrode film), it is necessary to transmit light of wavelengths other than the light each of the photoelectric conversion layer is detected, it is preferable to use a material that transmits 90% or more of the incident light to the electrode film, 95 it is more preferred to use% or more materials that transmit light.

Electrode film is preferably produced in a plasma-free. By making these electrode films by plasma-free, plasma Influence is reduced to a substrate electrode film is provided, the photoelectric conversion characteristics of the photoelectric conversion element can be improved. Here, the plasma-free and plasma is not generated during deposition of the electrode layer, or the distance from the plasma generation source to the substrate is 2cm or more, preferably more than 10cm, more preferably more than 20cm, to reach the substrate refers to a state such as plasma is reduced.

The apparatus generating no plasma during deposition of the electrode film, for example, an electron beam deposition apparatus (EB deposition apparatus) and a pulsed laser deposition apparatus. Hereinafter, the method of depositing the transparent electrode film by using an EB vapor deposition apparatus referred to as an EB evaporation method, a method of depositing the transparent electrode film by using a pulsed laser deposition apparatus is referred to as a pulsed laser deposition method.

Can be realized a state that can be reduced through the deposition plasma apparatus as is (hereinafter, referred deposition apparatus is a plasma-free), for example, the facing target sputtering apparatus or an arc plasma deposition apparatus or the like.

If the transparent conductive film as an electrode film (e.g., the first conductive film), which may increase the DC short or leak current, it occurs. One of the reasons is, fine cracks generated in the photoelectric conversion layer is covered by a dense film such as TCO (Transparent Conductive Oxide), the opposite side of the electrode film and the transparent conductive film (second conductive film) It is considered to increase the conduction between. Therefore, when a material having relatively poor film quality such as Al in the electrode, the leak current hardly increases. The thickness of the electrode film, by controlling in accordance with the thickness of the photoelectric conversion layer (the depth of the crack), it is possible to suppress an increase in leakage current.

Usually, when the conductive film is thinner than a predetermined value, it occurs a rapid increase in resistance. The sheet resistance of the conductive film in the imaging device for a photoelectric conversion element of the present embodiment is usually 100 to 10000 ohms / □, a large degree of freedom in film thickness. The amount of light absorbed more transparent conductive film is thin is reduced, the light transmittance is generally increased. When the light transmittance is high, highly preferred for improving the photoelectric conversion ability light absorbed by the photoelectric conversion layer is increased.

Photoelectric conversion element has (C) photoelectric conversion unit of the present invention comprises at least (c-1) a photoelectric conversion layer and (c-2) organic thin film layer other than the photoelectric conversion layer.

(C) constituting the photoelectric conversion section (c-1), but generally the organic semiconductor film is used for the photoelectric conversion layer, the organic semiconductor film is more, or may be a layer, if further is, P-type organic semiconductor film, N-type organic semiconductor film, or their mixed film (bulk structures) is used. On the other hand, if a plurality of layers, is about 2-10 layers, it has P-type organic semiconductor film, N-type organic semiconductor film, or a stacked structure of one of those mixed film (bulk structure), buffer layer may be inserted between the layers.

The organic semiconductor film of (c-1) a photoelectric conversion layer, depending on the wavelength band to be absorbed, triarylamine compounds, benzidine compounds, pyrazoline compounds, styryl compounds, hydrazone compounds, triphenylmethane compound, a carbazole compound, a polysilane compound , a thiophene compound, a phthalocyanine compound, a cyanine compound, a merocyanine compound, an oxonol compound, a polyamine compound, an indole compound, a pyrrole compound, a pyrazole compound, a polyarylene compound, a carbazole derivative, a naphthalene derivative, anthracene derivative, a chrysene derivative, a phenanthrene derivative, pentacene derivatives, phenyl butadiene derivative, a styryl derivative, a quinoline derivative, a tetracene derivative, pyrene derivative, perylene derivative, fluoranthene derivative, Kinakuri Emissions derivatives, coumarin derivatives, porphyrin derivatives, fullerene derivatives and metal complexes (Ir complexes, Pt complexes, Eu complexes, etc.), or the like can be used.

In the photoelectric conversion device of the present invention, (C) constituting the photoelectric conversion section (c-2) organic thin film layer, (c-1) The photoelectric conversion layer other layers, for example, an electron transport layer, a hole transport layer, electron blocking layer, a hole blocking layer, also used as a crystallization preventing layer or interlayer contact improving layer and the like. In particular the electron transport layer, a hole transport layer, by using as one or more thin film layers are selected from the group consisting of an electron blocking layer and hole blocking layer, element for converting into electricity efficiently signal can be obtained even with weak light energy for preferred.

The electron-transporting layer, an electron and (A) and serves to transport to the first electrode film, or (B) a second electrode layer, the electron transport destination of the electrode film generated in (c-1) a photoelectric conversion layer (c -1) holes into the photoelectric conversion layer plays a role of blocking the movement.

The hole transport layer has a function of transporting the holes generated (c-1) from the photoelectric conversion layer into (A) a first electrode film, or (B) a second electrode layer, a hole transport destination of the electrode film from electrons (c-1) the photoelectric conversion layer plays a role of blocking the movement.

The electron blocking layer, (A) interfere with the movement of electrons to the first electrode film, or (B) second from the electrode film (c-1) a photoelectric conversion layer, (c-1) in the photoelectric conversion layer prevent recombination serves to reduce dark current.

The hole blocking layer, (A) interfere with the movement of holes to the first electrode film, or (B) second from the electrode film (c-1) a photoelectric conversion layer, (c-1) a photoelectric conversion layer prevent recombination at has a function of reducing the dark current.

The hole blocking layer, to a layer containing a hole blocking material may be used alone or may be laminated two or more films. Alternatively, it may be formed by mixing a plurality of hole blocking material. The hole blocking material is not particularly limited as long as it is a compound capable of holes to prevent the flowing out of the electrodes outside the device.

Of these, comprising a compound represented by the general formula (1) (c-2) organic thin film layer can be used, particularly suitable as a hole blocking layer, other compounds such bathophenanthroline and bathocuproine phenanthroline derivatives and the like, silole derivatives, quinolinol derivative metal complexes, oxadiazole derivatives, can be used together oxazole derivatives, quinoline derivatives and. The thickness is thicker has good hole blocking layer from the viewpoint of preventing leakage current, as thin as possible is better film thickness from the viewpoint of obtaining a sufficient amount of current during the signal readout time of the light incident . To achieve both these contradictory properties, typically (c-1) a photoelectric conversion layer and (c-2) may include an organic thin film layer (C) layer of the photoelectric conversion portion thickness is about 5 to 500nm It is preferred.

The hole blocking layer and electron blocking layer, for (c-1) does not interfere with the light absorption of the photoelectric conversion layer preferably has high transmittance in the absorption wavelength in (c-1) a photoelectric conversion layer, it is preferred to use a thin film.

Typical element structure of a photoelectric conversion element for image pickup device of the present invention will be described in detail in FIG. 1, the present invention is not limited to these structures. In the embodiment example of FIG. 1, 1 is an insulating portion, 2 is one electrode film (first electrode film or the second electrode layer), 3 is an electron blocking layer, 4 is a photoelectric conversion layer, 5 is a hole blocking representing layers 6 and the other electrode layer (second electrode layer or the first electrode film), 7 is an insulating substrate, or a stacked photoelectric conversion device, respectively. Reading transistors (not described in the figure) has only to be connected to the 2 or 6 or of the electrode film, for example, if the photoelectric conversion layer 4 is transparent, the side opposite to the side where light is incident (upper electrode 2, or lower electrode 6) outside of the electrode film may be deposited. As long as the thin film layer other than the photoelectric conversion layer forming the photoelectric conversion element (electron blocking layer or hole blocking layer or the like) is not extremely shield the absorption wavelength of the photoelectric conversion layer, the direction in which light enters the top (FIG. It may be either insulating portion 1 side) or the lower (insulating board or other photoelectric conversion element 7 side in FIG. 1) in one. Note that the electron blocking layer 3, a hole blocking layer 5 may be interchanged.

Method for forming the (c-1) a photoelectric conversion layer and (c-2) organic thin film layer in the photoelectric conversion element of the present invention, generally, the resistance heating vapor deposition is a vacuum process, electron beam evaporation, sputtering, molecular accumulation Law, casting a solution process, spin coating, dip coating, blade coating, wire bar coating, or a coating method such as spray coating, ink jet printing, screen printing, offset printing, a printing method such as relief printing, micro contact printing method etc. soft lithography techniques, and more may be employed a method of combining a plurality of these methods. The thickness of each layer, can not be limited since it depends on the resistance value, the charge mobility of the respective materials, usually in the range of 0.5 to 5000 nm, preferably from 1 to 1000nm range, more preferably 5 or in the range of 500nm.

Condensed polycyclic aromatic compound represented by the formula (1) of the present invention, the organic EL device is suitably used as a material of an organic thin film of an organic electronic devices such as organic solar cell element and an organic transistor device.

The organic transistor element is in contact with the organic semiconductor has two electrodes (source and drain electrodes), a current flowing between the electrodes, there is controlled by voltage applied to another electrode called a gate electrode , organic film containing the fused polycyclic aromatic compound of the present invention is particularly preferably used as a semiconductor layer of an organic transistor element.

As a method for forming the organic thin film in the organic electronic devices such as organic transistor device, although such dry process and various solutions process such as an evaporation method and the like, is preferably formed by a solution process. The solution process for example, spin coating, drop casting, dip coating, spraying, flexographic printing, relief printing method such as a resin relief printing, offset printing method, a dry offset printing method, planographic printing methods such as pad printing method , intaglio printing method such as gravure printing, screen printing, mimeograph printing method, stencil printing method such as Ringurafu printing, ink jet printing, microcontact printing and the like, and further is a method of combining a plurality of these methods . When a film is formed by a solution process, the above coating, was printed, it is preferable that the solvent is evaporated to form a thin film.

Hereinafter, a more detailed explanation of the present invention to examples, the present invention is not limited to these examples.

Blocking layer described in the examples may be any of the hole blocking layer and electron blocking layer. Preparation of photoelectric conversion elements of Comparative Examples 1 to 3 and 9 is carried out at a deposition machine, it was applied measuring current voltage in the atmosphere. Preparation of photoelectric conversion element of Example 2 and Comparative Example 4 及至 8 is carried out in the vapor deposition apparatus that is integrated with a glove box, bottle-shaped measuring chamber of the photoelectric conversion element manufactured closed in a glove box with a nitrogen atmosphere (Eieruesu a photoelectric conversion element placed on technologies Inc.), was applied measuring current voltage. Applying measured current voltage, unless otherwise specified, it was performed using a semiconductor parameter analyzer 4200-SCS (Keithley Instruments). Irradiation of the incident light, unless otherwise specified, using PVL-3300 (manufactured by Asahi Spectra Co., Ltd.), the irradiation light wavelength 550 nm, was performed by irradiating light FWHM 20 nm. Contrast ratio in the examples shows a divided by the current value of the dark current value in the case of performing light irradiation. The phase change point using a thermal analyzer TGA / DSC 1 (METTLER TOLEDO Co., Ltd.) was measured at a heating rate of 10 ° C. / min.

Example 1 (Synthesis of condensed polycyclic aromatic compound of the present invention represented by the formula (1))
(Step 1)
200 parts of toluene, 4-bromo-1,1 ': 4', 1 '' - 5 parts terphenyl, bis (pinacolato) diboron 5 parts, 3 parts of potassium acetate and [1,1'-bis (diphenylphosphino ) ferrocene] were mixed palladium (II) dichloride dichloromethane adduct 0.5 parts under a nitrogen atmosphere and stirred for 4 hours at reflux temperature. After cooling the resulting reaction solution to room temperature, silica gel 20 parts and the mixture was stirred for 5 minutes. Thereafter, 2 solid was filtered off, represented by the following formula (4) by the solvent is removed in vacuo - ([1,1 ': 4', 1 '' - terphenyl] -4-yl) - the 4,4,5,5-tetramethyl-1,3,2-dioxaborolane 5.5 parts was obtained as a white solid.

Figure JPOXMLDOC01-appb-C000013

(Step 2A)
The DMF120 parts, obtained in Step 1 2 - ([1,1 ': 4', 1 '' - terphenyl] -4-yl) -4,4,5,5-tetramethyl-1,3, 2-dioxaborolane, 3.5 parts 2,7-diiodo [1] benzothieno [3,2-b] [1] 2.1 parts of benzothiophene, tripotassium 14 parts of phosphoric acid, water 4.0 parts of tetrakis (tri phenyl phosphine) palladium (0) 0.3 parts were mixed, under a nitrogen atmosphere and stirred for 6 hours at 90 ° C.. After cooling the resulting reaction solution to room temperature, 120 parts of water was added, was separated by filtration the solid. The resulting solids were washed with acetone drying, refined by sublimation, 2,7-bis formula (1) (1, 1 ': 4', 1 '' - terphenyl - 4-yl) - [1] benzothieno [3,2-b] [1] benzo-thiophene 3.0 parts.

(Step 2B)
By alternative synthetic method as in the step 2A, the formula (1) represented by 2,7-bis (1,1 ': 4', 1 '' - terphenyl-4-yl) - [1] benzothieno [3,2-b] was obtained [1] compounds of benzothiophene. Synthesis method is as follows. That is, DMF120 parts, commonly available is represented by the following formula (6) ([1,1 ': 4', 1 '' - terphenyl] -4-yl) 2.6 parts boronic acid, 2,7 - diiodo [1] benzothieno [3,2-b] [1] benzothiophene 2.0 parts of tripotassium phosphate, 14 parts of tetrakis (triphenylphosphine) palladium (0) were mixed 0.2 parts of a nitrogen atmosphere lower and stirred for 6 hours at 90 ° C.. After cooling the resulting reaction solution to room temperature, 120 parts of water was added, was separated by filtration the solid. The resulting solids were washed with acetone drying, refined by sublimation, 2,7-bis formula (1) (1, 1 ': 4', 1 '' - terphenyl - 4-yl) - [1] benzothieno [3,2-b] [1] benzo-thiophene 1.2 parts.

Figure JPOXMLDOC01-appb-C000014

Example 2 (Preparation and evaluation of a photoelectric conversion element using the condensed polycyclic aromatic compound represented by the formula (1))
ITO transparent conductive glass (GEOMATEC Co., Ltd., ITO film thickness 150 nm), the resulting 2,7-bis in Example 1 (1, 1 ': 4', 1 '' - terphenyl-4-yl) - [1] benzothieno [3,2-b] [1] benzothiophene was 50nm formed by resistance heating vacuum deposition as a block layer. Then, on the block layer, and the quinacridone as a photoelectric conversion layer and 100nm vacuum deposition. Finally, on the photoelectric conversion layer, aluminum was 100nm vacuum film as an electrode, to produce a photoelectric conversion element of the present invention. Contrast ratio when the 5V voltage is applied to the transparent conductive glass side of ITO and aluminum as an electrode was 140,000. Further, the phase change point of the compound obtained in Example 1 was 482 ° C..

Comparative Example 1 (Preparation and evaluation of a photoelectric conversion device using the compound for comparison)
Formula (11) represented by the image pickup device for a photoelectric conversion element for comparison except for using compound was prepared analogously as described in Example 2 in place of the condensed polycyclic aromatic compound represented by the formula (1) It was produced. Contrast ratio when the 5V voltage is applied to the transparent conductive glass side of ITO and aluminum as the electrode was 600. Further, the phase change point of the compound represented by the following formula (11) was 366 ° C..

Figure JPOXMLDOC01-appb-C000015

Comparative Example 2 (Preparation and evaluation of a photoelectric conversion device using the compound for comparison)
Formula (12) represented by the image pickup device for a photoelectric conversion element for comparison except for using compound was prepared analogously as described in Example 2 in place of the condensed polycyclic aromatic compound represented by the formula (1) It was produced. Contrast ratio when the 5V voltage is applied to the transparent conductive glass side of ITO and aluminum as an electrode was 3500. Further, the phase change point of the compound represented by the following formula (12) was 269 ° C..

Figure JPOXMLDOC01-appb-C000016

Comparative Example 3 (Preparation and evaluation of a photoelectric conversion device using the compound for comparison)
Formula (13) represented by the image pickup device for a photoelectric conversion element for comparison except for using compound was prepared analogously as described in Example 2 in place of the condensed polycyclic aromatic compound represented by the formula (1) It was produced. Contrast ratio when the 5V voltage is applied to the transparent conductive glass side of ITO and aluminum as an electrode was 3900. Further, the phase change point of the compound represented by the following formula (13) was 260 ° C..

Figure JPOXMLDOC01-appb-C000017

Comparative Example 4 (Preparation and evaluation of a photoelectric conversion device using the compound for comparison)
Formula (14) represented by the image pickup device for a photoelectric conversion element for comparison except for using compound was prepared analogously as described in Example 2 in place of the condensed polycyclic aromatic compound represented by the formula (1) It was produced. Contrast ratio when the 5V voltage is applied to the transparent conductive glass side of ITO and aluminum as an electrode was 15000. Further, the phase change point of the compound represented by the following formula (14) was 422 ° C..

Figure JPOXMLDOC01-appb-C000018

Comparative Example 5 (Preparation and evaluation of a photoelectric conversion device using the compound for comparison)
Formula (15) represented by the image pickup device for a photoelectric conversion element for comparison except for using compound was prepared analogously as described in Example 2 in place of the condensed polycyclic aromatic compound represented by the formula (1) It was produced. Contrast ratio when the 5V voltage is applied to the transparent conductive glass side of ITO and aluminum as an electrode was 1800. Further, the phase change point of the compound represented by the following formula (15) was 314 ° C..

Figure JPOXMLDOC01-appb-C000019

Comparative Example 6 (Preparation and evaluation of a photoelectric conversion device using the compound for comparison)
Equation (1) represented by condensed polycyclic aromatic compound formula (16) represented by the image pickup device for a photoelectric conversion element for comparison except for using compound was prepared analogously as described in Example 2 in place of It was produced. Contrast ratio when the 5V voltage is applied to the transparent conductive glass side of ITO and aluminum as the electrode was 690. Further, the phase change point of the compound represented by the following formula (16) was 379 ° C..

Figure JPOXMLDOC01-appb-C000020

Comparative Example 7 (Preparation and evaluation of a photoelectric conversion device using the compound for comparison)
Formula (17) represented by the image pickup device for a photoelectric conversion element for comparison except for using compound was prepared analogously as described in Example 2 in place of the condensed polycyclic aromatic compound represented by the formula (1) It was produced. Contrast ratio when the 5V voltage is applied to the transparent conductive glass side of ITO and aluminum as the electrode was 240. Further, the phase change point of the compound represented by the following formula (17) was 316 ° C..

Figure JPOXMLDOC01-appb-C000021

Comparative Example 8 (Production and evaluation of a photoelectric conversion device using the compound for comparison)
Formula (18) represented by the image pickup device for a photoelectric conversion element for comparison except for using compound was prepared analogously as described in Example 2 in place of the condensed polycyclic aromatic compound represented by the formula (1) It was produced. Contrast ratio when the 5V voltage is applied to the transparent conductive glass side of ITO and aluminum as the electrode was 47. Further, the phase change point of the compound represented by the following formula (18) was 371 ° C..

Figure JPOXMLDOC01-appb-C000022

Comparative Example 9 (Preparation and evaluation of a photoelectric conversion device using the compound for comparison)
To prepare a photoelectric conversion element for image pickup device for comparison is prepared analogously as described in Example 2 except for using tris (8-quinolinolato) aluminum in place of the condensed polycyclic aromatic compound represented by the formula (1) . Contrast ratio when the 5V voltage is applied to the transparent conductive glass side of ITO and aluminum as the electrode was 31.

From the above evaluation results, the compounds of the formula (1) of the present invention has a high heat resistance, a first embodiment of an imaging device for photoelectric conversion elements, image pickup elements of Comparative Examples 1 to 9 using the same it is clear that with superior properties than use photoelectric conversion element.

As described above, condensed polycyclic aromatic compound represented by the formula (1) of the present invention has excellent performance in the organic photoelectric conversion characteristics, organic image sensor having a high resolution and high response is well organic EL device, an organic solar cell device and organic electronic devices such as organic transistor device, an optical sensor, infrared sensor, ultraviolet sensor, X-rays sensors, photon counter or the like devices or cameras employing them, video cameras, infrared cameras application to the field of the like are expected.

First insulating portion 2 upper electrode 3 electron blocking layer 4 photoelectric conversion unit 5 hole blocking layer 6 lower electrode 7 insulated substrate or other photoelectric conversion element

Claims (6)

  1. The following formula (1)
    Figure JPOXMLDOC01-appb-C000001
    In condensed polycyclic aromatic compound represented.
  2. A method of manufacturing a condensed polycyclic aromatic compound represented by the formula (1) according to claim 1, the following formula (4)
    Figure JPOXMLDOC01-appb-C000002
    A compound represented in the following formula (5)
    Figure JPOXMLDOC01-appb-C000003
    (Equation (5), X represents. A halogen atom) comprising reacting a compound represented by the method for producing a condensed polycyclic aromatic compound.
  3. A method of manufacturing a condensed polycyclic aromatic compound represented by the formula (1) according to claim 1, formula (6)
    Figure JPOXMLDOC01-appb-C000004
    A compound represented in the following formula (5)
    Figure JPOXMLDOC01-appb-C000005
    (Equation (5), X represents. A halogen atom) comprising reacting a compound represented by the method for producing a condensed polycyclic aromatic compound.
  4. (A) a first electrode film, (B) a second electrode layer and disposed between said first electrode film and said second electrode layer (C) photoelectric conversion image pickup device having a photoelectric conversion unit a method of manufacturing a device, comprising the (C) photoelectric conversion unit of at least (c-1) a photoelectric conversion layer and (c-2) organic thin film layer other than the photoelectric conversion layer, wherein the (c-2) photoelectric conversion the organic thin film layer other than the layer comprises a condensed polycyclic aromatic compound according to claim 1, wherein the method includes the (c-2) organic thin film layer other than the photoelectric conversion layer, that is formed by vapor deposition comprising, a method for manufacturing a photoelectric conversion element for image pickup element.
  5. Wherein (c-2) the photoelectric conversion layer other than the organic thin film layer is an electron blocking layer, a hole blocking layer, an electron transport layer or a hole transport layer, the method of manufacturing the photoelectric conversion element for image pickup device according to claim 4 .
  6. (C-2) organic thin film layer other than the photoelectric conversion layer is an electron blocking layer or a hole blocking layer, a method for manufacturing a photoelectric conversion element for image pickup device according to claim 5.


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Citations (4)

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Publication number Priority date Publication date Assignee Title
JP2009203447A (en) * 2008-02-29 2009-09-10 Ricoh Co Ltd POLYMER CONTAINING BENZOTHIENO [3,2-b] BENZOTHIOPHENE STRUCTURE
JP2009275032A (en) * 2008-04-17 2009-11-26 Ricoh Co Ltd [1]BENZOTHIENO[3,2-b][1]BENZOTHIOPHENE DERIVATIVE HAVING LEAVING GROUP AND [1]BENZOTHIENO
JP2010232413A (en) * 2009-03-27 2010-10-14 Chiba Univ Vertical organic semiconductor device
WO2015163349A1 (en) * 2014-04-25 2015-10-29 日本化薬株式会社 Material for photoelectric conversion element for use in imaging element, and photoelectric conversion element including same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009203447A (en) * 2008-02-29 2009-09-10 Ricoh Co Ltd POLYMER CONTAINING BENZOTHIENO [3,2-b] BENZOTHIOPHENE STRUCTURE
JP2009275032A (en) * 2008-04-17 2009-11-26 Ricoh Co Ltd [1]BENZOTHIENO[3,2-b][1]BENZOTHIOPHENE DERIVATIVE HAVING LEAVING GROUP AND [1]BENZOTHIENO
JP2010232413A (en) * 2009-03-27 2010-10-14 Chiba Univ Vertical organic semiconductor device
WO2015163349A1 (en) * 2014-04-25 2015-10-29 日本化薬株式会社 Material for photoelectric conversion element for use in imaging element, and photoelectric conversion element including same

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