[go: up one dir, main page]

WO2012165612A1 - Matériau semi-conducteur organique et dispositif électronique organique - Google Patents

Matériau semi-conducteur organique et dispositif électronique organique Download PDF

Info

Publication number
WO2012165612A1
WO2012165612A1 PCT/JP2012/064268 JP2012064268W WO2012165612A1 WO 2012165612 A1 WO2012165612 A1 WO 2012165612A1 JP 2012064268 W JP2012064268 W JP 2012064268W WO 2012165612 A1 WO2012165612 A1 WO 2012165612A1
Authority
WO
WIPO (PCT)
Prior art keywords
organic
organic semiconductor
semiconductor material
compound
layer
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/JP2012/064268
Other languages
English (en)
Japanese (ja)
Inventor
和男 瀧宮
安達　千波矢
勇人 垣添
池田　征明
一樹 新見
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.)
INSTITUTE OF SYSTEMS INFORMATION TECHNOLOGIES AND NANOTECHNOLOGIES
Kyushu University NUC
Nippon Kayaku Co Ltd
Original Assignee
INSTITUTE OF SYSTEMS INFORMATION TECHNOLOGIES AND NANOTECHNOLOGIES
Kyushu University NUC
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 INSTITUTE OF SYSTEMS INFORMATION TECHNOLOGIES AND NANOTECHNOLOGIES, Kyushu University NUC, Nippon Kayaku Co Ltd filed Critical INSTITUTE OF SYSTEMS INFORMATION TECHNOLOGIES AND NANOTECHNOLOGIES
Publication of WO2012165612A1 publication Critical patent/WO2012165612A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/92—Naphthofurans; Hydrogenated naphthofurans
    • 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
    • H10K50/00—Organic light-emitting devices
    • H10K50/30—Organic light-emitting transistors

Definitions

  • the present invention relates to an organic thin film semiconductor material and an organic electronic device. More specifically, the present invention relates to an organic electronic device formed of a specific organic heterocyclic compound, and more particularly to an organic transistor, an organic light emitting transistor, and an organic light emitting element formed of a specific organic heterocyclic compound.
  • Typical devices include organic electroluminescence elements, organic transistor elements, organic solar cell elements, and the like.
  • Organic electroluminescence devices are applied from mobile phone displays to TVs, etc., and developments aiming at further enhancement of functions are being continued.
  • Organic solar cell elements and the like are inexpensive energy sources, and organic transistor elements and the like are actively researched and developed into flexible displays and inexpensive ICs.
  • a field effect transistor generally has a structure in which a semiconductor material on a substrate is provided with a source electrode, a drain electrode, and a gate electrode or the like via these electrodes and an insulator layer.
  • inorganic semiconductor materials centering on silicon are used for field effect transistors, and thin film transistors fabricated on a substrate such as glass using amorphous silicon are widely used for displays and the like.
  • it is necessary to process at a high temperature or a vacuum at the time of manufacturing a field effect transistor and it is not possible to use a film or plastic having poor heat resistance as a substrate to be used.
  • expensive capital investment and production require a lot of energy, resulting in high costs and limited application range.
  • the field effect transistor can be manufactured by a low temperature process, and the range of usable substrate materials is expanded. As a result, it has become possible to fabricate field effect transistors that are more flexible, lighter, and less likely to break.
  • Non-patent Document 3 Patent Document 2
  • Bibenzofuran compounds have been studied for pharmaceuticals, fluorescent dyes, production processes, etc.
  • Patent Document 3 Patent Document 2
  • bibenzothiophene derivatives which are sulfur analogues, have been studied as organic semiconductors.
  • An object of the present invention is to provide a practical organic electronics device, particularly an organic field effect transistor and an organic light emitting transistor, which have high luminous efficiency and charge mobility.
  • the present inventors have used a specific organic heterocyclic compound as a semiconductor material, so that a field effect transistor having a high charge transfer rate, a light-emitting transistor with good light emission efficiency, etc.
  • the inventors have found that an organic electronic device can be obtained, and have completed the present invention.
  • the present invention (1) An organic semiconductor material having a dibenzofuran basic skeleton represented by the following formula (1); However, 6,6′-didecyl-2,2′-binaphtho [2,3-b] furan is excluded. (2) The organic semiconductor material according to (1), wherein the organic semiconductor material is an organic semiconductor material represented by the following general formula (2).
  • R 1 to R 10 each independently represents a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, or a halogen atom.
  • the substituents of R 1 to R 10 are adjacent substituents.
  • organic semiconductor material according to (2) wherein the organic semiconductor material is an organic semiconductor material represented by a formula selected from the group consisting of the following general formulas (3) to (6).
  • each of R 11 ⁇ R 70 independently represent a hydrogen atom, a substituent of the .R 11 ⁇ R 70 representing a an aliphatic hydrocarbon group optionally having substituent or a halogen atom substituents together adjacent And can be linked to each other to form a ring which may have an aliphatic hydrocarbon group or a halogen atom.
  • R 11 to R 70 are all hydrogen atoms.
  • the organic electronic device which is an organic transistor, is provided with a source, drain and gate three electrodes, an insulator layer and an organic semiconductor layer on a substrate, and a current between the source and drain applies a voltage to the gate electrode.
  • (11) A single crystal of an organic semiconductor material represented by a formula selected from the group consisting of the following general formulas (3) to (6).
  • each of R 11 ⁇ R 70 independently represent a hydrogen atom, a substituent of the .R 11 ⁇ R 70 representing a an aliphatic hydrocarbon group optionally having substituent or a halogen atom substituents together adjacent And can be linked to each other to form a ring which may have an aliphatic hydrocarbon group or a halogen atom.
  • a transistor having practical semiconductor characteristics can be manufactured, and an organic electroluminescence element with high emission efficiency can be obtained. Electron mobility and light emission A light-emitting transistor having high efficiency can be obtained.
  • FIG. 1 is a schematic diagram illustrating one embodiment of a field effect transistor.
  • FIG. 2 is a schematic view of a process for manufacturing one embodiment (top contact type) of a field effect transistor.
  • FIG. 3 is a drain current-drain voltage curve of the top contact type organic transistor element obtained in the example.
  • FIG. 4 is a gate voltage-drain current curve of the top contact type organic transistor element obtained in the example.
  • an organic electronic device having excellent characteristics, in particular, an organic transistor, a light-emitting transistor, and an organic electroluminescence element can be obtained.
  • the compound having a skeleton represented by the above formula (1) only needs to have the dibenzofuran skeleton of the formula (1) in the compound of the organic semiconductor material.
  • the compound can be represented by the general formula (2).
  • R 1 to R 10 represent a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, or a halogen atom.
  • the substituents of R 1 to R 10 can form a ring in which adjacent substituents are linked to each other and may have an aliphatic hydrocarbon group or a halogen atom.
  • the aliphatic hydrocarbon group is a saturated or unsaturated linear, branched or cyclic aliphatic hydrocarbon group, preferably a saturated or unsaturated linear or branched aliphatic hydrocarbon group. More preferably, it is a saturated or unsaturated linear aliphatic hydrocarbon group.
  • the carbon number of the aliphatic hydrocarbon group is usually C1-C36, preferably C1-C24, more preferably C1-C20, and most preferably C1-C12. This aliphatic hydrocarbon group may be substituted with a halogen atom.
  • linear or branched saturated aliphatic hydrocarbon group examples include methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, t-butyl, n-pentyl, iso-pentyl, t- Pentyl, sec-pentyl, n-hexyl, iso-hexyl, n-heptyl, sec-heptyl, n-octyl, n-nonyl, sec-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl,
  • linear or branched unsaturated aliphatic hydrocarbon group examples include vinyl, allyl, eicosadienyl, 11,14-eicosadienyl, and geranyl (trans-3,7-dimethyl-2,6-octadien-1-yl).
  • the saturated or unsaturated aliphatic hydrocarbon group includes a saturated alkyl group, an alkenyl group containing a carbon-carbon double bond, and an alkynyl group containing a carbon-carbon triple bond.
  • an alkyl group or an alkynyl group is preferable, and an alkyl group is more preferable.
  • the aliphatic hydrocarbon residue is a combination of these saturated or unsaturated aliphatic hydrocarbon groups, that is, a carbon-carbon double bond, carbon-carbon triple bond at a site in the aliphatic hydrocarbon group. All cases involving bonds at the same time are also included.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, preferably a fluorine atom, a chlorine atom, and a bromine atom, and more preferably a fluorine atom and a bromine atom.
  • a compound having a skeleton represented by the following formula (1) can be obtained by the methods described in Patent Document 3 and Non-Patent Document 4, for example. That is, it can be obtained in a one-step reaction by condensing the corresponding benzofuran derivative (7) in the presence of a base as shown in the following reaction formula.
  • a benzofuran derivative is lithiated in the presence of a base such as n-butyllithium under low temperature conditions, and cuprous chloride or the like is added thereto and reacted to have a skeleton represented by the formula (1).
  • a compound can be obtained.
  • the purification method of the said compound is not specifically limited, Well-known methods, such as recrystallization, column chromatography, and vacuum sublimation purification, are employable. Moreover, you may use combining these methods as needed.
  • a single crystal of a compound having a skeleton represented by the formula (1) can be obtained.
  • a single crystal refers to a crystal whose crystal axis direction does not change in a crystalline solid.
  • As its manufacturing method there are a method of growing from a solution (solution method) and a method of growing from a gas phase (gas phase method).
  • solution method a compound having a skeleton represented by formula (1) is dissolved in a solvent, and the solution is slowly cooled or the solvent is gradually evaporated to generate and grow crystals. At this time, a seed crystal can be added to promote crystal growth.
  • a temperature difference is provided in a heater in a tubular high-temperature furnace, and a compound having a skeleton represented by the formula (1) sublimated in the high-temperature part is transported to the low-temperature part by an inert gas flow such as argon.
  • an inert gas flow such as argon.
  • the organic electronic device of the present invention can contain a heterocyclic compound having a skeleton represented by the above formula (1) as an electronic material for electronics applications.
  • Examples of the organic electronic device include an organic transistor, a light emitting transistor, an organic electroluminescence element, a liquid crystal display element, a photoelectric conversion element, an organic solar cell element, and an organic semiconductor laser element. These will be described in detail.
  • the heterocyclic compound having a skeleton represented by the formula (1) of the present invention As a semiconductor active layer of an organic transistor element, a light-emitting transistor, an organic electroluminescence element, an organic semiconductor laser element or the like, the compound has semiconductor characteristics. It must be the organic semiconductor compound shown.
  • An organic transistor has two electrodes (a source electrode and a drain electrode) in contact with a semiconductor, and controls a current flowing between the electrodes with a voltage applied to another electrode called a gate electrode.
  • a structure in which a gate electrode is insulated by an insulating film is often used for an organic transistor element.
  • An insulating film using a metal oxide film is called a MOS structure.
  • a gate electrode is formed through a Schottky barrier, that is, an MES structure, but in the case of an organic transistor using an organic semiconductor material, an MIS structure is often used.
  • FIG. 1 shows some embodiments of the organic transistor (element) of the present invention.
  • 1 is a source electrode
  • 2 is a semiconductor layer
  • 3 is a drain electrode
  • 4 is an insulator layer
  • 5 is a gate electrode
  • 6 is a substrate.
  • positioning of each layer and an electrode can be suitably selected according to the use of an element.
  • a to D are called lateral transistors because a current flows in a direction parallel to the substrate.
  • A is called a bottom contact structure, and B is called a top contact structure.
  • C is a structure often used for manufacturing an organic single crystal transistor.
  • a source and drain electrodes and an insulator layer are provided on a semiconductor, and a gate electrode is further formed thereon.
  • D has a structure called a top & bottom contact type transistor.
  • 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, SIT can be preferably applied to applications such as flowing a large current and performing high-speed switching.
  • E in FIG. 1 does not describe the substrate, in the normal case, the substrate is provided outside the source and drain electrodes represented by 1 and 3 in FIG. 1E.
  • the substrate 6 needs to be able to be held without peeling off each layer formed thereon.
  • insulating materials such as resin plates and films, paper, glass, quartz, ceramics, etc .; materials in which an insulating layer is formed on a conductive substrate such as metal or alloy by coating; materials consisting of various combinations such as resin and inorganic materials
  • 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, become flexible and lightweight, and improve 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.
  • metals such as platinum, gold, silver, aluminum, chromium, tungsten, tantalum, nickel, cobalt, copper, iron, lead, tin, titanium, indium, palladium, molybdenum, magnesium, calcium, barium, lithium, potassium, sodium, etc.
  • conductive alloys 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; 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. In addition, a conductive composite material in which carbon black, metal particles, or the like is dispersed in the above dopant is also used. 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. However, since a leak current or the like occurs, an appropriate channel length is required.
  • the width (channel width) between the source and drain electrodes 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-shaped structure, etc., and if it is adjusted to an appropriate length depending on the required amount of current and the structure of the element, etc. Good. Each structure (shape) of the source and drain electrodes will be described. The structure of the source and drain electrodes may be the same or different.
  • each electrode When it has a bottom contact structure, it is generally preferable to form each electrode using a lithography method and form it in a rectangular parallelepiped.
  • 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; 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 1 nm to
  • a heterocyclic compound having a skeleton represented by the formula (1) of the present invention or a composition containing the compound can be used as a material of the semiconductor layer 2.
  • the semiconductor layer 2 is formed as a thin film using the method described above. In order to improve the characteristics of the thin film transistor or impart 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 a heterocyclic compound having a skeleton represented by the above formula (1) can be used as an organic semiconductor material.
  • a thin film is formed using a heterocyclic compound having a skeleton represented by the formula (1) or a composition containing the compound, and when a solvent is used as the composition, it is substantially evaporated.
  • a thin film can be formed.
  • an organic semiconductor layer is formed by an evaporation method
  • a single compound may be used as the organic semiconductor material rather than a mixture of a plurality of heterocyclic compounds having a skeleton represented by the above 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 above additives are generally added in the range of 0.01 to 10% by mass, preferably 0.05 to 5% by mass, more preferably 0.1 to 3% by mass, where the total amount of the organic semiconductor material is 1. It is good.
  • a plurality of layers may also be formed for the semiconductor layer, 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 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.
  • the organic transistor for example, other layers can be provided as needed 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. There is also an advantage that 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; a film made of a dielectric such as a nitride film; and the like are preferably used.
  • a resin (polymer) having a low oxygen and moisture permeability and a low water absorption rate is preferable.
  • protective materials developed for organic electroluminescence displays can also be used.
  • the thickness of the protective layer can be selected according to the purpose, but is usually 100 nm to 1 mm.
  • 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, cyclohexene, octyltrichlorosilane, octadecyltrichlorosilane, etc .; acid treatment with hydrochloric acid, sulfuric acid, acetic acid, etc .; sodium hydroxide, Alkaline treatment with potassium hydroxide, calcium hydroxide, ammonia, etc .; ozone treatment; fluorination treatment; plasma treatment with oxygen or argon; Langmuir / Blodgett film formation treatment; other insulator or semiconductor thin film formation treatment; Examples include mechanical treatment; electrical treatment such as corona discharge; or rubbing treatment using fibers or the like.
  • 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 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. 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 be performed on the insulator 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 one type of heterocyclic compound having a skeleton represented by the above formula (1) or a composition containing the compound is used.
  • various methods can be used. Formation method in a vacuum process such as sputtering method, CVD method, molecular beam epitaxial growth method, vacuum deposition method; coating method such as dip coating method, die coater method, roll coater method, bar coater method, spin coating method, ink jet method, It is roughly classified into solution forming methods such as screen printing, offset printing, and microcontact printing.
  • the film is formed by a solution process such as printing or a vacuum process. And a method of forming an organic semiconductor layer.
  • the organic semiconductor layer is formed by growing the single crystal thin film directly on the substrate or by attaching the single crystal thin film prepared by the above method onto the substrate by electrostatic force or the like. can do.
  • a method for obtaining an organic semiconductor layer by forming an organic semiconductor material by a vacuum process will be described.
  • a method in which the organic semiconductor material is heated in a crucible or a metal boat under vacuum to deposit (evaporate) the evaporated organic semiconductor material on the insulator layer 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 at the time of vapor deposition is usually 0 to 200 ° C., preferably 10 to 150 ° C., more preferably 15 to 120 ° C., further preferably 25 to 100 ° C., and particularly preferably 40 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.
  • accelerated ions such as argon are made to collide with the material target and the material atoms are struck out.
  • a sputtering method for attaching to the layer may be used.
  • the heterocyclic compound having a skeleton represented by the formula (1) of the present invention is dissolved in a solvent or the like, and further applied to the insulator layer using a composition to which a binder or the like is added if necessary.
  • 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. The method of soft lithography, etc., or a method combining a plurality of these methods may be employed.
  • 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. It is also possible to adopt a method of sandwiching between substrates or introducing between substrates by capillary action.
  • the environment such as the temperature of the insulator layer and the composition to be applied at the time of film formation is also important, and the characteristics of the transistor may change depending on the temperature of the insulator layer and the composition. Is preferably selected.
  • the insulator layer temperature during vapor deposition is usually 0 to 200 ° C., preferably 10 to 120 ° C., more preferably 15 to 100 ° C. Special care must be taken because it depends greatly on the solvent in the composition to be used.
  • the organic semiconductor layer is formed by growing the single crystal thin film directly on the substrate or by attaching the single crystal thin film prepared by the above method onto the substrate by electrostatic force or the like. can do.
  • the film thickness of the organic semiconductor layer produced by these methods 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.
  • it is effective to perform this heat treatment when manufacturing the thin film transistor of the present invention.
  • the 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 about 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 about 1 minute to 24 hours, preferably about 2 minutes to 3 hours.
  • the atmosphere at that time may be air, but may be an inert atmosphere such as nitrogen or argon.
  • treatment with oxidizing or reducing gases such as oxygen or hydrogen or oxidizing or reducing liquids can induce changes in properties due to oxidation or reduction. it can. 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. An organic semiconductor layer is produced), and further, ions can be accelerated in a vacuum and collide with the film for doping.
  • 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.
  • Such doping is often used particularly in semiconductor elements using inorganic materials such as silicon.
  • 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, 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 in addition to the organic semiconductor layer, 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 having the skeleton represented by the above formula (1) since the heterocyclic compound having the skeleton represented by the above formula (1) is used as the 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.
  • Organic 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 thin film transistor of the present invention can change its characteristics by an external stimulus such as a chemical substance, it can be used as an FET sensor.
  • 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.
  • preferred embodiments of the organic electroluminescence element will be described.
  • An organic electroluminescence element is an element that emits light by electric energy in which an organic thin film having one or more layers is formed between an anode and a cathode.
  • the anode that can be used in the organic electroluminescence 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.
  • 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 electroluminescence 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.
  • 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 included in the organic electroluminescence 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.
  • the above 9) may be a single layer formed of a material generally called a bipolar light-emitting material; or only one layer including a light-emitting material and a hole transport material or an electron transport material.
  • a material generally called a bipolar light-emitting material or only one layer including a light-emitting material and a hole transport material or an electron transport material.
  • 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.
  • hole transport materials 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) or 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, or a polymer system, a polycarbonate, a styrene derivative, polyvinyl carbazole, polysilane or the like having
  • 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 Those prepared with carbazole derivatives and the like can be mentioned.
  • 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 impurities that become traps 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 derivative porphyrins. Derivatives and phosphorescent metal complexes (Ir complex, Pt complex, Eu complex, etc.) can be mentioned.
  • These thin film formation methods are generally vacuum heating processes such as resistance heating vapor deposition, electron beam vapor deposition, sputtering, molecular lamination method, solution processes such as casting, spin coating, dip coating, blade coating, wire bar coating, spraying.
  • a coating method such as coating, a printing method such as ink jet printing, screen printing, offset printing, and relief printing, a soft lithography method such as a microcontact printing method, and a combination of these methods may be employed.
  • 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 a plurality of 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 formula (1).
  • a heterocyclic compound having a skeleton an element that emits light efficiently even with low electrical energy can be obtained.
  • the organic electroluminescence element can be obtained by forming a heterocyclic compound having a skeleton represented by the above formula (1) by forming one or more layers between the anode and the cathode.
  • a heterocyclic compound having a skeleton represented by the above formula (1) by forming one or more layers between the anode and the cathode.
  • the heterocyclic compound having a skeleton represented by the above 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-mentioned electron transport material, hole transport material, light emitting material or the like, or can be used in combination.
  • quinolinol derivative metal complex represented by tris (8-quinolinolato) aluminum complex, tropolone metal complex, perylene derivative, perinone derivative, naphthalimide derivative, naphthalic acid derivative, bisstyryl derivative, pyrazine derivative, phenanthroline derivative, benzoxazole derivative Quinoxaline derivatives, triphenylamines, bis (N-allylcarbazole) or bis (N-alkylcarbazole) s, pyrazoline derivatives, stilbene compounds, hydrazone compounds, heterocyclic compounds represented by oxadiazole derivatives, etc. Although it is mentioned, it is not particularly limited. These can be used alone, but can also be used by laminating or mixing different materials.
  • a perylene derivative such as bis (diisopropylphenyl) perylenetetracarboxylic imide Perinone derivatives, 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 , Deazafurabin derivatives, coumarin derivatives, oxazine compounds, squarylium compounds, violanthrone compound, Nile red, pyrromethene derivatives such as 5-Shianopirometen -BF 4 complex, further acetylacetone and Ben as phosphorescent material Eu complexes having zoylacetone and phenanthroline as
  • 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, polyurethane resin, phenol resin, xylene resin, petroleum resin, urea resin, melamine resin
  • a curable resin such as an unsaturated polyester resin, an alkyd resin, an epoxy resin, or a silicone resin.
  • a method for forming a thin film used for an organic electroluminescence device is generally a vacuum process using a heterocyclic compound or composition having a skeleton represented by the above formula (1), such as resistance heating evaporation, electron beam Deposition, sputtering, molecular lamination, solution process casting, spin coating, dip coating, blade coating, wire bar coating, spray coating and other coating methods, inkjet printing, screen printing, offset printing, letterpress printing, etc.
  • a soft lithography technique such as a microcontact printing method, or a combination of a plurality of these techniques may be employed.
  • Resistance heating vapor deposition, electron beam vapor deposition, sputtering, molecular lamination method, coating method by dissolving and dispersing in solvent or resin (spin coating, casting, dip coating, etc.), LB method, ink jet method, etc. are not particularly limited. .
  • resistance heating vapor deposition is preferable in terms of characteristics.
  • the thickness of each layer is not limited because it is set according to the resistance value of the light-emitting substance, but is selected from 0.5 to 5000 nm. The thickness is preferably 1 to 1000 nm, more preferably 5 to 500 nm.
  • the organic electroluminescence 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. Similarly, it can be usefully used for illumination.
  • a light-emitting transistor that combines an organic transistor and an organic electroluminescent element has a structure in which a drive circuit and a light-emitting portion in a display are integrated, and can occupy a small area of the drive transistor circuit and can increase the aperture ratio of the display unit. it can. 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. It is also expected to be used as an organic photoelectric conversion element by taking advantage of the properties and flexible functionality inherent to organic matter.
  • CCD charge coupled device
  • the organic solar cell element By utilizing the organic semiconductor characteristics of the heterocyclic compound having a skeleton represented by the formula (1) of the present invention, it is expected to be used as an organic solar cell element which is flexible, low cost and easy to manufacture.
  • the organic solar cell element is advantageous in terms of flexibility and longevity because it does not use an electrolyte solution unlike the dye-sensitized solar cell.
  • Development of solar cells using semiconductors is the mainstream, but power conversion efficiency is a problem.
  • a heterocyclic compound having a skeleton represented by formula (1) of the present invention will be a method for solving this problem.
  • the heterocyclic compound having a skeleton represented by the formula (1) of the present invention is a compound having organic semiconductor characteristics and light emitting properties, utilization as an organic semiconductor laser element is expected. That is, a resonator structure is incorporated into an organic semiconductor element containing a heterocyclic compound having a skeleton represented by the formula (1) of the present invention, and carriers are efficiently injected to sufficiently increase the density of excited states. If possible, 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 proposed, it is expected that highly efficient light emission (electroluminescence) occurs by using an organic semiconductor element containing a heterocyclic compound having a skeleton represented by the formula (1) of the present invention.
  • Synthesis example 1 Synthesis of 2-bromo-3-methoxynaphthalene (Compound 102) Under a nitrogen atmosphere, a 1.67M n-BuLi hexane solution (186 ml, 0.31 mol) was added dropwise to 2-methoxynaphthalene (Compound 101, 47 g, 0.3 mol) in THF (350 ml) at ⁇ 78 ° C. . After stirring the mixture for 1.5 hours at room temperature, 1,2-dibromoethane (27.2 ml, 0.32 mol) was added at ⁇ 78 ° C. and stirring was continued for 48 hours at room temperature.
  • Synthesis example 2 Synthesis of 1-iodo-2-hydroxynaphthalene (Compound 108) Under a nitrogen atmosphere, TsOH (36 g, 0.2 mol) and NIS (53 g, 0.2 mol) were added to 2-hydroxynaphthalene (compound 107, 28.8 g, 0.2 mol) in acetonitrile (900 ml). Stir for hours at room temperature. An aqueous sodium hydrogen sulfite solution was added to the resulting mixture, and the mixture was extracted with acetonitrile and washed with brine. The combined organic layers were dried over MgSO 4 and concentrated in vacuo.
  • Synthesis example 3 Synthesis of 6-decyl-1-iodo-2-hydroxynaphthalene (compound 113) Under a nitrogen atmosphere, TsOH (5.4 g, 30 mmol) and NIS (7.8 g, 30 mmol) were added to 6-decyl-2-hydroxynaphthalene (compound 112, 8.5 mg, 30 mmol) in acetonitrile (500 ml). And stirred for 29 hours at room temperature. An aqueous sodium hydrogen sulfite solution was added to the resulting mixture, and the mixture was extracted with acetonitrile and washed with brine. The combined organic layers were dried over MgSO 4 and concentrated in vacuo.
  • Synthesis example 4 Synthesis of 3-bromo-2-methoxyanthracene (compound 119) Under a nitrogen atmosphere, a 1.67M n-BuLi hexane solution (36 ml, 60 mmol) was added dropwise at 0 ° C. to 2-methoxyanthracene (compound 118, 6.3 g, 30 mol) in THF (270 ml). After the mixture was stirred for 1 hour at room temperature, 1,2-dibromoethane (5.6 ml, 65 mol) was added at 0 ° C. and stirring was continued for 12 hours at room temperature.
  • Example 1 (Production of single crystal) The organic single crystal was grown using a two-zone heater (sublimation side Ts, growth side Tg) by vapor phase growth using a pure argon gas flow.
  • a thermal oxide film Si (SiO 2 300 nm) was used.
  • PMMA dissolved in toluene was formed by dip coating, and annealed at 80 ° C. overnight in a nitrogen atmosphere.
  • the substrate was returned to room temperature, and the organic single crystals of Compound 27 and Compound 44 obtained above were attached to the substrate using the electrostatic force of the substrate and the organic single crystal.
  • the source and drain electrodes were formed by vapor deposition through a metal mask from above the organic single crystal.
  • MoO 3 / Au as a source electrode (hole injection electrode) and Ca as a drain electrode (electron injection electrode) were vacuum deposited.
  • the current characteristics of the light-emitting transistor were measured using an Agilent B1500 semiconductor analyzer with a degree of vacuum of 1 ⁇ 10 ⁇ 3 Pa. As for the light emission characteristics, an optical power meter was attached to the upper part of the measurement chamber, and direct light emission was measured. All device characteristics were performed without atmospheric exposure. Absolute fluorescence quantum yield 72 ⁇ 2% in the device of the compound 27, the current characteristics can be confirmed emitting bipolar drive, respectively the mobility of holes and electrons, 0.1 cm 2 / Vs and 0.04 cm 2 / Vs Met. The external quantum efficiency at this time was 0.27%. In the device of Compound 44, the absolute fluorescence quantum yield was 61 ⁇ 2%, and only p-type driving was observed for the current characteristics. The hole mobility at that time was 0.04 cm 2 / Vs.
  • the heterocyclic compound having a skeleton represented by the formula (1) obtained by the present invention exhibits excellent characteristic values as an organic thin film transistor or a light emitting transistor, It can be said that it is a very useful compound having high versatility as a device.
  • Example 2 Preparation of organic transistor element and evaluation thereof 1,1,1,3,3,3-hexamethyldisilazane 200 nm n-doped silicon wafer with SiO 2 thermal oxide film was placed in a vacuum deposition apparatus. The inside was evacuated until the degree of vacuum became 5.0 ⁇ 10 ⁇ 3 Pa or less. The compound 52 was vapor-deposited to a thickness of 50 nm on this electrode under the condition of a substrate temperature of about 25 ° C. by a resistance heating vapor deposition method to form a semiconductor layer (2). Next, a shadow mask for electrode preparation is attached to this substrate, and it is placed in a vacuum vapor deposition apparatus.
  • 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 semiconductor characteristics were measured using a semiconductor parameter analyzer 4155C (manufactured by Agilent). For semiconductor characteristics, the gate voltage was scanned from 0 V to ⁇ 60 V in 10 V steps, the drain voltage was scanned from 0 V to ⁇ 60 V, and the drain current-drain voltage (output characteristics) was measured. As a result, current saturation was observed. The drain current was set to ⁇ 60V, the gate voltage was scanned from 20V to ⁇ 60V, and the gate voltage ⁇ drain current (transfer characteristic) was measured. From the obtained voltage-current curve, the device showed a p-type semiconductor, the carrier mobility was 1 ⁇ 10 ⁇ 2 cm 2 / Vs, and the threshold voltage was ⁇ 8V.
  • Synthesis example 5 Synthesis of 3-methoxythiophene Into a 500 ml three-necked round bottom flask equipped with a thermometer and a Dean-Stark apparatus, 60 ml of methanol was poured under a nitrogen atmosphere, cooled to 0 ° C., sodium (6.9 g, 300 mmol) was gradually added, and a sodium methoxide solution Got. Further, NMP (50 ml) was added and heated to 110 ° C. to distill off methanol.
  • Li-TMP lithium 2,2,6,6-tetramethylpiperidide
  • the reaction mixture was cooled to 0 ° C., 100 ml of ice water was added, extracted with dichloromethane, washed with water and brine, dried over anhydrous magnesium sulfate, and the organic layer was concentrated under reduced pressure.
  • reaction solution was cooled to 0 ° C., 1,2-dibromo-1,1,2,2-tetrachloroethane (244 mg, 0.75 mmol) was added, and the temperature was raised to room temperature, followed by stirring for 6 hours.
  • Water was added to the reaction solution, and the reaction product was extracted with dichloromethane, washed with brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure.
  • Example 3 Fabrication and Evaluation of Organic Transistor Element-2
  • the substrate temperature was set to 150 ° C. instead of 25 ° C.
  • the compound 60 was deposited to a thickness of 50 nm instead of the compound 52.
  • the same semiconductor characteristic measurement was carried out. From the obtained voltage-current curve, this device showed P-type semiconductor characteristics, carrier mobility was 0.89 cm 2 / Vs, and threshold voltage was ⁇ 18V.

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)
  • Electroluminescent Light Sources (AREA)
  • Furan Compounds (AREA)
  • Photovoltaic Devices (AREA)

Abstract

La présente invention a pour but de proposer un dispositif électrique organique pratique exerçant un rendement élevé d'émission lumineuse et une mobilité élevée des charges, des exemples du dispositif électronique organique étant un transistor organique à effet de champ et un transistor organique à émission lumineuse. La présente invention fournit un matériau semi-conducteur organique ayant le squelette de base de dibenzofuranes représentés par la formule (1) (dans laquelle un 6,6'didécyl-2,2'-dinaphto[2,3-b]furane est exclu de celle-ci) et un dispositif électronique organique utilisant ledit matériau semi-conducteur organique.
PCT/JP2012/064268 2011-06-03 2012-06-01 Matériau semi-conducteur organique et dispositif électronique organique Ceased WO2012165612A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011-125127 2011-06-03
JP2011125127 2011-06-03

Publications (1)

Publication Number Publication Date
WO2012165612A1 true WO2012165612A1 (fr) 2012-12-06

Family

ID=47259463

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/064268 Ceased WO2012165612A1 (fr) 2011-06-03 2012-06-01 Matériau semi-conducteur organique et dispositif électronique organique

Country Status (2)

Country Link
JP (1) JPWO2012165612A1 (fr)
WO (1) WO2012165612A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016121791A1 (fr) * 2015-01-29 2016-08-04 国立大学法人東京大学 Élément à semi-conducteur organique
JP2017535083A (ja) * 2014-09-05 2017-11-24 京東方科技集團股▲ふん▼有限公司Ｂｏｅ Ｔｅｃｈｎｏｌｏｇｙ Ｇｒｏｕｐ Ｃｏ．，Ｌｔｄ． 有機発光ダイオード表示装置及びその製造方法
WO2017210072A1 (fr) * 2016-06-03 2017-12-07 E. I. Du Pont De Nemours And Company Composés électroactifs
JP2017537350A (ja) * 2014-11-14 2017-12-14 エ・ティ・チ・エッセ・エッレ・エッレ 改善された画素アーキテクチャを含むディスプレイ

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001335622A (ja) * 2000-03-28 2001-12-04 Sharp Corp 新規化合物ならびにその製造および使用
US20040081853A1 (en) * 2002-10-25 2004-04-29 Eastman Kodak Company Dopant in an electroluminescent device
JP2010018529A (ja) * 2008-07-09 2010-01-28 Sumitomo Chemical Co Ltd ベンゾジフラン化合物及び有機半導体デバイス
JP2010205982A (ja) * 2009-03-04 2010-09-16 Mitsui Chemicals Inc 有機トランジスタ

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001335622A (ja) * 2000-03-28 2001-12-04 Sharp Corp 新規化合物ならびにその製造および使用
US20040081853A1 (en) * 2002-10-25 2004-04-29 Eastman Kodak Company Dopant in an electroluminescent device
JP2010018529A (ja) * 2008-07-09 2010-01-28 Sumitomo Chemical Co Ltd ベンゾジフラン化合物及び有機半導体デバイス
JP2010205982A (ja) * 2009-03-04 2010-09-16 Mitsui Chemicals Inc 有機トランジスタ

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
KAZUKI NIIMI ET AL.: "[2,2']Bi[naphtho[2,3-b] furanyl]: a versatile organic semiconductor with a furan-furan junction", CHEMICAL COMMUNICATIONS, vol. 48, 18 April 2012 (2012-04-18), pages 5892 - 5894 *
NAOTO HAYASHI ET AL.: "Twist Angles and Torsional Potentials of 2,2'-Bibenzothiophene, 2,2'-Biindole, and 2,2'-Bibenzofuran", HETEROCYCLES, vol. 74, 2007, pages 763 - 769 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017535083A (ja) * 2014-09-05 2017-11-24 京東方科技集團股▲ふん▼有限公司Ｂｏｅ Ｔｅｃｈｎｏｌｏｇｙ Ｇｒｏｕｐ Ｃｏ．，Ｌｔｄ． 有機発光ダイオード表示装置及びその製造方法
JP2017537350A (ja) * 2014-11-14 2017-12-14 エ・ティ・チ・エッセ・エッレ・エッレ 改善された画素アーキテクチャを含むディスプレイ
US10615233B2 (en) 2014-11-14 2020-04-07 Flexterra, Inc. Display containing improved pixel architectures
WO2016121791A1 (fr) * 2015-01-29 2016-08-04 国立大学法人東京大学 Élément à semi-conducteur organique
JP2016143675A (ja) * 2015-01-29 2016-08-08 国立大学法人 東京大学 有機半導体素子
WO2017210072A1 (fr) * 2016-06-03 2017-12-07 E. I. Du Pont De Nemours And Company Composés électroactifs
CN109153684A (zh) * 2016-06-03 2019-01-04 E.I.内穆尔杜邦公司 电活性化合物
KR20190006008A (ko) * 2016-06-03 2019-01-16 이 아이 듀폰 디 네모아 앤드 캄파니 전기활성 화합물
JP2019520349A (ja) * 2016-06-03 2019-07-18 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ 電気活性化合物
KR102290838B1 (ko) * 2016-06-03 2021-08-17 주식회사 엘지화학 전기활성 화합물
CN109153684B (zh) * 2016-06-03 2021-12-21 株式会社Lg化学 电活性化合物
US12384796B2 (en) 2016-06-03 2025-08-12 Lg Chem, Ltd. Electroactive compounds

Also Published As

Publication number Publication date
JPWO2012165612A1 (ja) 2015-02-23

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
JP5834014B2 (ja) 含カルコゲン芳香族化合物を含む有機半導体材料及び有機電子デバイス
JPWO2012115218A1 (ja) ジアントラ［２，３−ｂ：２’，３’−ｆ］チエノ［３，２−ｂ］チオフェンの製造方法並びにその用途
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
WO2012165612A1 (fr) Matériau semi-conducteur organique et dispositif électronique organique
WO2013031468A1 (fr) Composé hétérocyclique et son utilisation
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
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
JP7357880B2 (ja) 新規環状化合物およびその用途
JP2017132697A (ja) 有機化合物及びその利用

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: 12792125

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2013518185

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: 12792125

Country of ref document: EP

Kind code of ref document: A1