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WO2010058833A1 - Nouveau composé hétérocyclique et utilisation de celui-ci - Google Patents

Nouveau composé hétérocyclique et utilisation de celui-ci Download PDF

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WO2010058833A1
WO2010058833A1 PCT/JP2009/069688 JP2009069688W WO2010058833A1 WO 2010058833 A1 WO2010058833 A1 WO 2010058833A1 JP 2009069688 W JP2009069688 W JP 2009069688W WO 2010058833 A1 WO2010058833 A1 WO 2010058833A1
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group
formula
heterocyclic compound
organic
atom
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Japanese (ja)
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博一 桑原
池田　征明
和男 瀧宮
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Hiroshima University NUC
Nippon Kayaku Co Ltd
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Hiroshima University NUC
Nippon Kayaku Co Ltd
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Priority to US13/126,771 priority Critical patent/US8313671B2/en
Priority to JP2010539257A priority patent/JP5622585B2/ja
Priority to EP09827614.0A priority patent/EP2361915B1/fr
Priority to CN200980146586.XA priority patent/CN102224158B/zh
Publication of WO2010058833A1 publication Critical patent/WO2010058833A1/fr
Anticipated expiration legal-status Critical
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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 containing the same.
  • organic electronics devices In recent years, interest in organic electronics devices has increased. Its features include that it has a flexible structure and can have a large area, and further enables an inexpensive and high-speed printing method in the electronic device manufacturing process.
  • Typical devices include liquid crystal elements, organic solar cell elements, organic photoelectric conversion elements, organic EL elements, organic transistor elements, and the like. Liquid crystals using liquid crystal elements form a global industry as flat panel displays, and organic EL elements continue to be expected as main targets for next-generation display applications. In particular, organic EL elements are applied from mobile phone displays to TVs and the like, and development aimed at further enhancement of functionality continues.
  • the present invention is to provide a novel heterocyclic compound used for organic electronic devices and its application. More specifically, a novel benzotrithiophene (hereinafter abbreviated as BTT) derivative having liquid crystallinity and semiconductor properties applicable to organic electronic devices such as liquid crystal display elements, organic EL elements, organic solar cell elements, and organic transistor elements. It is to provide.
  • BTT benzotrithiophene
  • the present inventors have developed a novel BTT derivative, further examined its potential as an organic electronic device, and completed the present invention.
  • R 1 to R 6 are each independently an aromatic hydrocarbon group, aliphatic hydrocarbon group, halogen atom, hydroxyl group, alkoxyl group, mercapto group, alkylthio group, boron Represents an acid group, a nitro group, a substituted amino group, an amide group, an acyl group, a carboxyl group, an acyloxy group, a cyano group, a sulfo group, a sulfamoyl group, an alkylsulfamoyl group, a carbamoyl group or an alkylcarbamoyl group, and the remainder is a hydrogen atom
  • X 1 , X 2 and X 3 each independently represent a sulfur atom or a selenium atom
  • R 1 to R 6 in Formula (1-2) and Formula (1) are each independently Aromatic hydrocarbon group, aliphatic hydrocarbon group, halogen atom, hydroxyl group, alkoxyl group, mercapto group, alkylthio group, boronic acid group, nitro group, substituted amino group, amide group, acyl group, carboxyl group, acyloxy group, A cyano group, a sulfo group, a sulfamoyl group, an alkylsulfamoyl group, a carbamoyl group, an alkylcarbamoyl group, or a hydrogen atom, except when all are hydrogen atoms, Z in formula (1-2) is a halogen atom Represents.)
  • a liquid crystalline material comprising the heterocyclic compound according to any one of (1) to (15) or the composition according to (16).
  • the heterocyclic compound according to any one of (1) to (15), the composition according to (16), the organic semiconductor material according to (18), or the liquid crystal property according to (19) An organic electronic device comprising a material.
  • An organic electronic device wherein the device according to (20) is a photoelectric conversion element, an organic solar cell element, an organic EL element, an organic semiconductor laser element, a liquid crystal display element or a thin film transistor element.
  • An organic EL display device comprising the organic EL element according to (22).
  • (25) A liquid crystal display device in which the liquid crystal display element according to (24) is incorporated. , Regarding.
  • the present invention relates to a BTT derivative, since it can exhibit semiconductor characteristics and liquid crystal characteristics, an organic electronic device can be provided, and a flexible electronic product can also be provided.
  • FIG. 7 is a schematic view of a thin film transistor of the present invention obtained in Example 7.
  • FIG. The structure of the organic EL element in Examples 8 and 9 is shown.
  • 10 shows a drain current-drain voltage curve of an organic thin film transistor in Example 7.
  • 10 shows a drain current-gate voltage curve of an organic thin film transistor in Example 7.
  • FIG. 10 shows an IVL characteristic diagram (Tpa-BTT) of an organic EL element in Example 8.
  • FIG. 11 shows an IVL characteristic diagram (Ndpa-BTT) of an organic EL element in Example 9.
  • the present invention is described in detail below.
  • the present invention relates to a BTT derivative which is a specific heterocyclic compound and use thereof.
  • the compound of the above formula (1) will be described.
  • X 1 , X 2 and X 3 each independently represent a sulfur atom or a selenium atom.
  • R 1 to R 6 are each independently an aromatic hydrocarbon group, aliphatic hydrocarbon group, halogen atom, hydroxyl group, alkoxyl group, mercapto group, alkylthio group, boronic acid group, nitro group, substituted amino group, amide group, An acyl group, a carboxyl group, an acyloxy group, a cyano group, a sulfo group, a sulfamoyl group, an alkylsulfamoyl group, a carbamoyl group, an alkylcarbamoyl group, or a hydrogen atom (except when all are hydrogen atoms).
  • X 1 , X 2 and X 3 are each independently a sulfur atom or a selenium atom, preferably a sulfur atom.
  • X 1 , X 2 and X 3 are preferably the same.
  • Examples of the aromatic hydrocarbon group for R 1 to R 6 include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, and a benzopyrenyl group. Among these, a phenyl group, a naphthyl group, and a pyrenyl group are preferable.
  • the aromatic hydrocarbon group can have include, but are not limited to, an aliphatic hydrocarbon group that may have a substituent (for example, a halogen atom, a hydroxyl group, a mercapto group, Carboxylic acid group, sulfonic acid group, nitro group, alkoxyl group, alkyl-substituted amino group, aryl-substituted amino group, unsubstituted amino group, aryl group, acyl group, alkoxycarbonyl group, etc.); Group hydrocarbon groups (eg, alkyl groups, halogen atoms, hydroxyl groups, mercapto groups, carboxylic acid groups, sulfonic acid groups, nitro groups, alkoxyl groups, alkyl-substituted amino groups, aryl-substituted amino groups, unsubstituted amino groups) , Aryl group, acyl group, alkoxycarbonyl group, etc.); cyano
  • an aliphatic hydrocarbon group which may have a substituent an aromatic hydrocarbon group which may have a substituent, a cyano group, a nitro group, an acyl group, a halogen atom, a hydroxyl group, a mercapto group, a substitution Or an unsubstituted amino group, an alkoxyl group, an areneoxy group which may have a substituent, and the like are preferable.
  • Examples of the aromatic hydrocarbon group shown in the above are condensed polycyclic hydrocarbon groups such as pyrenyl group and benzopyrenyl group, pyridyl group, pyrazyl group, pyrimidyl group, quinolyl group, isoquinolyl group, pyrrolyl group, and indenyl group.
  • Heterocyclic hydrocarbon groups such as imidazolyl group, carbazolyl group, thienyl group, furyl group, pyranyl group, pyridonyl group, etc.
  • condensed heterocyclic hydrocarbon groups such as benzoquinolyl group, anthraquinolyl group, benzothienyl group, benzofuryl group, Etc.
  • examples of the aliphatic hydrocarbon group represented by R 1 to R 6 include a saturated or unsaturated linear, branched or cyclic aliphatic hydrocarbon group, and the number of carbon atoms is preferably 1 to 20.
  • examples of the saturated or unsaturated linear or branched aliphatic hydrocarbon group include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, iso-butyl group, allyl group, t -Butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-stearyl group, n-butenyl group and the like.
  • Examples of the cyclic aliphatic hydrocarbon group include cycloalkyl groups having 3 to 12 carbon atoms such as a cyclohexyl group, a cyclopentyl group, an adamantyl group, and a norbornyl group.
  • Examples of the substituent that the aliphatic hydrocarbon group may have are not particularly limited, and examples thereof include a halogen atom, a cyano group, a hydroxyl group, a mercapto group, a nitro group, an alkoxyl group, a carboxylic acid group, and a sulfonic acid group.
  • aromatic hydrocarbon group for example, alkyl group, halogen atom, hydroxyl group, mercapto group Carboxylic acid group, sulfonic acid group, nitro group, alkoxyl group, alkyl-substituted amino group, aryl-substituted amino group, unsubstituted amino group, aryl group, acyl group, alkoxycarbonyl group
  • an aromatic hydrocarbon group which may have a substituent, a cyano group, a nitro group, an acyl group, a halogen atom, a hydroxyl group, a mercapto group, a substituted or unsubstituted amino group, an alkoxyl group and a substituent Preferred areneoxy groups and the like are preferable.
  • the aromatic hydrocarbon groups shown therein are the same as those described above.
  • Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom, a chlorine atom, and a bromine atom are preferable.
  • Examples of the alkoxyl group include an alkoxyl group having 1 to 24 carbon atoms, and an alkoxyl group having 1 to 18 carbon atoms is preferable.
  • Examples of the alkylthio group include an alkylthio group having 1 to 24 carbon atoms, and an alkylthio group having 1 to 18 carbon atoms is preferable.
  • amino group examples include an unsubstituted amino group, a monosubstituted amino group, and a disubstituted amino group.
  • substituent an aromatic hydrocarbon group which may have a substituent (for example, an alkyl group, a halogen atom, a hydroxyl group, a mercapto group, a carboxylic acid group, a sulfonic acid group, a nitro group, an alkoxyl group) Group, an alkyl-substituted amino group, an aryl-substituted amino group, an unsubstituted amino group, an aryl group, an acyl group, an alkoxycarbonyl group, etc.), an aliphatic hydrocarbon group which may have a substituent (for example, a halogen atom as a substituent, Hydroxyl group, mercapto group, carboxylic acid group, sulfonic acid group, nitro group, alkoxyl group, alkyl-substitute
  • Examples of the amide group include an amide group having an aliphatic hydrocarbon group such as acetamide and an amide group having an aromatic hydrocarbon group such as benzamide.
  • Examples of the acyl group include an acyl group having an aliphatic hydrocarbon group such as a formyl group, an acetyl group, and an acyl group having an aromatic hydrocarbon group such as a benzoyl group.
  • the acyl group in the acyloxy group is the same as that described above for the acyl group.
  • Examples of the sulfamoyl group include an unsubstituted sulfamoyl group and a substituted sulfamoyl group.
  • Examples of the carbamoyl group include an unsubstituted carbamoyl group and a substituted carbamoyl group.
  • an aromatic hydrocarbon group which may have a substituent (for example, an alkyl group, a halogen atom, a hydroxyl group, a mercapto group, a carboxylic acid group, a sulfonic acid group, a nitro group, An alkoxyl group, an alkyl-substituted amino group, an aryl-substituted amino group, an unsubstituted amino group, an aryl group, an acyl group, an alkoxycarbonyl group, etc.), an aliphatic hydrocarbon group which may have a substituent (for example, a halogen atom as a substituent) Hydroxyl group, mercapto group, carboxylic acid group, sulfonic acid group, nitro group, alkoxyl group, alkyl-substituted amino group
  • the heterocyclic compound represented by the formula (1) is obtained by first using tetrahydrothiophene using butyllithium as a raw material dibromothiophene at a low temperature of ⁇ 70 ° C. as in the known method disclosed in Non-Patent Document 2.
  • -3-one can then be synthesized by sequentially reacting 2-thienylmagnesium bromide and finally cyclizing and condensing by a photo-oxidation reaction.
  • the BTT derivative thus obtained can be easily tribrominated to give compound (3) as described in Scheme 1 below, and an unsaturated aliphatic compound can be obtained by conducting a Sonogashira reaction using an acetylene derivative.
  • a compound (4) having a hydrocarbon group is obtained, and a compound (5) having a saturated aliphatic hydrocarbon group can be obtained by further performing a reduction reaction.
  • the compound (6) which has an aromatic hydrocarbon group is obtained by performing cross coupling with the boronic acid derivative of an aromatic hydrocarbon (Scheme 2), and the corresponding acetylene derivative from the trichlorotriiodobenzene (7)
  • the Sonogashira reaction is carried out using the compound, and the compound (8) can be easily synthesized.
  • the BTT derivative (9) can be efficiently obtained directly by cyclizing the compound (8).
  • the desired compound (9) can be easily obtained at a low yield and a high yield by reacting a sulfur compound (or selenium compound) in a solvent under heating conditions. This is a technique related to a method for synthesizing a benzochalcogen derivative.
  • X 1 , X 2 and X 3 each independently represent a sulfur atom or selenium atom
  • R 1 to R 6 in formula (1-2) and formula (1) are each independently aromatic Aromatic hydrocarbon group, aliphatic hydrocarbon group, halogen atom, hydroxyl group, alkoxyl group, mercapto group, alkylthio group, boronic acid group, nitro group, amino group, amide group, acyl group, carboxyl group, acyloxy group, cyano group , A sulfo group, a sulfamoyl group, an alkylsulfamoyl group, a carbamoyl group, an alkylcarbamoyl group, or a hydrogen atom. However, the case where all become hydrogen atoms is excluded.
  • Z represents a halogen atom.
  • the description regarding a preferable substituent etc. in said R ⁇ 1 >, R ⁇ 2 > and R ⁇ 3 > follows the description regarding said compound (1)
  • the halogen atom includes a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable.
  • the sulfur compound used in Scheme 4 is usually at least one selected from the group consisting of sulfur, hydrogen sulfide, metal hydrosulfide, and metal sulfide, and may be used alone or in combination.
  • the metal hydrosulfides include water-containing and / or anhydrous alkali metal hydrosulfides. Specific examples include sodium hydrosulfide and potassium hydrosulfide.
  • the metal sulfide include water-containing and / or anhydrous alkali metal sulfide and transition metal sulfide. Specific examples include sodium sulfide, potassium sulfide, iron sulfide, and copper sulfide.
  • Preferable sulfur compounds include sulfur, hydrous and / or anhydrous sodium hydrosulfide, hydrous and / or anhydrous sodium sulfide, and more preferably hydrous sodium hydrosulfide and hydrous sodium sulfide.
  • Examples of the selenium compound used in the scheme 4 include metal selenium, NaSeH, KSeH, and selenium oxide. Metal selenium and NaSeH are preferable, and metal selenium is more preferable.
  • the sulfur compound or selenium compound used in the reaction is usually used in an amount of 3 to 30 mol per 1 mol of the compound (1-2).
  • the amount is preferably 4 to 16 mol, more preferably 5 to 12 mol.
  • Examples of the solvent used in Scheme 4 include amides such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, and N, N-dimethylacetamide; glycols such as ethylene glycol, propylene glycol, and polyethylene glycol Or sulfoxides such as dimethyl sulfoxide are preferable, and N-methyl-2-pyrrolidone, N, N-dimethylformamide, and N, N-dimethylacetamide are preferable, and a solvent having a boiling point of 100 ° C. or higher is particularly preferable. Used for.
  • the above solvent is used in an amount of 0.01 to 100 mol, preferably 0.1 to 80 mol, more preferably 20 to 50 mol, relative to 1 mol of the compound (8).
  • the reaction temperature in the above production method is preferably ⁇ 50 ° C. to 300 ° C. Within this temperature range, the reaction temperature may be changed as necessary.
  • the temperature is preferably -10 ° C to 250 ° C, more preferably 40 ° C to 200 ° C.
  • a catalyst is preferably used.
  • metal catalysts used include copper atom, copper (I) chloride, copper (II) chloride, copper (I) bromide, copper (II) bromide, copper (I) iodide, and copper (II) iodide.
  • Metal halides, particularly copper halides are preferred. More preferably, they are a copper atom, copper (I) bromide, and copper (I) iodide.
  • the amount of the catalyst used is 0.01 to 1 mol, preferably 0.1 to 0.5 mol, more preferably 0.1 to 0.2 mol, per 1 mol of compound (8). .
  • the reaction time is usually from 1 hour to 50 hours, but it is preferable to appropriately adjust the reaction temperature, the halogenating agent, and the amount of the sulfur compound or selenium compound so as to be completed within about 24 hours.
  • a Formyl derivative is obtained by subjecting Compound (2), Compound (5), Compound (6) and Compound (9) to a Wilsmeier reaction, a sulfone derivative is obtained by usual sulfonation,
  • acyl derivatives can be obtained by Friedel-Crafts reaction with nitro derivatives and acyl halides.
  • bromo compound (3) cyano substitution by cyano substitution, amino derivative by Ullmann reaction with amino compound, alkoxyl derivative by reaction with alcohol compound, alkylthio derivative by reaction with thiol compound, boron by Grignard reaction An acid derivative is obtained.
  • the method for purifying the heterocyclic compound represented by the formula (1) represented by the above formula 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.
  • Table 1 below shows specific examples of the heterocyclic compound represented by the above formula (1).
  • the cyclohexyl group is CH
  • the phenyl group is Ph
  • the 4-dodecylphenyl group is DP
  • the 1-naphthyl group is Np
  • the 2-thienyl group is Th.
  • the heterocyclic compound represented by the formula (1) of the present invention can be used as a composition containing a solvent and / or a binder.
  • a solvent any solvent may be used as long as it dissolves or disperses the organic semiconductor material and the polymer compound and becomes a liquid in an appropriate temperature range.
  • the solvent include benzene, toluene, xylene, mesitylene, monochlorobenzene, dichlorobenzene, trichlorobenzene, tetrachlorobenzene, tetrahydrofuran, methylene chloride, chloroform, ether, hexane, cyclohexane, heptane, acetonitrile, acetone, cyclopentanone, Examples include, but are not limited to, cyclohexanone, 2-butanone, 2,4-dimethyl-3-pentanone, ethyl acetate, 1-butanol, fluorobenzene, 1,2-dimethoxyethane, methylnaphthalene, decalin, and tetrahydronaphthalene.
  • the binder a polymer compound and, if necessary, other various low molecular compounds and additives are mixed.
  • the polymer compound is a macromolecule formed by chemical bonding of a very large number of atoms, and a polymer having a repeating structural unit of a monomer is also included in the polymer compound.
  • a polymer having a molecular weight of about 10,000 or more is regarded as a polymer compound, but in a broad sense, a polymer having a low molecular weight called an oligomer is also called a polymer compound.
  • the polymer compound in the present invention includes not only a compound having a high molecular weight but also a polymer having a relatively small molecular weight.
  • the binder of the present invention is preferably a polymer compound that is solid at room temperature and is soluble in a solvent.
  • Specific examples of the polymer compound used in the present invention are roughly classified into an organic synthetic polymer compound, an organic natural polymer compound, and an inorganic polymer compound. Specific examples include the following compounds and derivatives, copolymers, and mixtures thereof, and all of these high molecular compounds described below can be used alone or in combination of two or more.
  • synthetic resin, plastic, polyvinyl polymers chloride, polystyrene-based polymer, polyethylene polymer, a phenolic resin polymer, acrylic resin and the like polymers are preferably a synthetic resin, plastic, polyvinyl polymers chloride, polystyrene-based polymer, polyethylene polymer, a phenolic resin polymer, acrylic resin and the like polymers.
  • organic natural polymers examples include cellulose, starch, and natural rubber. Cellulose and starch are more preferred.
  • examples of the inorganic polymer compound include silicone resin and silicone rubber.
  • These polymer compounds are roughly classified into conductive polymer compounds, semiconducting polymer compounds, and insulating polymer compounds when classified from the viewpoint of electrical characteristics.
  • the conductive polymer compound is a polymer compound characterized by having a ⁇ electron skeleton developed in the molecule and exhibiting electrical conductivity.
  • Specific examples of the conductive polymer compound include polyacetylene polymer, polydiacetylene polymer, polyparaphenylene polymer, polyaniline polymer, polythiophene polymer, polypyrrole polymer, polyparaphenylene vinylene polymer.
  • Polyethylene dioxythiophene polymer, polyethylene dioxythiophene / polystyrene sulfonic acid mixture generally name, PEDOT-PSS
  • nucleic acids and derivatives thereof many of which have improved conductivity by doping.
  • polyacetylene polymers polyparaphenylene polymers, polyaniline polymers, polythiophene polymers, polypyrrole polymers, polyparaphenylene vinylene polymers, and the like are more preferable.
  • the semiconducting polymer compound is a polymer compound characterized by exhibiting semiconductivity.
  • Specific examples of semiconducting polymer compounds include polyacetylene polymers, polydiacetylene polymers, polyparaphenylene polymers, polyaniline polymers, polythiophene polymers, polypyrrole polymers, polyparaphenylene vinylene polymers. , Polyethylenedioxythiophene polymers, nucleic acids and derivatives thereof. Specific examples thereof include polyacetylene polymers, polyaniline polymers, polythiophene polymers, polypyrrole polymers, polyparaphenylene vinylene polymers, and the like.
  • the semiconducting polymer compound exhibits conductivity by doping, and may have conductivity depending on the doping amount.
  • the insulating polymer compound is a polymer compound characterized by exhibiting insulating properties, and most of the polymer compound other than the conductive or semiconducting polymer compound is an insulating polymer compound.
  • Specific examples include acrylic polymers, polyethylene polymers, polymethacrylate polymers, polystyrene polymers, polyethylene terephthalate polymers, nylon polymers, polyamide polymers, polyester polymers, vinylon polymers. Molecules, polyisoprene polymers, cellulose polymers, copolymer polymers, and derivatives thereof are more preferable.
  • composition of the present invention As long as the effects obtained with the composition of the present invention are not impaired, other additives as appropriate, for example, carrier generating agents, conductive substances, viscosity modifiers, surface tension modifiers, leveling agents, penetrating agents, wetting preparation agents, A rheology modifier or the like may be added.
  • carrier generating agents for example, carrier generating agents, conductive substances, viscosity modifiers, surface tension modifiers, leveling agents, penetrating agents, wetting preparation agents, A rheology modifier or the like may be added.
  • the content of the compound (1) in the composition of the present invention is usually in the range of 0.01% to 95%, preferably 0.05% to 50%, more preferably 0.1% to 20%.
  • the “%” is based on weight, and the same applies hereinafter unless otherwise specified.
  • the content of the solvent in the composition of the present invention is usually in the range of 5% to 99.99%, preferably 50% to 99.95%, more preferably 80% to 99.9%.
  • the binder in the composition of the present invention may be used, but may not be used.
  • the content when used is usually in the range of 1% to 500%, preferably 5% to 300%, based on the heterocyclic compound represented by the above formula (1).
  • composition of the present invention may be used, but may not be used.
  • the content when used is usually in the range of 0.1% to 100%, preferably 0.2% to 50%, more preferably 0.5% to 30% with respect to the compound (1).
  • the heterocyclic compound represented by the above formula (1) and the binder are dissolved or dispersed in a solvent so as to have the content, and heat treatment and stirring are performed according to the respective solubility.
  • the method for preparing the composition is not limited to this.
  • a binder and other additives may or may not be used. When the other additives are added, they may be added as appropriate so as not to leave undissolved components, or undissolved components may be removed by a treatment such as filtration.
  • the thin film of the present invention is a thin film formed from the heterocyclic compound represented by the formula (1) of the present invention or a composition thereof.
  • the thickness of the thin film varies depending on the application, but is usually from 0.1 nm to 100 ⁇ m, preferably from 0.5 nm to 30 ⁇ m, more preferably from 1 nm to 20 ⁇ m.
  • the thin film forming method of the present invention generally includes resistance heating evaporation, which is a vacuum process, electron beam evaporation, sputtering, molecular lamination, etc., and spin coating, drop casting, dip coating, and spraying, which are solution processes.
  • Letterpress printing methods such as printing, flexographic printing, resin letterpress printing, offset printing methods, dry offset printing methods, pad printing methods, lithographic printing methods such as lithographic printing methods, intaglio printing methods such as gravure printing methods, silk screen printing methods, Examples thereof include a stencil printing method such as a stencil printing method and a lithographic printing method, an ink jet printing method, a microcontact printing method, and a method in which a plurality of these methods are combined.
  • a resistance heating vapor deposition method that is a vacuum process
  • a spin coating method that is a solution process
  • a dip coating method an ink jet method, screen printing, letterpress printing, and the like are preferable.
  • the organic electronic device of the present invention contains a heterocyclic compound represented by the above formula (1) as an electronic material for electronics use.
  • Examples of the organic electronic device include a thin film transistor, an organic EL 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.
  • heterocyclic compound represented by the formula (1) of the present invention As a semiconductor active layer of a thin film transistor element, an organic EL element, an organic semiconductor laser element or the like, it is necessary to be an organic semiconductor compound exhibiting semiconductor characteristics.
  • 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.
  • a thin film transistor element often has a structure in which a gate electrode is insulated by an insulating film (Metal-Insulator-Semiconductor: MIS structure).
  • An insulating film using a metal oxide film is called a MOS structure.
  • MOS structure Metal-Insulator-Semiconductor
  • a gate electrode is formed through a Schottky barrier, that is, a 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 embodiments of the thin film transistor (element) of the present invention.
  • 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 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, 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 and drain electrodes 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.
  • 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 between the source and drain electrodes (channel length) 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 is generated, 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. Further, this channel width can be made longer by forming the electrode structure into a comb structure, etc., and may be set to an appropriate length depending on the required amount of current and the structure of the element. .
  • 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 within a range where 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 10
  • a heterocyclic compound represented by the formula (1) of the present invention or a composition thereof is used as the material of the semiconductor layer 2.
  • the semiconductor layer 2 is formed as a thin film.
  • 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 above formula (1) is used as the organic semiconductor material.
  • an organic-semiconductor layer with a vapor deposition method it is especially preferable to use a single compound as an organic-semiconductor material rather than the mixture of the several heterocyclic compound represented by the said 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 usually added in the range of 0.01 to 10% by weight, preferably 0.05 to 5% by weight, more preferably 0.1 to 3% by weight, 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.
  • 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, the leakage current often increases as the film thickness increases. It is.
  • the film thickness of the semiconductor layer for exhibiting necessary functions is usually 1 nm to 10 ⁇ m, preferably 5 nm to 5 ⁇ m, more preferably 10 nm to 3 ⁇ m.
  • the thin film transistor of the present invention for example, 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 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 EL 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.
  • 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, 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; Mechanical treatment; electrical treatment such as corona discharge; and rubbing treatment using fibers and 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. 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.
  • 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 method of forming an oxide film on a metal such as a sol-gel method, alumite on aluminum, or silicon dioxide on silicon is 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 from 0.1 nm to 100 ⁇ m, preferably from 0.5 nm to 50 ⁇ m, more preferably from 5 nm to 10 ⁇ m.
  • 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 (4)).
  • Various additives can be used to reduce the contact resistance with the organic semiconductor layer.
  • the organic semiconductor material one type of heterocyclic compound represented by the above formula (1) or a composition thereof is used.
  • various methods can be used. Formation method in 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 organic semiconductor layer is formed by a solution process such as printing or a vacuum process.
  • a solution process such as printing or a vacuum process. The method of forming a 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.
  • a vapor deposition method is preferably employed.
  • the degree of vacuum is usually 1.0 ⁇ 10 ⁇ 1 Pa or less, preferably 1.0 ⁇ 10 ⁇ 3 Pa or less.
  • the characteristics of the organic semiconductor film and thus the thin film transistor may change depending on the substrate temperature during vapor deposition, it is preferable to select the substrate temperature carefully.
  • 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 collide with the material target to knock out the material atoms and adhere to the substrate.
  • a sputtering method may be used.
  • 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 can 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 substrate and the composition during 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 temperatures of the substrate and the composition.
  • the substrate 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 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 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.
  • 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 in an ambient 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.
  • 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 protective layer 7 When the protective layer 7 is formed on the organic semiconductor layer, there are advantages 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 used to form the protective layer.
  • the protective layer is made of a resin, for example, a method in which a resin solution is applied and then dried to form a resin film; a resin monomer is applied or evaporated 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 can be provided between the layers in addition to the organic semiconductor layer as necessary. These layers may help stabilize the electrical characteristics of the thin film transistor.
  • the heterocyclic compound represented by the above formula (1) since the heterocyclic compound represented by the above 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.
  • the thin film transistor of the present invention can be used as a digital element or an analog element such as a memory circuit element, a signal driver circuit element, or a signal processing circuit element. 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.
  • Organic EL elements have attracted 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 consists of a structure having two layers, 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 laminated 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 EL device of the present invention will be described.
  • the organic EL device of the present invention is a device that emits light by electric energy, in which a single-layer or multiple-layer organic thin film is formed between an anode and a cathode.
  • the anode that can be used in the organic EL device of the present invention is an electrode having a function of injecting holes into a hole injection layer, a hole transport layer, and a light emitting layer.
  • a metal oxide, metal, alloy, conductive material, or the like having a work function of 4.5 eV or more is 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.
  • the thickness of ITO can be arbitrarily selected according to the resistance value, but it is usually 5 to 500 nm, preferably 10 to 300 nm.
  • film forming methods such as ITO include a vapor deposition method, an electron beam method, a sputtering method, a chemical reaction method, and a coating method.
  • the cathode that can be used in the organic EL device of the present invention is an electrode having a function of injecting electrons into an electron injection layer, an electron transport layer, and a 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 device, but it is preferably low resistance from the viewpoint of power consumption of the device, 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, and germanium oxide, nitride, or a mixture thereof, polyvinyl alcohol, vinyl chloride, hydrocarbon polymer, 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.
  • 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 EL element of the present invention is formed of one or more layers between the anode and cathode electrodes.
  • the “layer” of one or more layers forming the organic thin film in the present invention 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
  • a hole transport layer As shown in the 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.
  • 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) 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 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 trapping impurities during manufacturing and use.
  • quinolinol derivative metal complexes represented by tris (8-quinolinolato) aluminum complexes, tropolone metal complexes, perylene derivatives, perinone derivatives, naphthalimide derivatives, naphthalic acid derivatives, oxazole derivatives, oxadiazoles Derivatives, thiazole derivatives, thiadiazole derivatives, triazole derivatives, bisstyryl derivatives, pyrazine derivatives, phenanthroline derivatives, benzoxazole derivatives, quinoxaline derivatives, and the like are exemplified, but are not particularly limited.
  • These electron transport materials are used alone, but may be laminated or mixed with different electron transport materials. Examples of the electron injection layer provided between the electron transport layer and the cathode for improving the electron injection property include metals such as cesium, lithium, and strontium, lithium fluoride, and the like.
  • the hole blocking layer is formed by laminating and mixing hole blocking substances alone or two or more kinds.
  • the hole blocking substance phenanthroline derivatives such as bathophenanthroline and bathocuproin, silole derivatives, quinolinol derivative metal complexes, oxadiazole derivatives and oxazole derivatives are preferable.
  • the hole blocking substance is not particularly limited as long as it is a compound that can prevent holes from flowing out from the cathode side to the outside of the device and thereby reducing luminous efficiency.
  • the light emitting layer means an organic thin film that emits light, and can be said to be, for example, a hole transporting layer, an electron transporting layer, or a bipolar transporting layer having strong light emitting properties.
  • the light emitting layer only needs to be formed of a light emitting material (host material, dopant material, etc.), which may be a mixture of a host material and a dopant material or a host material alone. Each of the host material and the dopant material may be one kind or a combination of a plurality of materials.
  • the dopant material may be included in the host material as a whole, or may be included partially.
  • the dopant material may be either laminated or dispersed.
  • Examples of the light emitting layer include the above-described hole transport layer and electron transport layer.
  • Materials used for the light-emitting layer include carbazole derivatives, anthracene derivatives, naphthalene derivatives, phenanthrene derivatives, phenylbutadiene derivatives, styryl derivatives, pyrene derivatives, perylene derivatives, quinoline derivatives, tetracene derivatives, perylene derivatives, quinacridone derivatives, coumarin 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 more thin films such as a light emitting layer, a hole transport layer, and an electron transport layer existing between the anode and the cathode are represented by the above formula (1).
  • a light emitting layer 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).
  • the heterocyclic compound represented an element that emits light efficiently even with low electrical energy can be obtained.
  • the organic EL device of the present invention can be obtained by forming one or more layers of the heterocyclic compound represented by the above formula (1) between the anode and cathode electrodes.
  • the heterocyclic compound represented by said Formula (1) can be used suitably as a host material combined with the utilization in a positive hole transport layer or a light emitting layer, and a dopant material.
  • the heterocyclic compound 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-described electron transport material, hole transport material, light emitting material, or the like.
  • 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.
  • the dopant material when the heterocyclic compound represented by the above formula (1) is used as a host material combined with the dopant material include perylene derivatives such as bis (diisopropylphenyl) perylenetetracarboxylic imide, and perinone derivatives.
  • 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 It is also possible to use it by dissolving or dispersing it in a curable resin such as an unsaturated polyester resin, an alkyd resin, an epoxy resin, or a silicone resin.
  • a curable resin such as an unsaturated polyester resin, an alkyd resin, an epoxy resin, or a silicone resin.
  • the method of forming a thin film used in the organic EL device according to the present invention is generally a vacuum process using the heterocyclic compound or composition represented by the above formula (1), such as resistance heating evaporation, electron beam evaporation. , Sputtering, molecular lamination method, 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 and other printing methods, A soft lithography technique such as a micro contact printing method, or a combination of a plurality of these techniques may be employed.
  • a soft lithography technique such as a micro contact 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 EL element of the present invention 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.
  • 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.
  • the liquid crystal display element of the present invention When the heterocyclic compound represented by the formula (1) of the present invention is used for a liquid crystal display element or the like, it is important to have liquid crystallinity. On the other hand, by utilizing this liquid crystallinity, it is possible to improve the semiconductor characteristics of the organic electronic device by controlling the orientation of the compound.
  • the liquid crystal display element includes a light anisotropic thin film such as a polarizing element and an optical compensation sheet in addition to the liquid crystal cell. It is considered that the derivative of the heterocyclic compound represented by the formula (1) of the present invention is suitable for use as a discotic liquid crystal compound as a constituent component of a discotic liquid crystal phase.
  • This discotic liquid crystal is attracting attention because it is applied to optical compensation sheets.
  • This optical compensation sheet is also called a phase difference plate, and by using the phase difference plate, it is possible to provide a liquid crystal display device with a small change in color of a display image and an enlarged viewing angle.
  • the heterocyclic compound represented by the formula (1) of the present invention has a liquid crystal phase, particularly a discotic liquid crystal phase. These may be used alone, or may be used as a mixture or may be used as a mixture with a compound other than the present invention. For example, it may be a liquid crystalline derivative or non-liquid crystalline, and is not particularly limited.
  • a vacuum process deposition method or a solution process such as casting, spin coating, dip coating, blade coating, wire bar coating, Manufactured using coating methods such as spray coating, printing methods such as inkjet printing, screen printing, offset printing and letterpress printing, soft lithography methods such as microcontact printing, and a combination of these methods. I can make a film.
  • the film thickness is usually 0.1 ⁇ m to 30 ⁇ m. 2 ⁇ m to 20 ⁇ m is preferable.
  • the above-mentioned composition can be used.
  • specific examples of the solvent include benzene, toluene, xylene, mesitylene, monochlorobenzene, dichlorobenzene, trichlorobenzene, tetrachlorobenzene, tetrahydrofuran, methylene chloride, chloroform, ether, hexane, cyclohexane, heptane, acetonitrile, acetone, cyclopenta Non-cyclohexanone, 2-butanone, 2,4-dimethyl-3-pentanone, ethyl acetate, 1-butanol, fluorobenzene, 1,2-dimethoxyethane, methylnaphthalene, decalin, tetrahydronaphthalene, etc.
  • the support substrate examples include substrates made of glass or polymer (polycarbonate, polypropylene, polyethersulfone, polyethylene terephthalate, acrylic substrate, etc.).
  • the liquid crystal thin film is formed on a support substrate by a coating and printing method, and after drying, a discotic phase is formed at a temperature within the liquid crystal phase formation temperature range, followed by thermal polymerization or photocrosslinking polymerization as desired.
  • a thin film of the optical compensation sheet can be obtained.
  • 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 By utilizing the organic semiconductor characteristics of the heterocyclic compound 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, and conventionally an organic thin film combining a conductive polymer, fullerene, etc.
  • Development of solar cells using semiconductors is the mainstream, but power conversion efficiency is a problem.
  • the heterocyclic compound represented by the formula (1) of the present invention will be a method for solving this problem.
  • 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 a resonator structure is incorporated in an organic semiconductor element containing a heterocyclic compound represented by the formula (1) of the present invention, and carriers can be efficiently injected to sufficiently increase the density of excited states, It is expected that 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 required for laser oscillation by electrical excitation into an organic semiconductor element to generate a high density excited 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).
  • Synthesis example 2 Synthesis of 1,3,5-Trichloro-2,4,6-tris [(trimethylsilyl) ethyl] benzene (equivalent to Scheme 3- (8)) Under a nitrogen atmosphere, the 1,3,5-trichloro-2,4,6-triiodobenzene (5.0 g, 8.94 mmol) obtained in Synthesis Example 1 in a 50 mL three-necked flask, diisopropylamine (4.5 mL), THF (29.8 mL) was added and degassed by Ar bubbling for 30 minutes.
  • Synthesis example 3 Synthesis of benzo [1,2-b: 3,4-b ′: 5,6-b ′′] trithiophene (Scheme 1- (2)) Sodium sulfide nonahydrate (7.74 g, 32.2 mmol) and NMP (138 mL) were added to a 30 mL round bottom flask and stirred for 15 minutes. Subsequently, 1,3,5-trichloro-2,4,6-tris (trimethylsilylethynyl) benzene (3.0 g, 6.38 mmol) obtained in Synthesis Example 2 was added and heated at 180 to 190 ° C. for 38 hours. .
  • Synthesis example 4 Synthesis of 1,3,5-Trichloro-2,4,6-trioct-1-ylbenzene (equivalent to Scheme 3- (8)) In a 20 mL two-necked flask under a nitrogen atmosphere, 1,3,5-trichloro-2,4,6-triiodobenzene (1.0 g, 1.8 mmol) obtained in Synthesis Example 1 and diisopropylamine (0.8 mL) were obtained. ) And toluene (9.0 mL) were added, and deaeration was performed by Ar bubbling for 30 minutes.
  • Synthesis example 5 Synthesis of 1,3,5-Trichloro-2,4,6-tris (phenylethyl) benzene (corresponding to Scheme 3- (8)) In a 100 mL three-necked flask under a nitrogen atmosphere, 1,3,5-trichloro-2,4,6-triiodobenzene (5.0 g, 8.94 mmol) obtained in Synthesis Example 1, diisopropylamine (4.5 mL), THF (40 mL) was added and degassed by Ar bubbling for 30 minutes.
  • Example 6 2,5,8-Tris (4- (N- (1-naphthyl) -N-phenyl-amino) phenyl) benzo [1,2-b: 3,4-b ′: 5,6-b ′′] Synthesis of trithiophene (1029) Ndpa-BTT Under a nitrogen atmosphere, 2,5,8-tribromobenzo [1,2-b: 3,4-b ′: 5,6-b ′′] trithiophene (450 mg, 0.93 mmol) obtained in Example 4 was used.
  • Example 7 Preparation and evaluation of thin film transistor elements-Part 1
  • An n-doped silicon wafer with a 200 nm SiO 2 thermal oxide film was placed in a vacuum deposition apparatus and evacuated until the degree of vacuum in the apparatus was 5.0 ⁇ 10 ⁇ 3 Pa or less.
  • this electrode was subjected to compound no. 142 was deposited to a thickness of 50 nm to form a semiconductor layer (2).
  • a shadow mask for electrode preparation is attached to this substrate, and it is placed in a vacuum vapor deposition apparatus.
  • the vacuum in the apparatus is evacuated to 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 80 nm to obtain a TC (top contact) type organic transistor element 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 serves as the substrate (6) and the gate electrode (5). ) (See FIG. 3).
  • 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 10 V to -100 V in 20 V steps, the drain voltage was scanned from 0 V to -60 V, and the drain current-drain voltage was measured. As a result, current saturation was observed.
  • the drain current was set to ⁇ 60V
  • the gate voltage was scanned from 20V to ⁇ 50V
  • the gate voltage ⁇ drain current was measured. From the obtained voltage-current curve, the device showed a p-type semiconductor, the carrier mobility was 10 ⁇ 3 cm 2 / Vs, and the threshold voltage was ⁇ 12V.
  • Example 8 Preparation and evaluation of organic EL elements-Part 1
  • a glass substrate manufactured by Tokyo Sanyo Vacuum Co., Ltd., 14 ⁇ / ⁇ or less
  • ITO transparent conductive film was deposited to 150 nm was cut into 25 ⁇ 25 mm and etched.
  • the obtained substrate was subjected to ultrasonic cleaning with a neutral detergent for 10 minutes, ultrasonic cleaning with ion exchange water for 5 minutes ⁇ 2 times, ultrasonic cleaning with acetone for 5 minutes ⁇ 2 times, followed by isopropyl alcohol for 5 minutes ⁇ 2 times.
  • the substrate was subjected to sonic cleaning, UV-ozone cleaning was performed for 10 minutes immediately before the device fabrication, and the substrate was placed in a vacuum vapor deposition apparatus, and evacuated until the degree of vacuum in the apparatus became 3.0 ⁇ 10 ⁇ 3 Pa or less.
  • a hole transport material by resistance heating vapor deposition No. 10 of Example 10 (synthesis example) was used.
  • a 1010 compound (Tpa-BTT) was deposited to a thickness of 50 nm to form a hole transport layer.
  • tris (8-quinolinolato) aluminum (AlQ3) was deposited to a thickness of 50 nm as a light emitting layer and an electron transporting layer.
  • lithium fluoride was vapor-deposited to a thickness of 0.8 nm and aluminum was vapor-deposited to a thickness of 100 nm to form a cathode, thereby producing a round organic EL element having a diameter of 2 mm.
  • the configuration of this organic EL element is shown in FIG.
  • the current density of the organic EL device was 100 mA / cm 2
  • the driving voltage was 9.5V.
  • the current efficiency was 3.64 cd / A (1000 cd / m 2).
  • Example 9 Preparation and evaluation of organic EL devices-Part 2 Compound No. 5 of Example 5 In place of 1010 (Tpa-BTT), Compound No. An organic EL device was produced in the same manner as in Example 8 except that 1029 (Ndpa-BTT) was used.
  • This organic EL element had a driving voltage of 11.7 V at a current density of 100 mA / cm 2. The current efficiency was 3.89 cd / A (1000 cd / m 2).
  • Example 10 Preparation and evaluation of organic EL devices-Part 3 Compound No. 5 of Example 5 In place of 1010 (Tpa-BTT), Compound No. An organic EL device was produced in the same manner as in Example 8 except that 67 was used. This organic EL element had a driving voltage of 7.8 V at a current density of 100 mA / cm 2. The current efficiency was 4.2 cd / A (1000 cd / m 2).
  • Example 11 Preparation and evaluation of thin-film transistor elements-Part 2 Compound No. 7 of Example 7 In place of 142, Compound No. A thin film transistor element was fabricated in the same manner as in Example 7 except that 1013 was used. This element was a p-type semiconductor, had a carrier mobility of 8 ⁇ 10 ⁇ 4 cm 2 / Vs, and a threshold voltage of ⁇ 20V.
  • Example 12 Synthesis of 2,5,8-Tris (4- (N-Carbazol) phenyl) benzo [1,2-b: 3,4-b ′: 5,6-b ′′] trithiophene (1013) Under a nitrogen atmosphere, 2,5,8-tribromobenzo [1,2-b: 3,4-b ′: 5,6-b ′′] trithiophene (33) obtained in Example 4 (500 mg, 1.04 mmol), 4- (N-carbazolyl) phenylboronic acid (1.34 g, 4.66 mmol) tripotassium phosphate hydrate (3.96 g, 18.6 mmol) was suspended in DMF (40 ml), Deaerated with Ar bubbling for 30 minutes.
  • Example 14 Alkylation reaction via Litation of BTT Benzo [1,2-b: 4,5-b ′: 5.6-b ′′] trithiophene (Scheme 1- (2)) (800 mg) obtained in Synthesis Example 3 in a 50 mL three-necked flask under a nitrogen atmosphere , 3.25 mmol) and tetrahydrofuran (22.7 mL) were cooled to 0 ° C., and 1.59 mol / l n-butyllithium hexane solution (4.5 ml, 7.15 mmol) was added thereto and stirred for 2 hours.
  • Example 16 Dibromination reaction of BTT by NBS bromination reaction Benzo [1,2-b: 4,5-b ′: 5.6-b ′′] trithiophene (Scheme 1- (2)) (800 mg) obtained in Synthesis Example 3 in a 50 mL three-necked flask under a nitrogen atmosphere , 3.25 mmol), methylene chloride (22.7 mL), acetic acid (5.7 mL) were added. NBS (1.16 g, 6.5 mmol) was added little by little under light-shielding conditions, and the mixture was stirred at room temperature for 24 hours.
  • Example 17 Dibromo BTT Sonogami Coupling Under a nitrogen atmosphere, the 2,5-dibromobenzo [1,2-b: 4,5-b ′: 5.6-b ′′] trithiophene (35) obtained in Example 16 was placed in a 20 mL two-necked flask. Diisopropylamine (0.6 mL) and toluene (7.0 mL) were added to a mixture containing (300 mg), and deaeration was performed by Ar bubbling for 30 minutes.
  • the heterocyclic compound represented by the formula (1) obtained by the present invention exhibits excellent characteristic values as an organic thin film transistor or an organic EL element, and as an organic electronic device. It can be said that it is a very useful compound having high versatility.

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  • Thin Film Transistor (AREA)
  • Liquid Crystal Substances (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Abstract

La présente invention concerne un composé hétérocyclique représenté par la formule (1) et une composition préparée avec celui-ci, ainsi qu'un dispositif électronique organique utilisant le composé. (Dans la formule (1), X1, X2 et X3 représentent chacun indépendamment un atome de soufre ou de sélénium, et les R1 à R6 représentent chacun indépendamment un groupe hydrocarboné aromatique, hydrocarboné aliphatique, halogéno, hydroxyle, alcoxy, mercapto, alkylthio, acide boronique, nitro, amino substitué, amido, acyle, carboxyle, acyloxy, cyano, sulfo, sulfamoyle, alkylsulfamoyle, carbamoyle ou alkylcarbamoyle, ou un atome d'hydrogène, à condition que tous les R1 à R6 ne soient pas en même temps des atomes d'hydrogène.) Le composé représenté par la formule (1) convient pour une utilisation dans un dispositif électronique organique tel qu'un élément électroluminescent organique, un élément de transistor organique ou un élément à cristaux liquides.
PCT/JP2009/069688 2008-11-21 2009-11-20 Nouveau composé hétérocyclique et utilisation de celui-ci Ceased WO2010058833A1 (fr)

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US13/126,771 US8313671B2 (en) 2008-11-21 2009-11-20 Heterocyclic compound and use thereof
JP2010539257A JP5622585B2 (ja) 2008-11-21 2009-11-20 新規な複素環式化合物及びその利用
EP09827614.0A EP2361915B1 (fr) 2008-11-21 2009-11-20 Nouveau composé hétérocyclique et utilisation de celui-ci
CN200980146586.XA CN102224158B (zh) 2008-11-21 2009-11-20 新的杂环化合物及其用途

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JP2013184904A (ja) * 2012-03-06 2013-09-19 Daicel Corp アンタントレン系化合物およびその製造方法
WO2015129581A1 (fr) * 2014-02-25 2015-09-03 日本化薬株式会社 Nouveau composé aromatique polycyclique organique et son utilisation
JPWO2015129581A1 (ja) * 2014-02-25 2017-03-30 日本化薬株式会社 新規な有機多環芳香族化合物、およびその利用
JP2015019114A (ja) * 2014-10-28 2015-01-29 ユー・ディー・シー アイルランド リミテッド 有機電界発光素子、表示装置及び照明装置
JP2017041559A (ja) * 2015-08-20 2017-02-23 日本化薬株式会社 光電変換素子、撮像素子、光センサー及び光電変換素子用材料
JP2017039662A (ja) * 2015-08-20 2017-02-23 日本化薬株式会社 有機多環芳香族化合物、およびその利用
JP2017039661A (ja) * 2015-08-20 2017-02-23 日本化薬株式会社 有機多環芳香族化合物、およびその利用
JP2017039663A (ja) * 2015-08-20 2017-02-23 日本化薬株式会社 有機多環芳香族化合物、およびその利用

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EP2361915B1 (fr) 2015-01-28
EP2361915A4 (fr) 2013-03-20
CN102224158A (zh) 2011-10-19
US8313671B2 (en) 2012-11-20
EP2361915A1 (fr) 2011-08-31
JP5622585B2 (ja) 2014-11-12
JPWO2010058833A1 (ja) 2012-04-19
KR20110091516A (ko) 2011-08-11
CN102224158B (zh) 2015-09-16
US20110204295A1 (en) 2011-08-25
KR101556095B1 (ko) 2015-09-30

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