[go: up one dir, main page]

WO2015129581A1 - Nouveau composé aromatique polycyclique organique et son utilisation - Google Patents

Nouveau composé aromatique polycyclique organique et son utilisation Download PDF

Info

Publication number
WO2015129581A1
WO2015129581A1 PCT/JP2015/054827 JP2015054827W WO2015129581A1 WO 2015129581 A1 WO2015129581 A1 WO 2015129581A1 JP 2015054827 W JP2015054827 W JP 2015054827W WO 2015129581 A1 WO2015129581 A1 WO 2015129581A1
Authority
WO
WIPO (PCT)
Prior art keywords
organic
layer
photoelectric conversion
film
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2015/054827
Other languages
English (en)
Japanese (ja)
Inventor
山本　達也
秀典 薬師寺
俊文 井内
池田　征明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Kayaku Co Ltd
Original Assignee
Nippon Kayaku Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Kayaku Co Ltd filed Critical Nippon Kayaku Co Ltd
Priority to JP2016505182A priority Critical patent/JP6436590B2/ja
Publication of WO2015129581A1 publication Critical patent/WO2015129581A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • C07D495/12—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 three hetero rings
    • C07D495/14—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
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • 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
    • H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K39/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic radiation-sensitive element covered by group H10K30/00
    • H10K39/30—Devices controlled by radiation
    • H10K39/32—Organic image sensors
    • 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

Definitions

  • the present invention relates to novel organic polycyclic aromatic compounds and their application as organic electronics materials.
  • organic electronics devices In recent years, interest in organic electronics devices has increased. Its features include a flexible structure and a large area, and further enabling an inexpensive and high-speed printing method in the electronic device manufacturing process.
  • Typical devices include organic EL (electroluminescence) elements, organic solar cell elements, organic photoelectric conversion elements, organic transistor elements, and the like.
  • Organic EL elements are expected as a main target for next-generation display applications as flat panel displays, and are applied from mobile phone displays to TVs (TV receivers), etc., and developments aiming at further enhancement of functionality are being continued.
  • Research and development have been made on organic solar cell elements as flexible and inexpensive energy sources, and organic transistor elements on flexible displays and inexpensive ICs (integrated circuits).
  • organic electronic devices In the development of organic electronic devices, it is very important to develop the materials that make up the devices. For this reason, many materials have been studied in each field, but they cannot be said to have sufficient performance, and even now, materials that are useful for various devices are being actively developed.
  • compounds having benzotrithiophene as a mother skeleton have also been developed as organic electronics materials, such as organic transistors (Patent Documents 1 and 2, Non-Patent Document 1), organic EL (Patent Documents 1 and 2), Application to thin film solar cells (Patent Literature 1, Non-Patent Literature 2), dye-sensitized solar cells (Patent Literature 3), and the like have been reported. However, even these materials cannot be said to have sufficient performance, and have not been utilized commercially. Therefore, it is important to develop higher performance organic electronic materials.
  • organic photoelectric conversion elements are expected to be developed into next-generation imaging elements, and several groups have reported them.
  • a quinacridone derivative or a quinazoline derivative is used as a photoelectric conversion element (Patent Document 4)
  • a diketopyrrolopyrrole derivative There is an example (Patent Document 6).
  • it is considered that the performance of an imaging device is improved by aiming at reduction of dark current for the purpose of high contrast and labor saving. Therefore, in order to reduce the leakage current from the photoelectric conversion part in the dark, a technique of inserting a hole block layer or an electron block layer between the photoelectric conversion part and the electrode part is taken.
  • the hole blocking layer and the electron blocking layer are generally widely used in the field of organic electronics devices, and are arranged at the interface between the electrode or the conductive film and the other films in the component film of the device, respectively. It is a film that has the function of controlling the reverse movement of holes or electrons, and adjusts the leakage of unnecessary holes or electrons.
  • heat resistance, transmission wavelength, film formation method, etc. are selected and used in consideration of the characteristics.
  • the required performance of materials especially for photoelectric conversion elements is high, and the conventional hole blocking layer or electron blocking layer is sufficient in terms of leakage current prevention characteristics, heat resistance to process temperature, transparency to visible light, etc. It cannot be said that it has a good performance and has not been utilized commercially.
  • An object of the present invention is to provide a novel organic polycyclic aromatic compound that can be used in an organic electronic device. More specifically, it is to provide an organic polycyclic aromatic compound represented by the following formula (1) applicable to organic electronic devices such as organic EL elements, organic solar cell elements, organic transistor elements, and photoelectric conversion elements. .
  • organic electronic devices such as organic EL elements, organic solar cell elements, organic transistor elements, and photoelectric conversion elements.
  • materials for various organic electronics devices, including photoelectric conversion elements have high performance requirements such as hole or electron leakage prevention characteristics, heat resistance to process temperature, and visible light transparency, and have sufficient performance. Is required to provide.
  • the present inventor has developed a novel organic polycyclic aromatic compound, studied the possibility as an organic electronic device, and completed the present invention. That is, the present invention is as follows.
  • An organic semiconductor material comprising the organic polycyclic aromatic compound according to [1].
  • a thin film comprising the organic semiconductor material according to [2].
  • a hole blocking layer comprising the thin film according to [3] above.
  • An electronic block layer comprising the thin film as described in [3] above.
  • An organic electronic device comprising the organic semiconductor material according to [2].
  • Organic electronic device comprising the thin film according to [3], the hole blocking layer according to [4], or the electron blocking layer according to [5]
  • An image sensor in which a plurality of the photoelectric conversion elements according to [8] are arranged in an array.
  • An optical sensor including the photoelectric conversion element according to [8] above.
  • An imaging device including the photoelectric conversion device according to [8].
  • the present invention relates to a novel organic polycyclic aromatic compound. Since the compound has good semiconductor properties, a new organic electronic device, photoelectric conversion element, imaging element, and optical sensor can be obtained by using the compound. It becomes possible to provide.
  • R 1 to R 6 in the compound represents an aryl group having at least one cyano group.
  • Aryl groups include aromatic hydrocarbon groups such as phenyl, naphthyl, anthryl, phenanthryl, pyrenyl, benzopyrenyl, pyridyl, pyrazyl, pyrimidyl, quinolyl, isoquinolyl, pyrrolyl, indolenyl.
  • a phenyl group, a naphthyl group, and a pyridyl group are preferable.
  • a phenyl group is particularly preferable.
  • the substituent that at least one aryl group of R 1 to R 6 in the formula may have in addition to the cyano group includes an aryl group, an alkyl group, a cycloalkyl group, a halogen group, a hydroxy group, an alkoxy group, Examples include mercapto group, alkylthio group, nitro group, substituted amino group, amide group, acyl group, carboxyl group, acyloxy group, sulfo group, sulfamoyl group, alkylsulfamoyl group, carbamoyl group, and alkylcarbamoyl group.
  • Alkyl groups include methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, tertiary butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl Group, dodecyl group and the like.
  • Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group.
  • the halogen group include a fluoro group, a chloro group, a bromo group, and an iodo group.
  • alkoxy group examples include those in which the above alkyl group is bonded to an oxygen atom, but the number, position, and number of branches of the oxygen atom are not limited. Further, the number of substituents that R 1 to R 6 may have is not particularly limited, and the compound may have different substituents.
  • R 1 to R 6 in the formula are not aryl groups having a cyano group
  • examples of those represented by R 1 to R 6 other than the aryl group having a cyano group include a hydrogen atom, a cyano group
  • Examples of the substituent other than the aryl group and the cyano group that the aryl group may have, an alkyl group, a cycloalkyl group, a halogen group, and an alkoxy group are the same as described for the aryl group having a cyano group.
  • Examples of the substituent that the alkyl group or cycloalkyl group may have are listed as examples of the substituent that at least one aryl group of R 1 to R 6 in the formula may have in addition to the cyano group. In addition to the above, a cyano group can be mentioned.
  • the organic polycyclic aromatic compound represented by the formula (1) can be obtained, for example, by the following reaction step. Suzuki-Miyaura coupling reaction of intermediate compound represented by formula (2) and boronic acid compound (Miyaura, Norio; Yamada, Kinji; Suzuki, Akira, Tetrahedron Letters. 1979, vol. 20, issue. 36, p. 3437 -3440), an organic polycyclic aromatic compound represented by the general formula (3) can be obtained.
  • R is defined as R 1 to R 6 in the general formula (1).
  • the method for purifying the organic polycyclic aromatic compound represented by the formula (1) including the above is not particularly limited, and known methods such as recrystallization, column chromatography, and vacuum sublimation purification are employed. it can. Moreover, you may use combining these methods as needed.
  • organic polycyclic aromatic compound represented by the general formula (1) Specific examples of the organic polycyclic aromatic compound represented by the general formula (1) are shown below, but the present invention is not limited thereto.
  • a thin film can be produced using a material containing an organic polycyclic aromatic compound represented by the general formula (1) of the present invention.
  • the film thickness of the thin film varies depending on the application, but is usually from 0.01 nm to 10 ⁇ m, preferably from 0.05 nm to 3 ⁇ m, more preferably from 0.1 nm to 1 ⁇ m.
  • Thin film formation methods are generally vacuum processes such as resistance heating vapor deposition, electron beam vapor deposition, sputtering, molecular layer deposition and other gas phase methods, spin coating, drop casting, dip coating, spraying and other solution methods, flexographic printing.
  • Letterpress printing methods such as resin letterpress printing, offset printing, dry offset printing, lithographic printing methods such as pad printing, intaglio printing methods such as gravure printing, stencil printing methods such as silk screen printing, photocopier printing and lithographic printing, inkjet Examples thereof include printing, microcontact printing, and a combination of these techniques.
  • the resistance heating vapor deposition method that is a vacuum process the spin coating method that is a solution process, the dip coating method, the ink jet method, screen printing, letterpress printing, and the like are preferable.
  • An organic electronic device can be produced using the organic polycyclic aromatic compound represented by the general formula (1) as a material for electronics.
  • the organic electronic device include a thin film transistor, a photoelectric conversion element, an organic solar cell element, an organic EL element, an organic light emitting transistor element, and an organic semiconductor laser element. These will be described in detail.
  • a thin film transistor has two electrodes (a source electrode and a drain electrode) in contact with a semiconductor, and a current flowing between the electrodes is controlled by a voltage applied to another electrode called a gate electrode.
  • MOS Metal-Oxide-Semiconductor
  • MES Metal-Semiconductor
  • FIGS. 1A to 1F 1A to 1F
  • 1 represents a source electrode
  • 2 represents a semiconductor layer
  • 3 represents a drain electrode
  • 4 represents an insulator layer
  • 5 represents a gate electrode
  • 6 represents a substrate.
  • positioning of each layer and an electrode can be suitably selected according to the use of an element.
  • 1A to 1D and FIG. 1F are called lateral transistors because electrodes flow in a direction parallel to the substrate.
  • 1A is called a bottom contact bottom gate structure
  • FIG. 1B is called a top contact bottom gate structure.
  • FIG. 1C source and drain electrodes and an insulator layer are provided on a semiconductor, and a gate electrode is further formed thereon, which is called a top contact top gate structure.
  • FIG. 1D shows a structure called a top & bottom contact transistor.
  • FIG. 1F shows a bottom contact top gate structure.
  • FIG. 1E is a schematic diagram of a transistor having a vertical structure, that is, a static induction transistor (SIT). In this SIT, the current flow spreads out in a plane, so that a large amount of carriers can move at one time. Further, since the source electrode and the drain electrode are arranged vertically, the distance between the electrodes can be reduced, so that the response is fast.
  • SIT static induction transistor
  • a substrate is not shown in FIG. 1E, in the normal case, a substrate is provided outside the source electrode represented by 1 or the drain electrode represented by 3 in FIG. 1E.
  • the substrate 6 needs to be able to hold each layer formed thereon without peeling off.
  • insulating materials such as resin plates, resin films, paper, glass, quartz, ceramics, etc .; products in which an insulating layer is formed on a conductive substrate such as metal or alloy by coating, etc .; from various combinations such as resin and inorganic materials
  • the resin film that can be used include films of resins such as polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, polyamide, polyimide, polycarbonate, cellulose triacetate, and polyetherimide.
  • the element can have flexibility, is flexible and lightweight, and improves practicality.
  • the thickness of the substrate 6 is usually 1 ⁇ m to 10 mm, preferably 5 ⁇ m to 5 mm.
  • a conductive material is used for the source electrode 1, the drain electrode 3, and the gate electrode 5.
  • the conductive material include platinum, gold, silver, aluminum, chromium, tungsten, tantalum, nickel, cobalt, copper, iron, lead, tin, titanium, indium, palladium, molybdenum, magnesium, calcium, barium, Metals such as lithium, potassium and sodium and alloys containing them; Conductive oxides such as InO 2 , ZnO 2 , SnO 2 and ITO; Conductivity such as polyaniline, polypyrrole, polythiophene, polyacetylene, polyparaphenylene, vinylene and polydiacetylene A high molecular compound; a semiconductor such as silicon, germanium, and gallium arsenide; a carbon material such as carbon black, fullerene, carbon nanotube, and graphite; In addition, the conductive polymer compound or the semiconductor may be doped.
  • the dopant examples include inorganic acids such as hydrochloric acid and sulfuric acid; organic acids having an acidic functional group such as sulfonic acid; Lewis acids such as PF 5 , AsF 5 and FeCl 3 ; halogen atoms such as iodine; lithium, Metal atoms such as sodium and potassium; and the like. Boron, phosphorus, arsenic and the like are also frequently used as dopants for inorganic semiconductors such as silicon.
  • a conductive composite material in which carbon black or metal particles are dispersed in the above dopant is also used.
  • the source electrode 1 and the drain electrode 3 that are in direct contact with the semiconductor layer 4 it is important to select an appropriate work function or to treat the surface in order to reduce the contact resistance.
  • the distance (channel length) between the source electrode 1 and the drain electrode 3 is an important factor that determines the characteristics of the device.
  • the channel length is usually 0.1 to 300 ⁇ m, preferably 0.5 to 100 ⁇ m. If the channel length is short, the amount of current that can be extracted increases, but conversely, short channel effects such as the influence of contact resistance occur and control becomes difficult, so an appropriate channel length is required.
  • the width (channel width) between the source electrode 1 and the drain electrode 3 is usually 10 to 10000 ⁇ m, preferably 100 to 5000 ⁇ m. Further, this channel width can be made longer by making the structure of the source electrode 1 and the drain electrode 3 into a comb structure, etc., and an appropriate channel width can be obtained depending on the required amount of current and the structure of the element. Need to be length.
  • the structures (shapes) of the source electrode 1 and the drain electrode 3 will be described.
  • the structure of the source electrode 1 and the structure of the drain electrode 3 may be the same or different.
  • a top contact structure having the electrodes 1, 3, and 5 on the semiconductor layer 2 it can be deposited using a shadow mask or the like, and an electrode pattern can also be directly printed and formed using a technique such as inkjet.
  • the length of the electrodes 1 and 3 may be the same as the channel width.
  • the widths of the electrodes 1, 3 and 5 are not particularly limited, but are preferably shorter in order to reduce the area of the element within a range where the electrical characteristics can be stabilized.
  • the width of the electrodes 1, 3, and 5 is usually 0.1 to 1000 ⁇ m, preferably 0.5 to 100 ⁇ m.
  • the thickness of the electrodes 1, 3, and 5 is usually 0.1 to 1000 nm, preferably 1 to 500 nm, and more preferably 5 to 200 nm.
  • a wiring is connected to each of the electrodes 1, 3, and 5, but the wiring is also made of substantially the same material as the electrodes 1, 3, and 5.
  • An insulating material is used for the insulator layer 4.
  • the insulating material include polyparaxylylene, polyacrylate, polymethyl methacrylate, polystyrene, polyvinylphenol, polyamide, polyimide, polycarbonate, polyester, polyvinyl alcohol, polyvinyl acetate, polyurethane, polysulfone, epoxy resin, and phenol.
  • Polymers such as resins and copolymers combining them; Metal oxides such as silicon dioxide, aluminum oxide, titanium oxide, and tantalum oxide; Ferroelectric metal oxides such as SrTiO 3 and BaTiO 3 ; Silicon nitride, aluminum nitride, etc.
  • the film thickness of the insulator layer 4 varies depending on the material, but is usually 0.1 nm to 100 ⁇ m, preferably 0.5 nm to 50 ⁇ m, more preferably 1 nm to 10 ⁇ m.
  • At least one compound of the organic polycyclic aromatic compound represented by the general formula (1) of the present invention can be used as the organic semiconductor material.
  • the solvent is positively evaporated. It is preferable to use for.
  • the semiconductor layer 2 is formed by a vapor deposition method, it is particularly preferable to use a single compound as the organic semiconductor rather than a mixture of a plurality of organic polycyclic aromatic compounds represented by the general formula (1). preferable.
  • additives such as dopants for the purpose of improving the characteristics of the transistor as described above are not prevented from being contained.
  • the case where the semiconductor layer 2 is formed by a solution process is not limited to this.
  • the above additives are usually added in the range of 0.01 to 10% by weight, preferably 0.05 to 5% by weight, more preferably 0.1 to 3% by weight, when the total amount of the organic semiconductor material is 1. It is good to do.
  • the semiconductor layer 2 may be formed with a plurality of layers, but a single layer structure is more preferable.
  • the thickness of the semiconductor layer 2 is preferably as thin as possible without losing necessary functions. In the lateral thin film transistor as shown in FIGS. 1A, 1B, and 1D, if the semiconductor layer 2 has a film thickness greater than a predetermined value, the characteristics of the element do not depend on the film thickness, while the semiconductor layer 2 has a large film thickness. This is because the leakage current often increases.
  • the film thickness of the semiconductor layer 2 for exhibiting a necessary function is usually 1 nm to 10 ⁇ m, preferably 5 nm to 5 ⁇ m, more preferably 10 nm to 3 ⁇ m.
  • other layers can be provided as necessary, for example, between the substrate 6 and the insulator layer 4, between the insulator layer 4 and the semiconductor layer 2, or on the outer surface of the element.
  • a protective layer is formed directly on the semiconductor layer 2 or via another layer, the influence of outside air such as humidity can be reduced, and the ON / OFF ratio of the element can be increased.
  • the electrical characteristics can be stabilized.
  • the material of the protective layer is not particularly limited.
  • films made of various resins such as acrylic resin such as epoxy resin and polymethyl methacrylate, polyurethane, polyimide, polyvinyl alcohol, fluororesin, polyolefin, etc .; silicon oxide, aluminum oxide, nitriding
  • a film made of an inorganic oxide film such as silicon and a dielectric film such as a nitride film is preferably used, and a resin (polymer) having a low oxygen or moisture permeability and a low water absorption rate is particularly preferable.
  • a protective material developed for organic EL displays can also be used as a material for the protective layer.
  • the film thickness of the protective layer can be selected according to the purpose, but is usually 100 nm to 1 mm.
  • the surface treatment on the substrate or the like controls the molecular orientation at the interface between the substrate and the semiconductor layer to be formed thereafter, and reduces the trap sites on the substrate and the insulator layer. It is considered that characteristics such as carrier mobility are improved.
  • the trap site refers to a functional group such as a hydroxyl group present in an untreated substrate. When such a functional group is present, electrons are attracted to the functional group, and as a result, carrier mobility is lowered. Therefore, reducing trap sites is often effective for improving characteristics such as carrier mobility.
  • Examples of the substrate treatment for improving the characteristics as described above include hydrophobizing treatment with hexamethyldisilazane, octyltrichlorosilane, octadecyltrichlorosilane, etc .; acid treatment with hydrochloric acid, sulfuric acid, acetic acid, etc .; sodium hydroxide, water Alkaline treatment with potassium oxide, calcium hydroxide, ammonia, etc .; Ozone treatment; Fluorination treatment; Plasma treatment with oxygen, argon, etc .; Langmuir / Blodgett film formation process; Other insulator and semiconductor thin film formation process; Machine Electric treatment such as corona discharge; rubbing treatment using fibers or the like; and combinations thereof.
  • a vacuum deposition method, a sputtering method, a coating method, a printing method, a sol-gel method, etc. are appropriately employed as a method of providing each layer such as a substrate layer and an insulating film layer, or an insulating film layer and an organic semiconductor layer. it can.
  • the thin film transistor of the present invention is manufactured by providing various layers and electrodes necessary on the substrate 6 (see FIG. 2A).
  • the substrate 6 those described above can be used. It is also possible to perform the above-described surface treatment on the substrate 6.
  • the thickness of the substrate 6 is preferably thin as long as necessary functions are not hindered.
  • the thickness of the substrate 6 varies depending on the material, but is usually 1 ⁇ m to 10 mm, preferably 5 ⁇ m to 5 mm. Further, if necessary, the substrate 6 may have an electrode function.
  • a gate electrode 5 is formed on the substrate 6 (see FIG. 2B).
  • the electrode material described above is used as the electrode material.
  • various methods can be used. For example, a vacuum deposition method, a sputtering method, a coating method, a thermal transfer method, a printing method, a sol-gel method, and the like are employed. It is preferable to perform patterning as necessary so as to obtain a desired shape during or after film formation.
  • Various methods can be used as the patterning method, and examples thereof include a photolithography method in which patterning and etching of a photoresist are combined.
  • the film thickness of the gate electrode 5 varies depending on the material, but is usually 0.1 nm to 10 ⁇ m, preferably 0.5 nm to 5 ⁇ m, more preferably 1 nm to 3 ⁇ m.
  • the thickness of the gate electrode 5 may be larger than the above thickness.
  • An insulator layer 4 is formed over the gate electrode 5 (see FIG. 2 (3)).
  • the insulator material those described above are used.
  • Various methods can be used to form the insulator layer 4. For example, spin coating, spray coating, dip coating, casting, bar coating, blade coating and other coating methods, screen printing, offset printing, inkjet printing methods, vacuum deposition, molecular beam epitaxial growth, ion cluster beam method, ion plating Examples thereof include dry process methods such as a coating method, a sputtering method, an atmospheric pressure plasma method, and a CVD method.
  • a sol-gel method, alumite on aluminum, a method of forming an oxide film on a metal such as silicon dioxide on silicon, and the like are employed.
  • the molecules constituting the semiconductor at the interface between the two layers for example, the molecules of the organic polycyclic aromatic compound represented by the above formula (1) are well oriented. Therefore, a predetermined surface treatment can be performed on the insulator layer 4.
  • the surface treatment method the same surface treatment as that of the substrate 6 can be used.
  • the thickness of the insulator layer 4 is preferably as thin as possible without impairing its function. Usually, the thickness is 0.1 nm to 100 ⁇ m, preferably 0.5 nm to 50 ⁇ m, more preferably 5 nm to 10 ⁇ m.
  • the organic polycyclic aromatic compound represented by the above general formula (1) of the present invention is used as an organic semiconductor material, and is used for forming a semiconductor layer 2 that is an organic semiconductor layer (see FIG. 2 (4)).
  • Various methods can be used for forming the semiconductor layer 2. Specifically, forming methods in vacuum processes such as sputtering, CVD, molecular beam epitaxial growth, and vacuum deposition; coating methods such as dip coating, die coater, roll coater, bar coater, and spin coat , Forming methods by solution process such as inkjet method, screen printing method, offset printing method, microcontact printing method, and the like.
  • the film is formed by a solution process such as printing or a vacuum process. And the method of forming the semiconductor layer 2 is mentioned.
  • a method for obtaining a semiconductor layer 2 by forming an organic semiconductor material by a vacuum process will be described.
  • the organic semiconductor material is heated in a crucible or a metal boat under vacuum, and the evaporated organic semiconductor material is used as a substrate (substrate 6, insulator layer 4, source electrode 1 and drain electrode). 3) and the like, that is, a vacuum deposition method is preferably employed.
  • the degree of vacuum is usually 1.0 ⁇ 10 ⁇ 1 Pa or less, preferably 1.0 ⁇ 10 ⁇ 3 Pa or less.
  • the substrate temperature during vapor deposition is usually 0 to 200 ° C., preferably 5 to 150 ° C., more preferably 10 to 120 ° C., further preferably 15 to 100 ° C., and particularly preferably 20 to 80 ° C. ° C.
  • the vapor deposition rate is usually 0.001 to 10 nm / second, preferably 0.01 to 1 nm / second.
  • the film thickness of the semiconductor layer 2 formed from an organic semiconductor material is usually 1 nm to 10 ⁇ m, preferably 5 nm to 5 ⁇ m, more preferably 10 nm to 3 ⁇ m.
  • a composition in which the organic polycyclic aromatic compound represented by the general formula (1) of the present invention is dissolved in a solvent or the like, and an additive or the like is added if necessary is used as a substrate (insulator layer 4, source electrode). 1 and the exposed portion of the drain electrode 3).
  • Coating methods include casting, spin coating, dip coating, blade coating, wire bar coating, spray coating, and other coating methods, inkjet printing, screen printing, offset printing, letterpress printing, and other micro contact printing methods. And a method of combining a plurality of these techniques.
  • a Langmuir project method in which a monomolecular film of an organic semiconductor material produced by dropping the above-described ink on a water surface is transferred to a substrate and laminated, and two materials in a liquid crystal or melt state are used.
  • a method of sandwiching between substrates and introducing them between the substrates by capillary action can also be adopted.
  • the environment such as the temperature of the substrate and the composition at the time of film formation is also important, and the characteristics of the transistor may change depending on the temperature of the substrate and the composition. Therefore, it is preferable to carefully select the temperature of the substrate and the composition.
  • the substrate temperature is usually from 0 to 200 ° C., preferably from 10 to 120 ° C., more preferably from 15 to 100 ° C. Care must be taken because it greatly depends on the solvent in the composition to be used.
  • the film thickness of the semiconductor layer 2 produced by this method is preferably thinner as long as the function is not impaired. There is a concern that the leakage current increases as the film thickness increases.
  • the film thickness of the semiconductor layer 2 is usually 1 nm to 10 ⁇ m, preferably 5 nm to 5 ⁇ m, more preferably 10 nm to 3 ⁇ m.
  • the characteristics of the semiconductor layer 2 thus formed can be further improved by post-processing. For example, it is considered that the distortion in the film (semiconductor layer 2) generated at the time of film formation is reduced by heat treatment, pinholes and the like are reduced, and the arrangement and orientation in the film can be controlled. For this reason, the organic semiconductor characteristics can be improved and stabilized.
  • this heat treatment is effective for improving the characteristics.
  • This heat treatment is performed by heating the substrate after forming the semiconductor layer 2.
  • the temperature of the heat treatment is not particularly limited, but is usually from room temperature to 150 ° C., preferably 40 to 120 ° C., more preferably 45 to 100 ° C.
  • the heat treatment time at this time is not particularly limited, but is usually 10 seconds to 24 hours, preferably about 30 seconds to 3 hours.
  • the atmosphere at that time may be air, but may be an inert atmosphere such as nitrogen or argon.
  • a change in characteristics due to oxidation or reduction is induced by treatment with an oxidizing or reducing gas such as oxygen or hydrogen or an oxidizing or reducing liquid. You can also. This is often used for the purpose of increasing or decreasing the carrier density in the film, for example.
  • the characteristics of the semiconductor layer 2 can be changed by adding a trace amount of elements, atomic groups, molecules, and polymers to the semiconductor layer 2 in a technique called doping.
  • the semiconductor layer 2 is doped with an acid such as oxygen, hydrogen, hydrochloric acid, sulfuric acid, or sulfonic acid; a Lewis acid such as PF 5 , AsF 5 , or FeCl 3 ; a halogen atom such as iodine; a metal atom such as sodium or potassium; can do. This can be achieved by bringing these gases into contact with the semiconductor layer 2, immersing them in a solution, or performing an electrochemical doping process.
  • These dopings may be added at the time of synthesizing the organic semiconductor compound even after the semiconductor layer 2 is not manufactured, or may be added to the ink in the process of manufacturing the semiconductor layer 2 using the ink for manufacturing the organic semiconductor element.
  • the thin film (semiconductor layer 2) can be added in a process step or the like. Further, a material used for doping is added to the material for forming the semiconductor layer 2 at the time of vapor deposition, and co-evaporation is performed, or the material is mixed in an ambient atmosphere when the semiconductor layer 2 is manufactured (in an environment where the doping material is present). The semiconductor layer 2 is produced), and further, ions can be accelerated in a vacuum and collide with the film for doping.
  • These doping effects include changes in electrical conductivity due to increase or decrease in carrier density, changes in carrier polarity (P-type and N-type), changes in Fermi level, and the like.
  • the protective layer 7 Forming the protective layer 7 on the semiconductor layer 2 has an advantage that the influence of outside air can be minimized and the electrical characteristics of the organic thin film transistor can be stabilized (see FIG. 2 (6)).
  • the material for the protective layer 7 those described above are used.
  • the protective layer 7 may have any film thickness depending on the purpose, but is usually 100 nm to 1 ⁇ m.
  • the protective layer is made of a resin
  • a method of applying a resin solution and then drying to form a resin film applying a resin monomer or vapor deposition And then polymerizing.
  • Cross-linking treatment may be performed after film formation.
  • the protective layer is made of an inorganic material, for example, a formation method in a vacuum process such as a sputtering method or a vapor deposition method, or a formation method in a solution process such as a sol-gel method can be used.
  • a protective layer can be provided between the layers as necessary. These layers may help stabilize the electrical characteristics of the thin film transistor.
  • the organic polycyclic aromatic compound represented by the above general formula (1) is used as an organic semiconductor material, it can be manufactured in a relatively low temperature process. Therefore, flexible materials such as plastic plates and plastic films that could not be used under conditions exposed to high temperatures can also be used as the substrate. As a result, it is possible to manufacture a light, flexible, and hard-to-break element, which can be used as a switching element for an active matrix of a display.
  • Thin film transistors can be used as digital elements and analog elements such as memory circuit elements, signal driver circuit elements, and signal processing circuit elements. Further, by combining these, it is possible to produce an IC card or an IC tag. Furthermore, since the characteristics of the thin film transistor can be changed by an external stimulus such as a chemical substance, the thin film transistor can be used as an FET sensor.
  • Organic EL elements are attracting attention and can be used for applications such as solid, self-luminous large-area color display and illumination, and many developments have been made.
  • the structure has a structure having two layers of a light emitting layer and a charge transport layer between a counter electrode composed of a cathode and an anode; an electron transport layer, a light emitting layer and a hole transport layer stacked between the counter electrodes.
  • Known are those having a structure having three layers; and those having three or more layers; and those having a single light-emitting layer.
  • the hole transport layer has a function of injecting holes from the anode, transporting holes to the light emitting layer, facilitating the injection of holes into the light emitting layer, and a function of blocking electrons.
  • the electron transport layer has a function of injecting electrons from the cathode, transporting electrons to the light emitting layer, facilitating injection of electrons into the light emitting layer, and blocking holes. Further, in the light emitting layer, excitons are generated by recombination of the injected electrons and holes, and the energy emitted in the process of radiative deactivation of the excitons is detected as light emission.
  • the preferable aspect of an organic EL element is described below.
  • An organic EL element is an element in which an organic thin film having one or more layers is formed between an anode and a cathode, and emits light by electric energy.
  • the anode that can be used in the organic EL element is an electrode having a function of injecting holes into the hole injection layer, the hole transport layer, and the light emitting layer.
  • metal oxides, metals, alloys, conductive materials, and the like having a work function of 4.5 eV or more are suitable.
  • conductive metal oxides such as tin oxide (NESA), indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), gold, silver, platinum, chromium And metals such as aluminum, iron, cobalt, nickel and tungsten, inorganic conductive materials such as copper iodide and copper sulfide, conductive polymers such as polythiophene, polypyrrole and polyaniline, and carbon.
  • ITO or NESA it is preferable to use ITO or NESA.
  • the anode may be made of a plurality of materials or may be composed of two or more layers if necessary.
  • the resistance of the anode is not limited as long as it can supply a current sufficient for light emission of the element, but it is preferably low resistance from the viewpoint of power consumption of the element.
  • an ITO substrate having a sheet resistance value of 300 ⁇ / ⁇ or less functions as an element electrode, but since it is possible to supply a substrate of several ⁇ / ⁇ , it is desirable to use a low-resistance product.
  • the thickness of ITO can be arbitrarily selected according to the resistance value, but is usually 5 to 500 nm, preferably 10 to 300 nm. Examples of film forming methods such as ITO include a vapor deposition method, an electron beam method, a sputtering method, a chemical reaction method, and a coating method.
  • the cathode that can be used in the organic EL element is an electrode having a function of injecting electrons into the electron injection layer, the electron transport layer, and the light emitting layer.
  • a metal or an alloy having a small work function (approximately 4 eV or less) is suitable.
  • Specific examples include platinum, gold, silver, copper, iron, tin, zinc, aluminum, indium, chromium, lithium, sodium, potassium, calcium, and magnesium, but increase the electron injection efficiency to improve device characteristics.
  • lithium, sodium, potassium, calcium and magnesium are preferred.
  • the alloy an alloy with a metal such as aluminum or silver containing these low work function metals, or an electrode having a structure in which these are laminated can be used.
  • An inorganic salt such as lithium fluoride can be used for the electrode having a laminated structure.
  • a transparent electrode that can be formed at a low temperature may be used.
  • the film forming method include a vapor deposition method, an electron beam method, a sputtering method, a chemical reaction method, and a coating method, but are not particularly limited.
  • the resistance of the cathode is not limited as long as it can supply a current sufficient for light emission of the element, but it is preferably low resistance from the viewpoint of power consumption of the element, and preferably about several hundred to several ⁇ / ⁇ .
  • the film thickness is usually 5 to 500 nm, preferably 10 to 300 nm.
  • oxides such as titanium oxide, silicon nitride, silicon oxide, silicon nitride oxide, germanium oxide, nitrides, or mixtures thereof, polyvinyl alcohol, vinyl chloride, hydrocarbon polymers, fluorine
  • a dehydrating agent such as barium oxide, phosphorus pentoxide, or calcium oxide.
  • the transparent substrate include a glass substrate and a polymer substrate.
  • soda lime glass, non-alkali glass, quartz, or the like is used.
  • the glass substrate may have a thickness sufficient to maintain mechanical and thermal strength, and a thickness of 0.5 mm or more is preferable.
  • the material of the glass it is better that there are few ions eluted from the glass, and alkali-free glass is preferred.
  • soda lime glass provided with a barrier coat such as SiO 2 is commercially available, it can also be used.
  • the substrate made of a polymer other than glass include polycarbonate, polypropylene, polyethersulfone, polyethylene terephthalate, and an acrylic substrate.
  • the organic thin film of the organic EL element is formed of one layer or a plurality of layers between the anode and cathode electrodes.
  • the “layer” of one or more layers forming the organic thin film is a hole transport layer, an electron transport layer, a hole transport light-emitting layer, an electron transport light-emitting layer, a hole block layer, an electron block layer, a positive layer.
  • the hole injection layer, the electron injection layer, the light emitting layer, or the following structural example 9 it means a single layer having the functions of these layers.
  • Examples of the configuration of the layer forming the organic thin film in the present invention include the following configuration examples 1) to 9), and any configuration may be used.
  • a single layer formed of a material generally called a bipolar luminescent material; or only one layer including a luminescent material and a hole transport material or an electron transport material may be provided.
  • charges, that is, holes and / or electrons can be efficiently transported and these charges can be recombined.
  • the stability of the element can be prevented from being lowered and the light emission efficiency can be improved.
  • the hole injection layer and the hole transport layer are formed by laminating a hole transport material alone or a mixture of two or more of the materials.
  • hole transport materials N, N′-diphenyl-N, N′-di (3-methylphenyl) -4,4 ′′ -diphenyl-1,1′-diamine, N, N′-dinaphthyl-N , N′-diphenyl-4,4′-diphenyl-1,1′-diamine and the like, bis (N-allylcarbazole) or bis (N-alkylcarbazole) s, pyrazoline derivatives, stilbene compounds,
  • a hydrazone compound a triazole derivative, a heterocyclic compound typified by an oxadiazole derivative or a porphyrin derivative, or a polymer system, a polycarbonate, a styrene derivative, polyvinyl carbazole, polysilane, or the like having the monomer in
  • holes can be injected from the electrodes, and holes can be transported.
  • a phthalocyanine derivative m-MTDATA (4,4 ′, 4 ′′ -tris [phenyl (m-tolyl) ) Amino] triphenylamine
  • PEDOT poly (3,4-ethylenedioxythiophene)
  • polyvinylcarbazole derivatives and the like.
  • the electron transport layer is formed by laminating an electron transport material alone or a mixture of two or more kinds of the materials.
  • an electron transport material it is necessary to efficiently transport electrons from the negative electrode between electrodes to which an electric field is applied.
  • the electron transport material has high electron injection efficiency, and it is preferable to transport the injected electrons efficiently.
  • the substance has a high electron affinity, a high electron mobility, excellent stability, and a substance that does not easily generate trapping impurities during manufacturing and use.
  • quinolinol derivative metal complexes represented by tris (8-quinolinolato) aluminum complexes, tropolone metal complexes, perylene derivatives, perinone derivatives, naphthalimide derivatives, naphthalic acid derivatives, oxazole derivatives, oxadiazoles Derivatives, thiazole derivatives, thiadiazole derivatives, triazole derivatives, bisstyryl derivatives, pyrazine derivatives, phenanthroline derivatives, benzoxazole derivatives, quinoxaline derivatives, and the like are exemplified, but are not particularly limited.
  • These electron transport materials are used alone, but may be laminated or mixed with different electron transport materials. Examples of the electron injection layer provided between the electron transport layer and the cathode for improving the electron injection property include metals such as cesium, lithium, and strontium, lithium fluoride, and the like.
  • the hole blocking layer is formed by laminating and mixing hole blocking substances alone or two or more kinds.
  • the hole blocking substance phenanthroline derivatives such as bathophenanthroline and bathocuproin, silole derivatives, quinolinol derivative metal complexes, oxadiazole derivatives and oxazole derivatives are preferable.
  • the hole blocking substance is not particularly limited as long as it is a compound that can prevent holes from flowing out from the cathode side to the outside of the device and thereby reducing luminous efficiency.
  • the light emitting layer means an organic thin film that emits light, and can be said to be, for example, a hole transporting layer, an electron transporting layer, or a bipolar transporting layer having strong light emitting properties.
  • the light emitting layer only needs to be formed of a light emitting material (host material, dopant material, etc.), which may be a mixture of a host material and a dopant material or a host material alone. Each of the host material and the dopant material may be one kind or a combination of a plurality of materials.
  • the dopant material may be included in the host material as a whole, or may be included partially.
  • the dopant material may be either laminated or dispersed.
  • Examples of the light emitting layer include the above-described hole transport layer and electron transport layer.
  • Materials used for the light-emitting layer include carbazole derivatives, anthracene derivatives, naphthalene derivatives, phenanthrene derivatives, phenylbutadiene derivatives, styryl derivatives, pyrene derivatives, perylene derivatives, quinoline derivatives, tetracene derivatives, perylene derivatives, quinacridone derivatives, coumarin derivatives, Examples include porphyrin derivatives and phosphorescent metal complexes (Ir complex, Pt complex, Eu complex, etc.).
  • the organic thin film formation method of the organic EL element is generally a resistance heating evaporation that is a vacuum process, electron beam evaporation, sputtering, molecular lamination method, casting that is a solution process, spin coating, dip coating, blade coating, wire bar.
  • Uses coating methods such as coating and spray coating, printing methods such as inkjet printing, screen printing, offset printing and letterpress printing, soft lithography methods such as microcontact printing, and a combination of these methods.
  • the thickness of each layer depends on the resistance value and charge mobility of each substance and cannot be limited, but is selected from 0.5 to 5000 nm. The thickness is preferably 1 to 1000 nm, more preferably 5 to 500 nm.
  • one or more thin films such as a light emitting layer, a hole transport layer, and an electron transport layer existing between the anode and the cathode are represented by the above general formula (1).
  • the organic polycyclic aromatic compound By containing the organic polycyclic aromatic compound, an element that efficiently emits light even with low electric energy can be obtained.
  • the organic polycyclic aromatic compound represented by the general formula (1) can be suitably used as a hole transport layer, a light emitting layer, or an electron transport layer.
  • a hole transport layer a hole transport layer
  • a light emitting layer a light emitting layer
  • an electron transport layer a hole transport layer
  • it can be used in combination with the above-described electron transport material, hole transport material, light emitting material, or the like.
  • the dopant material when the organic polycyclic aromatic compound represented by the general formula (1) is used as a host material in combination with the dopant material include perylene derivatives such as bis (diisopropylphenyl) perylenetetracarboxylic imide.
  • Perinone derivatives 4- (dicyanomethylene) -2methyl-6- (p-dimethylaminostyryl) -4H pyran (DCM) and its analogs, metal phthalocyanine derivatives such as magnesium phthalocyanine and aluminum chlorophthalocyanine, rhodamine compounds, deazaflavin derivatives, coumarin derivatives, oxazine compounds, squarylium compounds, violanthrone compound, Nile red, 5- Shianopirometen -BF 4 pyrromethene derivatives complexes, further acetylacetone and benzoyl as phosphorescent material Eu complexes having acetone and phenanthroline as ligands, porphyrins such as Ir complexes, Ru complexes, Pt complexes, Os complexes, ortho metal metal complexes and the like can be used, but are not particularly limited thereto.
  • metal phthalocyanine derivatives such as magnesium phthalocyanine and aluminum chlorophthalo
  • the amount of dopant material used is usually used at 30% by mass or less based on the host material. Preferably it is 20 mass% or less, More preferably, it is 10 mass% or less.
  • a method for doping the host material with the dopant material in the light emitting layer it can be formed by a co-evaporation method with the host material. It is also possible to use it sandwiched between host materials. In this case, you may laminate
  • dopant layers can form each layer alone, or may be used by mixing them.
  • the dopant material may be polyvinyl chloride, polycarbonate, polystyrene, polystyrene sulfonic acid, poly (N-vinylcarbazole), poly (methyl) (meth) acrylate, polybutyl methacrylate, polyester, polysulfone, as a polymer binder.
  • Solvent-soluble resins such as polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polysulfone, polyamide, ethyl cellulose, vinyl acetate, ABS resin (acrylonitrile-butadiene-styrene resin), polyurethane resin, phenol resin, xylene resin, It can also be used by dissolving or dispersing in curable resin such as petroleum resin, urea resin, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, silicone resin. .
  • Organic EL elements can be suitably used as flat panel displays. It can also be used as a flat backlight. In this case, either a light emitting colored light or a light emitting white light can be used.
  • the backlight is mainly used for the purpose of improving the visibility of a display device that does not emit light, and is used for a liquid crystal display device, a clock, an audio device, an automobile panel, a display board, a sign, and the like.
  • liquid crystal display devices, particularly thin backlights for personal computers, which have been a problem for thinning are difficult to thin because they are made of fluorescent lamps and light guide plates. Since the backlight using the element is thin and lightweight, the above problems are solved. Similarly, it can be usefully used for illumination.
  • an organic EL display device having high luminous efficiency and a long lifetime can be obtained. Further, by combining the thin film transistor element of the present invention, it becomes possible to supply an organic EL display device in which the applied voltage on / off phenomenon is electrically controlled with high accuracy at low cost.
  • a flexible and low-cost organic solar cell element can be easily produced using the organic polycyclic aromatic compound represented by the general formula (1). That is, the organic solar cell element is advantageous in terms of flexibility and improved life because it does not use an electrolyte solution unlike the dye-sensitized solar cell.
  • the development of solar cells using organic thin film semiconductors combined with conductive polymers, fullerenes and the like has been mainstream, but power generation conversion efficiency is a problem.
  • an organic solar cell element is similar to a silicon solar cell, in which a layer for generating power (a power generation layer) is sandwiched between an anode and a cathode, and holes and electrons generated by absorbing light are received by each electrode. It functions as a solar cell.
  • the power generation layer is composed of a P-type material, an N-type material, and other materials such as a buffer layer, and an organic material used for the material is called an organic solar cell.
  • Structures include Schottky junctions, heterojunctions, bulk heterojunctions, nanostructure junctions, hybrids, etc. Each material efficiently absorbs incident light and generates charges, and the generated charges (holes and electrons) It functions as a solar cell by separating, transporting and collecting.
  • the anode and cathode in the organic solar cell element are the same as those of the organic EL element described above. Since it is necessary to take in light efficiently, it is desirable to use an electrode having transparency in the absorption wavelength region of the power generation layer. Moreover, in order to have a favorable solar cell characteristic, it is preferable that sheet resistance is 20 ohms / square or less.
  • the power generation layer is formed of at least one or more layers of an organic thin film containing the organic polycyclic aromatic compound represented by the general formula (1).
  • the organic solar cell can take the structure shown above, but basically includes a P-type material, an N-type material, and a buffer layer.
  • a compound capable of transporting holes in the same manner as the hole injection and hole transport layer described in the section of the organic EL element examples include ⁇ -conjugated polymers such as polyaniline derivatives, carbazole and other polymers having a heterocyclic ring in the side chain.
  • pentacene derivatives, rubrene derivatives, porphyrin derivatives, phthalocyanine derivatives, indigo derivatives, quinacridone derivatives, merocyanine derivatives, cyanine derivatives, squalium derivatives, benzoquinone derivatives, and the like can be given.
  • the N-type layer basically has a compound capable of transporting electrons, an oligomer or a polymer having skeleton of pyridine and its derivatives, and a quinoline and its derivatives as the electron transport layer described in the section of the organic EL element.
  • Polymer materials such as oligomers and polymers, polymers having benzophenanthrolines and derivatives thereof, cyanopolyphenylene vinylene derivatives (CN-PPV (cyanopolyphenylene vinylene), etc.), fluorinated phthalocyanine derivatives, perylene derivatives, naphthalene derivatives, bathocuproin derivatives, low molecular materials such as fullerene derivatives such as C 60 and C 70, PCBM (phenyl C 61 butyric acid methyl ester), and the like. Each of them preferably absorbs light efficiently and generates a charge, and the material used has a high extinction coefficient.
  • CN-PPV cyanopolyphenylene vinylene
  • fluorinated phthalocyanine derivatives fluorinated phthalocyanine derivatives
  • perylene derivatives perylene derivatives
  • naphthalene derivatives naphthalene derivatives
  • bathocuproin derivatives low molecular materials
  • the organic polycyclic aromatic compound represented by the general formula (1) can be suitably used particularly as an N-type material.
  • the method for forming the thin film for the power generation layer of the organic solar cell may be the same as the method described in the section of the organic EL element.
  • the thickness of the thin film varies depending on the configuration of the solar cell, it is better to thicken it to absorb light sufficiently and prevent short-circuiting, but it is better to transport the generated charge because the shorter distance is better. Is suitable.
  • the thickness of the power generation layer is preferably about 10 to 5000 nm.
  • the organic polycyclic aromatic compound represented by the general formula (1) is a compound having organic semiconductor characteristics, utilization as an organic semiconductor laser element is expected. That is, a resonator structure can be incorporated into the organic semiconductor element containing the organic polycyclic aromatic compound represented by the general formula (1), and carriers can be efficiently injected to sufficiently increase the density of excited states. For example, it is expected that the light is amplified and causes laser oscillation. Conventionally, only laser oscillation by optical excitation has been observed, and it is very difficult to inject high-density carriers necessary for laser oscillation by electrical excitation into an organic semiconductor element to generate a high-density excitation state. Although proposed, the use of an organic semiconductor element containing the organic polycyclic aromatic compound represented by the general formula (1) is expected to cause highly efficient light emission (electroluminescence).
  • the organic polycyclic aromatic compound represented by the general formula (1) can also be used for an organic light-emitting transistor.
  • a light-emitting transistor that combines an organic transistor and an organic electroluminescent element has a structure in which the drive circuit and light-emitting part of the display are integrated, reducing the area occupied by the drive transistor circuit and increasing the aperture ratio of the display unit. Can do. That is, the number of parts can be reduced and the manufacturing process is simplified, so that a display with lower cost can be obtained.
  • light is emitted by simultaneously injecting electrons and holes from the source and drain electrodes of the organic transistor into the organic light emitting material and recombining them. The adjustment of the light emission amount is controlled by the electric field from the gate electrode.
  • the structure may be the same as that described in the section of the organic transistor, and a light emitting transistor material can be used instead of the structure of the semiconductor layer for the organic transistor.
  • the material and process to be used can be selected as appropriate depending on the characteristics of the semiconductor compound, and a configuration for extracting light to the outside is desirable.
  • ordinary organic transistors only one of electrons or holes need to be injected, but in the case of light-emitting transistors, light is emitted by the combination of electrons and holes in the semiconductor layer.
  • -A structure that promotes bonding and light emission is preferable.
  • the organic polycyclic aromatic compound represented by the general formula (1) can be used as a photoelectric conversion element.
  • An organic photoelectric conversion element is an element in which a photoelectric conversion unit including a photoelectric conversion film is disposed between two opposing electrode films, which are an upper electrode and a lower electrode, and light is incident on the photoelectric conversion unit from above one electrode. It is incident.
  • the photoelectric conversion unit generates electrons and holes according to the amount of incident light, and a signal corresponding to the charge is read out by a semiconductor to indicate the amount of incident light according to the absorption wavelength of the photoelectric conversion film unit. It is an element. In some cases, a transistor for reading is connected to the lower electrode film.
  • the photoelectric conversion element becomes an imaging element.
  • the incidence of light when the photoelectric conversion element including the electrode existing in the rear part is not disturbed by the photoelectric conversion element existing in the front part, even if a plurality of photoelectric conversion elements are stacked. good.
  • the above-described plurality of photoelectric conversion elements absorb different visible lights, a multicolor imaging element is formed, and a full color photodiode is obtained.
  • FIG. 3 shows an example of a photoelectric conversion element. 3, 11 is an insulating portion, 12 is an upper electrode, 13 is an electron blocking layer, 14 is a photoelectric conversion portion, 15 is a hole blocking layer, 16 is a lower electrode, 17 is an insulating base material, or photoelectric. Each conversion element is represented. Although the readout transistor is not shown in the drawing, it may be connected to the lower electrode, and further, it may be formed under the lower electrode if the semiconductor is transparent. The incident light may be incident from any of the upper and lower portions as long as the light other than the photoelectric conversion portion does not extremely disturb the absorption wavelength of the photoelectric conversion portion.
  • the photoelectric conversion part is often composed of a plurality of layers such as 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, It is not limited to this.
  • an organic semiconductor film is used for the photoelectric conversion layer.
  • 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, Alternatively, a mixed film (bulk heterostructure) thereof is used.
  • a mixed film (bulk heterostructure) thereof is used.
  • a plurality of layers it is about 2-10 layers, and is a structure in which either a P-type organic semiconductor film, an N-type organic semiconductor film, or a mixed film thereof (bulk heterostructure) is laminated.
  • a buffer layer may be inserted in
  • triarylamine compounds, benzidine compounds, pyrazoline compounds, styrylamine compounds, hydrazone compounds, triphenylmethane compounds, carbazole compounds, polysilane compounds, thiophene compounds, phthalocyanine compounds, cyanine compounds depending on the wavelength band to be absorbed , Merocyanine compound, oxonol compound, polyamine compound, indole compound, pyrrole compound, pyrazole compound, polyarylene compound, carbazole derivative, naphthalene derivative, anthracene derivative, phenanthrene derivative, phenylbutadiene derivative, styryl derivative, quinoline derivative, tetracene derivative, pyrene derivative , Perylene derivatives, fluoranthene derivatives, quinacridone derivatives, coumarin derivatives, porphyrin derivatives and phosphorescence Metal complex (Ir complexes, Pt complexes, Eu complexes, etc.), or the like can benzolamine
  • the hole transport layer transports the generated holes from the photoelectric conversion layer to the electrode, facilitates movement of holes from the photoelectric conversion layer to the electrode, and functions to block electron transfer from the electrode.
  • the electron transport layer has a function of transporting generated electrons from the photoelectric conversion layer to the electrode, facilitating movement of electrons from the photoelectric conversion layer to the electrode, and a function of blocking movement of holes from the electrode.
  • the hole blocking layer has a function of preventing movement of holes from the electrode to the photoelectric conversion layer, preventing recombination in the photoelectric conversion layer, and reducing dark current.
  • the electron blocking layer has a function of preventing movement of electrons from the electrode to the photoelectric conversion layer, preventing recombination in the photoelectric conversion layer, and reducing dark current.
  • the hole block layer and the electron block layer preferably have high transmittance at the absorption wavelength of the photoelectric conversion layer, or are preferably used as a thin film, in order not to prevent light absorption of the photoelectric conversion film.
  • the generated electrons and holes are transported to the electrodes, and are sent as electrical signals to the readout circuit.
  • the electrode film that can be used in the organic photoelectric conversion element collects holes from a hole transport photoelectric conversion film or a hole transport film contained in the photoelectric conversion layer, or is included in the photoelectric conversion layer
  • adjacent films such as a hole transport photoelectric conversion film and a hole transport film, or an electron transport photoelectric conversion film and an electron transport Since it is selected in consideration of adhesion with an adjacent film such as a film, electron affinity, ionization potential, stability, etc., it is not particularly limited.
  • tin oxide indium oxide
  • indium tin oxide ITO
  • Conductive metal oxides such as zinc oxide indium (IZO)
  • metals such as gold, silver, platinum, chromium, aluminum, iron, cobalt, nickel, tungsten, iodine Copper
  • inorganic conductive materials such as copper sulfide, polythiophene, polypyrrole, and conductive polymers or carbon such as polyaniline. If necessary, a plurality of materials may be used, or two or more layers may be used.
  • the resistance of the electrode is not limited, but is not limited as long as it does not interfere with the light reception of the element more than necessary. From the viewpoint of signal strength of the element and power consumption, the resistance is preferably low.
  • an ITO substrate having a sheet resistance value of 300 ⁇ / ⁇ or less functions as an element electrode, but since it is possible to supply a substrate of several ⁇ / ⁇ , it is desirable to use a low-resistance product.
  • the thickness of ITO can be arbitrarily selected according to the resistance value, but is usually 5 to 500 nm, preferably 10 to 300 nm.
  • film forming methods such as ITO include a vapor deposition method, an electron beam method, a sputtering method, a chemical reaction method, and a coating method. If necessary, UV-ozone treatment, plasma treatment or the like can be performed.
  • the material for the transparent electrode film are 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).
  • the light transmittance of the transparent electrode film is preferably 60% or more, more preferably 80% or more, more preferably 90% or more, at the absorption peak wavelength of the photoelectric conversion film included in the photoelectric conversion part including the transparent electrode film. More preferably, it is 95% or more.
  • the electrodes inside the stacked films need to transmit light having a wavelength other than the light detected by each photoelectric conversion film, and preferably 90%, more preferably, the absorbed light. It is preferable to use a material that transmits 95% or more of light.
  • the electrode film is preferably made plasma-free.
  • plasma free means that no plasma is generated during the formation of the electrode film, 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 the plasma to be reduced decreases.
  • Examples of apparatuses that do not generate plasma during the formation of 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 or an arc plasma deposition method can be considered.
  • the sheet resistance may be preferably 100 to 10,000 ⁇ / ⁇ , and the film thickness can be reduced.
  • the degree of freedom is large.
  • the increase in light transmittance is very preferable because it increases the light absorption in the photoelectric conversion film and increases the photoelectric conversion ability.
  • the hole blocking layer is formed by laminating and mixing hole blocking substances alone or two or more kinds.
  • the hole blocking substance phenanthroline derivatives such as bathophenanthroline and bathocuproin, silole derivatives, quinolinol derivative metal complexes, oxadiazole derivatives, oxazole derivatives, and the like are used.
  • the compound is not particularly limited as long as it is a compound that can prevent flowing out of the element.
  • the organic polycyclic aromatic compound represented by the general formula (1) can be particularly preferably used as a material for the hole blocking layer.
  • the method for forming the hole blocking layer thin film of the organic photoelectric conversion element may be as described below. For the purpose of preventing leakage current, it is better that the film thickness is thin. However, since a sufficient amount of current is required for signal readout at the time of light incidence, the film thickness should be as thin as possible.
  • the power generation layer is preferably about 5 to 500 nm.
  • the organic thin film of the organic photoelectric conversion device is formed by resistance heating vapor deposition which is a vacuum process, electron beam vapor deposition, sputtering, molecular lamination method, casting which is a solution process, spin coating, dip coating, blade coating, wire.
  • Coating methods such as bar coating and spray coating, printing methods such as ink jet printing, screen printing, offset printing and letterpress printing, soft lithography methods such as microcontact printing, and a combination of these methods Can be adopted.
  • the thickness of each layer depends on the resistance value and charge mobility of each substance and cannot be limited, but is selected from 0.5 to 5000 nm. The thickness is preferably 1 to 1000 nm, more preferably 5 to 500 nm.
  • organic thin films constituting the organic photoelectric conversion element one or more thin films such as a photoelectric conversion layer, a hole transport layer, a hole block layer, an electron transport layer, and an electron block layer, which are present between the electrodes, are described above.
  • the organic polycyclic aromatic compound represented by the general formula (1) it is possible to obtain an element that efficiently converts even a weak light energy into an electric signal.
  • Irradiation of incident light was performed using PVL-3300 (Asahi Spectroscopy Co., Ltd.) at an irradiation light wavelength of 550 nm and an irradiation light half width of 20 nm unless otherwise specified.
  • Example 1 Synthesis Example 2,5,8-tris (4-cyanophenyl) benzo [1,2-b: 3,4-b ′: 5,6-b ′′] trithiophene (compound (11)) Under a nitrogen atmosphere, 242 mg (0.50 mmol) of 2,5,8, -tribromobenzo [1,2-b: 3,4-b ′: 5,6-b ′′] trithiophene and dimethylformamide were placed in a flask.
  • Example 2 Synthesis Example 2,5,8-tris (3-cyanophenyl) benzo [1,2-b: 3,4-b ′: 5,6-b ′′] trithiophene (Compound (12)) Under a nitrogen atmosphere, place 2,5,8, -tris (tributylstannyl) benzo [1,2-b: 3,4-b ′: 5,6-b ′′] trithiophene (3.3 mmol) in a flask.
  • Example 4 Production and Evaluation of Photoelectric Conversion Element 2,5,8-Tris (4-cyanophenyl) benzo [1,2 obtained in Example 1 above was applied to ITO transparent conductive glass (Geomatec Corporation, ITO film thickness 150 nm). ⁇ b: 3,4-b ′: 5,6-b ′′] trithiophene was deposited as a hole 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. A 100 nm vacuum film of aluminum was formed thereon as an electrode to produce a photoelectric conversion element.
  • Example 5 Production and Evaluation of Photoelectric Conversion Element 2,5,8-Tris (3-cyanophenyl) benzo [1,2 obtained in Example 2 above was applied to ITO transparent conductive glass (Geomatec Corporation, ITO film thickness 150 nm). ⁇ b: 3,4-b ′: 5,6-b ′′] trithiophene was deposited as a hole 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. A 100 nm vacuum film of aluminum was formed thereon as an electrode to produce a photoelectric conversion element.
  • Example 6 Production and Evaluation of Photoelectric Conversion Element 2,5,8-Tris (2-cyanophenyl) benzo [1,2 obtained in Example 3 above was applied to ITO transparent conductive glass (Geomatec Co., Ltd., ITO film thickness 150 nm).
  • quinacridone was formed into a 100 nm vacuum film as a photoelectric conversion layer.
  • a 100 nm vacuum film of aluminum was formed thereon as an electrode to produce a photoelectric conversion element.
  • Tris (8-quinolinolato) aluminum was formed as a hole blocking layer on ITO transparent conductive glass (manufactured by Geomat Co., Ltd., ITO film thickness 150 nm) to a thickness of 50 nm by resistance heating vacuum deposition.
  • quinacridone was formed into a 100 nm vacuum film as a photoelectric conversion layer.
  • a 100 nm vacuum film of aluminum was formed thereon as an electrode to produce a photoelectric conversion element.
  • ITO and aluminum were used as electrodes and a voltage of 5 V was applied, the current in the dark place was ⁇ 1.06 ⁇ 10 ⁇ 10 A / cm 2 .
  • a voltage of 5 V was applied to the transparent conductive glass side and light irradiation was performed, the current was ⁇ 3.33 ⁇ 10 ⁇ 9 A / cm 2 .
  • the photoelectric conversion elements were evaluated in the above examples and comparative examples, and the obtained dark current-voltage graphs are shown in FIGS.
  • the organic polycyclic aromatic compound obtained by the present invention exhibited semiconductor characteristics and further exhibited good dark current prevention characteristics. It can be said that it is a useful compound having high versatility for electronic devices.
  • the device using the organic polycyclic aromatic compound according to the present invention has a very high leakage current suppressing effect and does not inhibit the on-current at the time of light incidence. It is a power consumption type organic electronics device.
  • the organic polycyclic aromatic compound of the present invention is useful as a material for organic semiconductors.
  • the organic polycyclic aromatic compound of the present invention is effectively used as a material for organic electronic devices. For this reason, this invention has high industrial applicability.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Thin Film Transistor (AREA)
  • Light Receiving Elements (AREA)
  • Electroluminescent Light Sources (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Photovoltaic Devices (AREA)

Abstract

　La présente invention concerne un composé aromatique polycyclique organique représenté par la formule générale (1), le composé étant applicable à des éléments électroluminescents organiques, des éléments de cellule solaire organiques, des éléments de transistor organiques, des transducteurs photoélectriques, et à d'autres dispositifs électroniques organiques. En particulier, un matériau destiné à être appliqué à divers dispositifs électroniques organiques, tels que des transducteurs photoélectriques, est un matériau présentant des propriétés de prévention contre les fuites d'électrons ou les trous, une résistance à la chaleur à la température de traitement, des critères élevés de performance, tels que la transparence à la lumière visible, et d'autres attributs de ce types. La présente invention concerne également un composé imide représenté par la formule générale (1). (Dans la formule, au moins l'un parmi R1 à R6 représente un groupe aryle possédant au moins un groupe cyano).
PCT/JP2015/054827 2014-02-25 2015-02-20 Nouveau composé aromatique polycyclique organique et son utilisation Ceased WO2015129581A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2016505182A JP6436590B2 (ja) 2014-02-25 2015-02-20 新規な有機多環芳香族化合物、およびその利用

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014-034614 2014-02-25
JP2014034614 2014-02-25

Publications (1)

Publication Number Publication Date
WO2015129581A1 true WO2015129581A1 (fr) 2015-09-03

Family

ID=54008901

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/054827 Ceased WO2015129581A1 (fr) 2014-02-25 2015-02-20 Nouveau composé aromatique polycyclique organique et son utilisation

Country Status (2)

Country Link
JP (1) JP6436590B2 (fr)
WO (1) WO2015129581A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017039662A (ja) * 2015-08-20 2017-02-23 日本化薬株式会社 有機多環芳香族化合物、およびその利用
JP2017039661A (ja) * 2015-08-20 2017-02-23 日本化薬株式会社 有機多環芳香族化合物、およびその利用
KR20180068971A (ko) * 2015-10-13 2018-06-22 도레이 카부시키가이샤 2축 배향 폴리프로필렌 필름, 금속막 적층 필름 및 필름 콘덴서
CN108912139A (zh) * 2018-06-15 2018-11-30 南京邮电大学 一种有机太阳能电池电子受体材料及其制备方法与应用
CN110194778A (zh) * 2019-06-11 2019-09-03 南京邮电大学 一种多臂结构有机光伏材料及其制备方法与应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010058833A1 (fr) * 2008-11-21 2010-05-27 国立大学法人広島大学 Nouveau composé hétérocyclique et utilisation de celui-ci
JP2011006388A (ja) * 2009-05-28 2011-01-13 Hiroshima Univ 新規な化合物及びその利用
JP2012231134A (ja) * 2011-04-12 2012-11-22 Fujifilm Corp 有機電界発光素子、有機電界発光素子用材料、膜、発光層、及び有機電界発光素子の作製方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5590552B2 (ja) * 2010-04-13 2014-09-17 国立大学法人広島大学 色素増感型光電変換素子
CN103288848B (zh) * 2013-06-28 2016-02-03 中国科学院宁波材料技术与工程研究所 苯并三噻吩类化合物及其制备方法和用途

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010058833A1 (fr) * 2008-11-21 2010-05-27 国立大学法人広島大学 Nouveau composé hétérocyclique et utilisation de celui-ci
JP2011006388A (ja) * 2009-05-28 2011-01-13 Hiroshima Univ 新規な化合物及びその利用
JP2012231134A (ja) * 2011-04-12 2012-11-22 Fujifilm Corp 有機電界発光素子、有機電界発光素子用材料、膜、発光層、及び有機電界発光素子の作製方法

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017039662A (ja) * 2015-08-20 2017-02-23 日本化薬株式会社 有機多環芳香族化合物、およびその利用
JP2017039661A (ja) * 2015-08-20 2017-02-23 日本化薬株式会社 有機多環芳香族化合物、およびその利用
KR20180068971A (ko) * 2015-10-13 2018-06-22 도레이 카부시키가이샤 2축 배향 폴리프로필렌 필름, 금속막 적층 필름 및 필름 콘덴서
KR102451416B1 (ko) 2015-10-13 2022-10-07 도레이 카부시키가이샤 2축 배향 폴리프로필렌 필름, 금속막 적층 필름 및 필름 콘덴서
CN108912139A (zh) * 2018-06-15 2018-11-30 南京邮电大学 一种有机太阳能电池电子受体材料及其制备方法与应用
CN110194778A (zh) * 2019-06-11 2019-09-03 南京邮电大学 一种多臂结构有机光伏材料及其制备方法与应用

Also Published As

Publication number Publication date
JP6436590B2 (ja) 2018-12-12
JPWO2015129581A1 (ja) 2017-03-30

Similar Documents

Publication Publication Date Title
JP5622585B2 (ja) 新規な複素環式化合物及びその利用
JP6208133B2 (ja) 複素環化合物及びその利用
JP6465350B2 (ja) 新規な有機化合物およびその利用
JP6907187B2 (ja) 有機化合物、近赤外吸収色素、光電変換素子及びその光センサー、撮像素子
TWI774816B (zh) 二苯并吡咯甲川硼螯合化合物、近紅外光吸收材料、薄膜及有機電子裝置
JP6478278B2 (ja) 有機多環芳香族化合物、およびその利用
JP6436590B2 (ja) 新規な有機多環芳香族化合物、およびその利用
WO2012115218A1 (fr) Procédé de fabrication de dianthra[2,3-b:2',3'-f]thiéno[3,2-b]thiophène et son utilisation
WO2013031468A1 (fr) Composé hétérocyclique et son utilisation
JP2021015963A (ja) 光電変換素子用材料及びその用途
JP6592863B2 (ja) 有機化合物及びその用途
JP6572473B2 (ja) 有機化合物及びその用途
JP5600267B2 (ja) 新規な化合物及びその利用
JP2018076241A (ja) 縮合多環化合物及びその利用
WO2012165612A1 (fr) Matériau semi-conducteur organique et dispositif électronique organique
JP6478279B2 (ja) 有機多環芳香族化合物、およびその利用
JP6478277B2 (ja) 有機多環芳香族化合物、およびその利用
JP2017041559A (ja) 光電変換素子、撮像素子、光センサー及び光電変換素子用材料
JP2017132697A (ja) 有機化合物及びその利用
JP7357880B2 (ja) 新規環状化合物およびその用途

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15755784

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2016505182

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15755784

Country of ref document: EP

Kind code of ref document: A1