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WO2013031468A1 - Composé hétérocyclique et son utilisation - Google Patents

Composé hétérocyclique et son utilisation Download PDF

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Publication number
WO2013031468A1
WO2013031468A1 PCT/JP2012/069663 JP2012069663W WO2013031468A1 WO 2013031468 A1 WO2013031468 A1 WO 2013031468A1 JP 2012069663 W JP2012069663 W JP 2012069663W WO 2013031468 A1 WO2013031468 A1 WO 2013031468A1
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organic
layer
thin film
organic semiconductor
substrate
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PCT/JP2012/069663
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English (en)
Japanese (ja)
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和男 瀧宮
安達　千波矢
池田　征明
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国立大学法人九州大学
日本化薬株式会社
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Publication of WO2013031468A1 publication Critical patent/WO2013031468A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • 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
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/484—Insulated gate field-effect transistors [IGFETs] characterised by the channel regions
    • 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
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • 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
    • H10K30/50—Photovoltaic [PV] devices
    • 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 a novel heterocyclic compound and use thereof. More specifically, the present invention relates to a specific heterocyclic organic compound and an organic electronic device using the same.
  • 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 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 to mobile phones from displays to TVs.
  • Research and development have been made on organic solar cell elements and the like as flexible and inexpensive energy sources, and organic transistor elements and the like on flexible displays and inexpensive ICs. In developing these organic electronic devices, it is very important to develop materials constituting the devices.
  • acene-based organic semiconductors such as pentacene are actively studied as organic transistor materials.
  • Heterocyclic heteroacene compounds have been studied mainly with materials containing sulfur and selenium atoms, including benzodithiophene (DPh-BDT), naphthodithiophene (NDT), and benzothienobenzothiophene.
  • Air stable and high performance materials such as (DPh-BTBT, AlkylBTBT) and dinaphthodithiophene (DNTT) materials have been developed (Patent Documents 1-5 and Non-Patent Documents 1-5).
  • DPh-BTBT, AlkylBTBT dinaphthodithiophene
  • DNTT dinaphthodithiophene
  • An object of the present invention is to provide a novel heterocyclic compound that can be used in an organic electronic device. More specifically, an object of the present invention is to provide a heterocyclic 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 organic semiconductor laser elements.
  • the present inventor has developed a novel oxygen-based heterocyclic derivative, further studied its possibility as an organic electronic device, and completed the present invention. That is, the present invention is as follows.
  • a compound represented by the following general formula (1) (In the formula, X represents an oxygen atom, and R represents an unsubstituted aryl group or an aryl group having at least one substituent.)
  • X represents an oxygen atom
  • R represents an unsubstituted aryl group or an aryl group having at least one substituent.
  • R is an unsubstituted aryl group or an aryl group having at least one C1-C3 lower alkyl group as a substituent.
  • the compound according to [2], wherein the aryl group is an aromatic hydrocarbon group.
  • the present invention relates to a novel heterocyclic compound, but since the compound has good semiconductor properties, it is possible to provide an organic electronic device by using this compound, and also to provide a flexible electronic product. It becomes.
  • R in the said compound represents the aryl group which may have a substituent.
  • Aryl groups include aromatic hydrocarbon groups such as phenyl, naphthyl, anthryl, phenanthryl, pyrenyl, benzopyrenyl, pyridyl, pyrazyl, pyrimidyl, quinolyl, isoquinolyl, pyrrolyl, indolenyl.
  • Groups imidazolyl groups, carbazolyl groups, thienyl groups, furyl groups, pyranyl groups, pyridonyl groups and other heterocyclic groups, and condensed heterocyclic groups such as benzoquinolyl groups, anthraquinolyl groups, benzothienyl groups, and benzofuryl groups.
  • a phenyl group, a naphthyl group, a pyridyl group, and a thienyl group are preferable, and a phenyl group is particularly preferable.
  • Examples of the substituent that R in the formula may have are not particularly limited, and examples thereof include an aryl group, a halogen atom, an alkyl group, and a cycloalkyl group.
  • the aryl group may be the same as described above, and the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • alkyl group examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n -Dodecyl group, n-stearyl group and the like.
  • cycloalkyl groups such as cyclic cyclohexyl group, cyclopentyl group, adamantyl group, norbornyl group, are mentioned.
  • a C1-C3 lower alkyl group is preferred.
  • the compound represented by the formula (1) can be obtained, for example, by the following reaction step, starting from 1,5-dibromo-2,6-dihydroxynaphthalene, acylated, and further converted into an acetylene derivative in the presence of a palladium catalyst or the like.
  • a precursor diethynylnaphthalene derivative can be obtained.
  • this precursor is hydrolyzed with cesium carbonate, the target naphthodifuran compound of the general formula (1) is obtained.
  • the method for purifying the heterocyclic compound represented by the general formula (1) is not particularly limited, and known methods such as recrystallization, column chromatography, and vacuum sublimation purification can be employed. Moreover, you may use these methods in combination as needed.
  • heterocyclic compound in which X in the general formula (1) is an oxygen atom are shown below.
  • a thin film can be produced using an organic semiconductor material containing a heterocyclic compound represented by the general formula (1) of the present invention.
  • the thickness of the thin film varies depending on the use, but is usually 0.1 nm to 100 ⁇ m, preferably 0.5 nm to 30 ⁇ m, more preferably 1 nm to 20 ⁇ m.
  • Thin film formation methods generally include vacuum heating such as resistance heating evaporation, electron beam evaporation, sputtering, and molecular lamination, and solution processes such as spin coating, drop casting, dip coating, spraying, and flexo.
  • Printing letterpress printing methods such as resin letterpress printing, offset printing methods, dry offset printing methods, pad printing methods, flat plate printing methods such as lithographic printing methods, intaglio printing methods such as gravure printing methods, silk screen printing methods, photocopier printing methods
  • a stencil printing method such as a lingraph printing method, an ink jet printing method, a microcontact printing method, and the like, and a method in which a plurality of these methods are combined.
  • the resistance heating vapor deposition method that is a vacuum process and the spin coating method, dip coating method, ink jet method, screen printing, letterpress printing, and the like that are solution processes are preferable.
  • An organic electronic device can be produced using the heterocyclic 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 structure Metal-Insulator-Semiconductor MIS structure
  • MOS structure Metal-Insulator-Semiconductor MIS structure
  • MOS structure Metal-Insulator-Semiconductor MIS structure
  • a gate electrode is formed through a Schottky barrier (that is, an MES structure), but in the case of a thin film transistor using an organic semiconductor material, a MIS structure is often used.
  • FIG. 1 shows some examples of thin film transistors (elements).
  • 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.
  • A-D and F are called lateral transistors because current flows in a direction parallel to the substrate.
  • A is called a bottom contact bottom gate structure
  • B is called a top contact bottom gate structure.
  • C has a source and drain electrode and an insulator layer on a semiconductor, and further has a gate electrode formed thereon, which is called a top contact top gate structure.
  • D has a structure called a top & bottom contact type transistor.
  • F is a bottom contact top gate structure.
  • E is a schematic diagram of a transistor having a vertical structure, that is, a static induction transistor (SIT).
  • SIT static induction transistor
  • a large amount of carriers can move at a time because the current flow spreads in a plane.
  • the source electrode and the drain electrode are arranged vertically, the distance between the electrodes can be reduced, so that the response is fast. Therefore, it can be preferably applied to uses such as flowing a large current or performing high-speed switching.
  • FIG. 1E does not show a substrate, but in the normal case, a substrate is provided outside the source or drain electrode represented by 1 and 3 in FIG. 1E.
  • the substrate 6 needs to be able to hold each layer formed thereon without peeling off.
  • an insulating material such as a resin plate, film, paper, glass, quartz, ceramic, etc .; a material in which an insulating layer is formed on a conductive substrate such as a metal or alloy by coating; a material composed of various combinations such as a resin and an inorganic material; Etc.
  • the resin film that can be used include polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, polyamide, polyimide, polycarbonate, cellulose triacetate, polyetherimide, and the like.
  • the element can have flexibility, is flexible and lightweight, and improves practicality.
  • the thickness of the substrate 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.
  • conductive oxides such as InO 2 , ZnO 2 , SnO 2 , ITO
  • conductive polymer compounds such as polyaniline, polypyrrole, polythiophene, polyacetylene, polyparaphenylene, vinylene, polydiacetylene
  • silicon germanium And semiconductors such as gallium arsenide
  • carbon materials such as carbon black, fullerene, carbon nanotubes, and graphite
  • 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. In addition, a conductive composite material in which carbon black, metal particles, or the like is dispersed in the above dopant is also used. For the source electrode 1 and the drain electrode 3 that are in direct contact with the semiconductor, 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 and drain electrodes 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, a short channel effect such as the influence of contact resistance occurs and control becomes difficult, so an appropriate channel length is required.
  • the width between the source and drain electrodes (channel width) is usually 10 to 10,000 ⁇ m, preferably 100 to 5000 ⁇ m. In addition, this channel width can be made longer by making the electrode structure a comb type structure, etc., and it is necessary to make it an appropriate length depending on the required amount of current and the structure of the element. is there.
  • the structure of the source and drain electrodes may be the same or different.
  • the length of the electrode may be the same as the channel width. There is no particular limitation on the width of the electrode, but a shorter one is preferable in order to reduce the area of the element as long as the electrical characteristics can be stabilized.
  • the width of the electrode is usually 0.1 to 1000 ⁇ m, preferably 0.5 to 100 ⁇ m.
  • the thickness of the electrode is usually 0.1 to 1000 nm, preferably 1 to 500 nm, more preferably 5 to 200 nm.
  • a wiring is connected to each of the electrodes 1, 3, and 5, and the wiring is also made of the same material as the electrode.
  • An insulating material is used for the insulator layer 4.
  • polymers such as polyparaxylylene, polyacrylate, polymethyl methacrylate, polystyrene, polyvinylphenol, polyamide, polyimide, polycarbonate, polyester, polyvinyl alcohol, polyvinyl acetate, polyurethane, polysulfone, epoxy resin, phenol resin, and combinations thereof Copolymers;
  • Metal oxides such as silicon dioxide, aluminum oxide, titanium oxide and tantalum oxide; Ferroelectric metal oxides such as SrTiO 3 and BaTiO 3 ; Nitrides such as silicon nitride and aluminum nitride, sulfides, fluorides Dielectrics such as compounds; or polymers in which particles of these dielectrics are dispersed; and the like can be used.
  • 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
  • the semiconductor layer 2 As the material of the semiconductor layer 2, a heterocyclic compound represented by the general formula (1) of the present invention can be used.
  • the semiconductor layer 2 is formed as a thin film using the method described above. For the purpose of improving the characteristics of the thin film transistor and imparting other characteristics, other organic semiconductor materials and various additives may be mixed as necessary.
  • the semiconductor layer 2 may be composed of a plurality of layers.
  • At least one compound of the heterocyclic compound represented by the general formula (1) can be used as the organic semiconductor material.
  • a thin film is formed using the heterocyclic compound represented by the general formula (1) and a composition containing the compound, and the solvent is used for the film formation, it is used after substantially evaporating the solvent. It is preferable to do.
  • an organic semiconductor layer is formed by a vapor deposition method, it is particularly preferable to use a single compound as the organic semiconductor material rather than a mixture of a plurality of heterocyclic compounds represented by the general formula (1).
  • additives such as dopants are not prevented from being contained.
  • the case where the semiconductor layer is formed by a solution process is not limited thereto.
  • the additive is generally 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, where the total amount of the organic semiconductor material is 1. It is good.
  • the thickness of the semiconductor layer 2 is preferably as thin as possible without losing necessary functions. In a horizontal type thin film transistor as shown in A, B and D, if the film thickness exceeds a predetermined value, the characteristics of the element do not depend on the film thickness. On the other hand, as the film thickness increases, the leakage current often increases. It is.
  • the film thickness of the semiconductor layer for exhibiting the 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 between the substrate layer and the insulating film layer, between the insulating film layer and the semiconductor layer, or on the outer surface of the element.
  • a protective layer is formed directly on the organic semiconductor layer 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
  • An inorganic oxide film such as silicon; and a film made of a dielectric material such as a nitride film are preferably used.
  • a resin (polymer) having a low oxygen or moisture permeability and a low water absorption rate is preferable.
  • Gas barrier protective materials developed for organic EL displays can also be used.
  • the film thickness of the protective layer can be selected according to the purpose, but is usually 100 nm to 1 mm.
  • characteristics as a thin film transistor element can be improved.
  • the degree of hydrophilicity / hydrophobicity of the substrate surface the film quality of the film formed thereon can be improved.
  • the characteristics of organic semiconductor materials can vary greatly depending on the state of the film, such as molecular orientation.
  • the surface treatment on the substrate or the like can control the molecular orientation at the interface between the substrate and the organic semiconductor layer to be formed thereafter, and can reduce the trap sites on the substrate and the insulator layer. Therefore, 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.
  • a functional group such as a hydroxyl group present in an untreated substrate.
  • 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 hydrophobization treatment with hexamethyldisilazane, octyltrichlorosilane, octadecyltrichlorosilane, etc .; acid treatment with hydrochloric acid, sulfuric acid, acetic acid, etc .; sodium hydroxide, hydroxide Alkaline treatment with potassium, 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; mechanical Treatment; electrical treatment such as corona discharge; and rubbing treatment using fibers and the like, and combinations thereof.
  • a vacuum deposition method, a sputtering method, a coating method, a printing method, a sol-gel method, or the like can be 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. .
  • 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 those described above can be used. It is also possible to perform the above-described surface treatment or the like on this substrate.
  • the thickness of the substrate 6 is preferably thin as long as necessary functions are not hindered. Although it varies depending on the material, it is usually 1 ⁇ m to 10 mm, preferably 5 ⁇ m to 5 mm. Further, if necessary, the substrate 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 combining photoresist patterning and etching.
  • Patterning can also be performed using a printing method such as ink jet printing, screen printing, offset printing, letterpress printing, soft lithography such as a microcontact printing method, and a combination of these methods.
  • 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, and more preferably 1 nm to 3 ⁇ m. Moreover, when it serves as a gate electrode and a board
  • 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.
  • a predetermined surface treatment can also be performed on the body layer.
  • the surface treatment method the same surface treatment as that of the substrate 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 semiconductor material containing the heterocyclic compound represented by the general formula (1) of the present invention is used for forming an organic semiconductor layer (see FIG. 2 (4)).
  • various methods can be used. 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 heterocyclic compound represented by the general formula (1) of the present invention when using the heterocyclic compound represented by the general formula (1) of the present invention as an organic semiconductor material and forming an organic semiconductor layer, it is formed by a solution process such as printing or a vacuum process, The method of forming an organic-semiconductor layer is mentioned.
  • a method for obtaining an organic semiconductor layer 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 applied to a substrate (substrate, insulator layer, source electrode, drain electrode, etc.).
  • a method of attaching (evaporating), that is, a vacuum evaporation 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 deposition rate is usually 0.001 nm / second to 10 nm / second, preferably 0.01 nm / second to 1 nm / second.
  • the film thickness of the organic semiconductor layer formed from the organic semiconductor material is usually 1 nm to 10 ⁇ m, preferably 5 nm to 5 ⁇ m, more preferably 10 nm to 3 ⁇ m.
  • 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 layer produced by dropping the above ink on a water surface is transferred to a substrate and laminated, and two materials of liquid crystal or a 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 organic semiconductor layer 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 organic semiconductor layer is usually 1 nm to 10 ⁇ m, preferably 5 nm to 5 ⁇ m, more preferably 10 nm to 3 ⁇ m.
  • the characteristics of the organic semiconductor layer thus formed can be further improved by post-processing.
  • heat treatment reduces strain in the film generated during film formation, reduces pinholes, etc., and can control the arrangement and orientation in the film.
  • the semiconductor characteristics can be improved and stabilized.
  • This heat treatment is performed by heating the substrate after forming the organic semiconductor layer.
  • the temperature of the heat treatment is not particularly limited, but is usually from room temperature to about 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 about 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 property change due to oxidation or reduction is induced by treating 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.
  • characteristics of the organic semiconductor layer can be changed by adding a trace amount of elements, atomic groups, molecules, and polymers to the organic semiconductor layer.
  • elements for example, oxygen, hydrogen, hydrochloric acid, sulfuric acid, sulfonic acid and other acids; Lewis acids such as PF 5 , AsF 5 and FeCl 3 ; halogen atoms such as iodine; metal atoms such as sodium and potassium; .
  • This can be achieved by bringing these gases into contact with the organic semiconductor layer, immersing them in a solution, or performing an electrochemical doping treatment.
  • dopings may be added during the synthesis of the organic semiconductor compound, even after the organic semiconductor layer is not prepared, or may be added to the ink in the process of preparing the organic semiconductor layer using the ink for preparing the organic semiconductor element. It can be added in the process step of forming a thin film.
  • a material used for doping is added to the material for forming the organic semiconductor layer at the time of vapor deposition, and co-evaporation is performed, or the organic semiconductor layer is mixed with the surrounding atmosphere when the organic semiconductor layer is formed (in an environment where the doping material is present). An organic semiconductor layer is produced), and further, ions can be accelerated in a vacuum and collide with the film for doping.
  • These doping effects include a change in electrical conductivity due to an increase or decrease in carrier density, a change in carrier polarity (p-type or n-type), a change in Fermi level, and the like.
  • the source electrode 1 and the drain electrode 3 can be formed in accordance with the case of the gate electrode 5 (see FIG. 2 (5)).
  • Various additives can be used to reduce the contact resistance with the organic semiconductor layer.
  • the protective layer 7 When the protective layer 7 is formed on the organic semiconductor layer, there is 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 materials described above are used as the material for the protective layer.
  • the protective layer 7 may have any thickness depending on the purpose, but is usually 100 nm to 1 mm.
  • Various methods can be employed to form the protective layer.
  • the protective layer is made of a resin, for example, a method of applying a resin solution and then drying to form a resin film; applying or vapor-depositing a resin monomer And then a method of polymerizing. Cross-linking treatment may be performed after film formation.
  • the protective layer is made of an inorganic material
  • 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 heterocyclic compound represented by the above general formula (1) is used as the organic semiconductor material, it can be manufactured in a relatively low temperature process. Accordingly, flexible materials such as plastic plates and plastic films that could not be used under conditions exposed to high temperatures can 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 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 that emits light by electric energy, in which one or more organic thin films are formed between electrodes of an anode and a cathode.
  • 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. Lithium, sodium, potassium, calcium, and magnesium are preferable for increasing the electron injection efficiency and improving the device characteristics.
  • As 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
  • the cathode can be protected with a polymer, etc., and sealed with a dehydrating agent such as barium oxide, phosphorus pentoxide, or calcium oxide.
  • 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 transport layer are formed by laminating a hole transport material alone or a mixture of two or more kinds of the materials.
  • the hole transport material include N, N′-diphenyl-N, N′-di (3-methylphenyl) -4,4′-diphenyl-1,1′-diamine, N, N′-dinaphthyl-N, Triphenylamines such as N′-diphenyl-4,4′-diphenyl-1,1′-diamine, bis (N-allylcarbazole), bis (N-alkylcarbazole) s, pyrazoline derivatives, stilbene compounds, hydrazones
  • a polymer compound a triazole derivative, a heterocyclic compound typified by an oxadiazole derivative or a porphyrin derivative, and a polymer system, a polycarbonate, a styrene derivative, polyvinyl carbazole, polysilane, or the
  • the hole injection layer provided between the hole transport layer and the anode for improving the hole injection property includes phthalocyanine derivatives, starburst amines such as m-MTDATA, polythiophene such as PEDOT in the polymer system, polyvinyl Examples thereof include those prepared using carbazole derivatives and the like.
  • the electron transport material As 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 material 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, trobolone 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 derivative porphyrins. Derivatives and phosphorescent metal complexes (Ir complex, Pt complex, Eu complex, etc.) can be mentioned.
  • the organic thin film forming method of the organic EL element is generally a vacuum process, such as resistance heating vapor deposition, electron beam vapor deposition, sputtering, molecular lamination method, solution process casting, 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.
  • 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.
  • the above general formula (1) is applied to one or more thin films such as a light emitting layer, a hole transport layer, and an electron transport layer present between the anode and cathode electrodes.
  • a heterocyclic compound represented by the following an element that emits light efficiently even with low electrical energy can be obtained.
  • the layer containing the heterocyclic compound represented by the general formula (1) can be obtained by forming one layer or a plurality of layers between the anode and the cathode.
  • the layer containing the heterocyclic compound represented by the general formula (1) can be obtained by forming one layer or a plurality of layers between the anode and the cathode.
  • the heterocyclic compound represented by the general formula (1) can be suitably used as a hole transport layer or a light emitting 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 heterocyclic compound represented by the above formula (1) is used as a host material in combination with the dopant material include perylene derivatives such as bis (diisopropylphenyl) perylenetetracarboxylic imide, and perinone derivatives.
  • DCM 4- (dicyanomethylene) -2-methyl-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 compounds, Nile Red, pyromethene derivatives such as 5-cyanopyromethene-BF 4 complex, and acetylacetone and benzoylacetate as phosphorescent materials Eu complexes having lanthanum 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 chloro
  • 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 can be polyvinyl chloride, polycarbonate, polystyrene, polystyrene sulfonic acid, poly (N-vinylcarbazole), poly (methyl) (meth) acrylate, polybutyl methacrylate, polyester, polysulfone as a polymer binder.
  • a curable resin such as a resin, an unsaturated polyester resin, an alkyd resin, an epoxy resin, or a silicone resin.
  • the organic EL element can be suitably used as a flat panel display. 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.
  • a conventional backlight for a liquid crystal display device especially a personal computer application where thinning is an issue, is difficult to thin because it is made of a fluorescent lamp or a light guide plate. Since the used backlight is characterized by thinness and light weight, the above problems are solved.
  • the heterocyclic compound represented by the general formula (1) of the present invention is used, 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 light-emitting transistor that combines an organic transistor and an organic electroluminescent element has a structure in which the drive circuit and the light-emitting part of the display are integrated, which can reduce the area occupied by the drive transistor circuit and increase 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.
  • In ordinary organic transistors only one of electrons or holes need to be injected, but in the case of this light emitting transistor, light is emitted by the combination of electrons and holes in the semiconductor layer, so that effective charge injection from the electrodes is possible.
  • -A structure that promotes bonding and light emission is preferable.
  • an image sensor that is a solid-state imaging element includes a charge coupled device (CCD) having a function of converting a video signal such as a moving image or a still image into a digital signal.
  • CCD charge coupled device
  • the organic solar cell element is advantageous in terms of flexibility and improvement in life because it does not use an electrolyte solution like the dye-sensitized solar cell.
  • a combination of a conductive polymer or fullerene is used. Development of solar cells using organic thin film semiconductors has been the 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 donor material, an N-type acceptor 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 structure of an example of the heterojunction element which is a structure of a general solar cell is shown in FIG.
  • 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 one or more organic thin films containing at least the compound represented by the general formula (1) of the present invention.
  • the organic solar cell element can take the structure shown above, but basically comprises a P-type donor material, an N-type acceptor material, and a buffer layer.
  • P-type donor materials include compounds that can transport holes in the same manner as the hole injection and hole transport layers described in the section of organic EL elements, polyparaphenylene vinylene derivatives, polythiophene derivatives, and polyfluorene derivatives.
  • ⁇ -conjugated polymers such as polyaniline derivatives, carbazole and other polymers having a heterocyclic side chain.
  • low molecular compounds such as a pentacene derivative, a rubrene derivative, a porphyrin derivative, a phthalocyanine derivative, an indigo derivative, a quinacridone derivative, a merocyanine derivative, a cyanine derivative, a squalium derivative, a benzoquinone derivative, are also mentioned.
  • the N-type acceptor layer is basically composed of a compound capable of transporting electrons, such as the electron transport layer described in the section of the organic EL device, an oligomer or polymer having a skeleton of pyridine and its derivatives, a quinoline and a derivative thereof.
  • Examples thereof include low molecular weight materials such as C70 and fullerene derivatives such as PCBM. Each of them preferably absorbs light efficiently and generates a charge, and the material used has a high extinction coefficient.
  • the compound of the general formula (1) of the present invention can be suitably used particularly as a P-type donor 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 above-mentioned 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 in order to absorb light sufficiently and prevent short circuiting. Is suitable.
  • the thickness of the power generation layer is preferably about 10 to 5000 nm.
  • the heterocyclic compound represented by the formula (1) of the present invention is a compound having organic semiconductor characteristics, it is expected to be used as an organic semiconductor laser element. That is, if the resonator structure is incorporated in the organic semiconductor element containing the heterocyclic compound represented by the general formula (1) of the present invention and carriers are efficiently injected, the density of excited states can be sufficiently increased. It is expected that the light will be amplified and cause 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 it has been proposed, the use of an organic semiconductor element containing the heterocyclic compound represented by the formula (1) of the present invention is expected to cause highly efficient light emission (electroluminescence).
  • Example 1 Production of Field Effect Transistor Using Compound (1-1) (DPh-NDF) 200 nm SiO 2 Thermally Oxidized N-Doped Silicon Wafer Treated with Octyltrichlorosilane (Surface Resistance 0.02 ⁇ ⁇ cm or Less) ) was placed in a vacuum vapor deposition apparatus and evacuated until the degree of vacuum in the apparatus was 1.0 ⁇ 10 ⁇ 3 Pa or less.
  • the compound (1-1) was deposited on this electrode at a substrate temperature of about 100 ° C. at a deposition rate of 1 to 2 liters / sec to a thickness of 50 nm by a resistance heating deposition method to form a semiconductor layer (2). .
  • a shadow mask for electrode preparation is attached to this substrate, placed in a vacuum vapor deposition apparatus, evacuated until the degree of vacuum in the apparatus is 1.0 ⁇ 10 ⁇ 4 Pa or less, and a gold electrode is formed by resistance heating vapor deposition. That is, the source electrode (1) and the drain electrode (3) were deposited to a thickness of 40 nm to obtain a TC (top contact) type field effect transistor (channel length 50 ⁇ m, channel width 1.5 mm) of the present invention. .
  • the thermal oxide film in the n-doped silicon wafer with the thermal oxide film has the function of the insulating layer (4), and the n-doped silicon wafer is the substrate (6) and the gate electrode (5).
  • the obtained field effect transistor was installed in a prober, and the semiconductor characteristics were measured using a semiconductor parameter analyzer 4200SCS (manufactured by Keithley). The semiconductor characteristics were such that the drain voltage was ⁇ 60 V, the gate voltage was scanned from 60 V to ⁇ 60 V, and the drain current-gate voltage (transfer) characteristics were measured. From the obtained voltage-current curve, the carrier mobility of this device was 0.63 cm 2 / Vs, the threshold voltage was ⁇ 3 V, and I on / I off was 10 6 .
  • Example 2 Production of Organic Solar Cell Using Compound (1-1) (DPh-NDF) (1)
  • a well-cleaned ITO substrate (15 ⁇ / cm 2 or less) was placed in a vacuum deposition apparatus and evacuated until the degree of vacuum in the apparatus was 1.0 ⁇ 10 ⁇ 3 Pa or less.
  • the compound (1-1) was deposited on this electrode at a thickness of 50 nm at a deposition rate of 1 to 2 cm / sec, and then C60 was deposited at a thickness of 50 nm and BCP was deposited at a thickness of 10 nm, thereby forming an organic semiconductor layer.
  • a shadow mask for electrode preparation is attached to this substrate, and it is placed in a vacuum vapor deposition apparatus, evacuated until the degree of vacuum in the apparatus is 1.0 ⁇ 10 ⁇ 4 Pa or less, and LiF and Al by resistance heating vapor deposition.
  • An electrode was deposited to a thickness of 50 nm to obtain an organic solar cell of the present invention (see FIG. 3).
  • the anode was an ITO substrate
  • the P-type layer was Compound (1-1)
  • the N-type layer was C60
  • the buffer layer was BCP
  • the cathode was LiF and Al electrodes.
  • This organic solar cell element was irradiated with pseudo-sunlight (100 mW / cm 2 ) through an AM 1.5 filter with a solar simulator, and the conversion efficiency was 1.3% (short-circuit current 2.98 mA / cm 2 , open-circuit voltage 0.69 V, A photoelectric conversion characteristic with a fill factor of 0.64) was obtained (see FIG. 6).
  • Example 2 Comparative Example 1 Production of Organic Solar Cell Using DPh-NDT
  • the photoelectric conversion characteristics were obtained in the same manner using DPh-NDT (diphenylnaphthodithiophene) instead of compound (1-1).
  • a conversion efficiency of 1.0% (short-circuit current 3.16 mA / cm 2 , open-circuit voltage 0.52 V, fill factor 0.60) was shown (see FIG. 6).
  • the compound (1-1) was superior.
  • Example 3 Production of Organic Solar Cell Using Compound (1-1) (DPh-NDF) (2)
  • a solar cell element was produced in the same manner as in Example 2 except that C70 was used instead of C60 in Example 2.
  • a photoelectric conversion characteristic with a conversion efficiency of 2.0% (short-circuit current 4.59 mA / cm 2 , open-circuit voltage 0.69 V, fill factor 0.63) was obtained.
  • the heterocyclic compound represented by the general formula (1) of the present invention exhibits excellent characteristics as an organic thin film transistor and an organic solar cell element, and is highly versatile as an organic electronic device. It can be said that it is a very useful compound having properties.

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Abstract

La présente invention concerne un composé de formule générale (1). (Dans la formule, X représente un atome d'oxygène et R un groupe aryle non substitué ou un groupe aryle comportant au moins un groupe substituant.)
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TWI698036B (zh) * 2015-08-04 2020-07-01 日商富士軟片股份有限公司 有機薄膜電晶體、有機薄膜電晶體的製造方法、有機薄膜電晶體用材料、有機薄膜電晶體用組成物、有機半導體膜、化合物
CN109153684A (zh) * 2016-06-03 2019-01-04 E.I.内穆尔杜邦公司 电活性化合物
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WO2023085188A1 (fr) * 2021-11-10 2023-05-19 ソニーセミコンダクタソリューションズ株式会社 Film semi-conducteur organique, élément de conversion photoélectrique et dispositif d'imagerie

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