WO2011071018A1 - Thiénopyrazine et transistor à effet de champ l'incluant - Google Patents

Thiénopyrazine et transistor à effet de champ l'incluant Download PDF

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WO2011071018A1
WO2011071018A1 PCT/JP2010/071829 JP2010071829W WO2011071018A1 WO 2011071018 A1 WO2011071018 A1 WO 2011071018A1 JP 2010071829 W JP2010071829 W JP 2010071829W WO 2011071018 A1 WO2011071018 A1 WO 2011071018A1
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group
ring
organic
substituent
substituents
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敬郎 山下
光 中山
杉岡　尚
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国立大学法人東京工業大学
株式会社クラレ
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Priority to JP2011514931A priority Critical patent/JP5650107B2/ja
Priority to CN201080055572XA priority patent/CN102781945A/zh
Priority to US13/514,371 priority patent/US8987447B2/en
Priority to EP10835938.1A priority patent/EP2511278B1/fr
Publication of WO2011071018A1 publication Critical patent/WO2011071018A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • 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
    • 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
    • H10K10/488—Insulated gate field-effect transistors [IGFETs] characterised by the channel regions the channel region comprising a layer of composite material having interpenetrating or embedded materials, e.g. a mixture of donor and acceptor moieties, that form a bulk heterojunction
    • 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
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/621—Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
    • 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
    • H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
    • 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
    • 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
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole

Definitions

  • the present invention relates to a thienopyrazine compound useful for an organic semiconductor material and an organic field effect transistor using the compound as a carrier transfer layer.
  • Field effect transistors are widely used as important switches and amplifying elements together with bipolar transistors.
  • the structure includes a semiconductor layer that forms a current path between a source electrode and a drain electrode, a gate electrode that applies a voltage to control the flow of current, and an insulator that separates the gate electrode from the semiconductor layer Consists of layers.
  • the characteristics of the field effect transistor are determined by the characteristics of the semiconductor used, but the carrier mobility and on / off value of the semiconductor are particularly important.
  • inorganic materials such as amorphous silicon and polysilicon have been widely used as semiconductor materials.
  • Such an inorganic semiconductor typified by silicon is a single crystal composed of a single element, and has a simple structure and stable physical properties.
  • a high temperature treatment is required, it is difficult to use a plastic substrate or a plastic film as a substrate for a field effect transistor.
  • the device manufacturing process is performed in a vacuum, expensive manufacturing equipment is required, resulting in high costs.
  • organic field effect transistors using organic semiconductors have attracted attention in place of inorganic semiconductors, and organic semiconductor materials are being researched from the viewpoint of basic optoelectronics.
  • organic semiconductor materials are being researched from the viewpoint of basic optoelectronics.
  • the organic field effect transistor can be reduced in weight, flexible, and have a large area, and the manufacturing process can be simplified.
  • Organic semiconductors include p-type semiconductors, which are semiconductors in which positively charged holes carry current, and n-type semiconductors, in which free electrons with negative charge carry current. There is an ambipolar type semiconductor that plays a role.
  • Patent Document 1 discloses a field effect transistor using a benzodifuranone-based organic compound as a semiconductor material.
  • the field effect transistor has n-type, p-type, and ambipolar type electrical characteristics.
  • Such organic semiconductor materials have high carrier mobility and high on / off ratio, regardless of p-type, n-type, and ambipolar types, and have high workability to which printing methods such as solution coating and ink jet can be applied. It is desired.
  • a transistor using an ambipolar organic semiconductor enables p-type and n-type driving with a single material, so that a complementary metal oxide semiconductor (CMOS) circuit with low power consumption can be easily manufactured. Therefore, development of such an organic semiconductor material is desired (see Non-Patent Document 1).
  • CMOS complementary metal oxide semiconductor
  • the current organic semiconductor materials have problems such as low solubility, difficulty in synthesis, insufficient carrier mobility, and the like.
  • the present invention has been made to solve the above-mentioned problems, and a thienopyrazine compound useful for an organic semiconductor material and an organic semiconductor layer easily produced from the organic semiconductor material containing the same by a coating method or a printing method.
  • An object of the present invention is to provide an organic field effect transistor capable of forming a film and exhibiting high carrier mobility and current on / off ratio, and further an organic field effect transistor having ambipolar characteristics.
  • the thienopyrazine compound according to claim 1 which has been made to achieve the above object, has the following chemical formula (I): (In the formula, Ar 1 and Ar 2 are aryl groups optionally having substituents, R 1 and R 2 are hydrogen atoms independent of each other, alkyl groups optionally having substituents, or substituents; Or an aryl group which may have a ring or a group which is bonded to each other to form a ring.
  • the thienopyrazine compound described in claim 2 is the compound described in claim 1, wherein the groups bonded to each other to form a ring are: (R 3 to R 6 are each independently a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent), To do.
  • the thienopyrazine compound described in claim 3 is the compound described in claim 2 and has the following chemical formula (II): (Wherein, R 3 ⁇ R 6 is as defined R 3 ⁇ R 6 groups form a ring bonded to the mutually, R 7 ⁇ R 12 is closed independently of one another hydrogen atom, a substituent And a hydrocarbon group having 1 to 20 carbon atoms, or an aryl group which may have a substituent, and n is a positive number of 1 to 20).
  • the organic semiconductor material according to claim 4 has the following chemical formula (I): (In the formula, Ar 1 and Ar 2 are aryl groups optionally having substituents, R 1 and R 2 are hydrogen atoms independent of each other, alkyl groups optionally having substituents, or substituents; A thienopyrazine compound represented by an aryl group optionally having a ring or a group bonded to each other to form a ring.
  • the organic semiconductor material described in claim 5 is the organic semiconductor material described in claim 4, wherein the groups that are bonded to each other to form a ring are: (Wherein R 3 to R 6 are each independently a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent) It is characterized by containing.
  • An organic semiconductor material described in claim 6 is the organic semiconductor material described in claim 4 and has the following chemical formula (II): (Wherein, R 3 ⁇ R 6 is as defined R 3 ⁇ R 6 groups form a ring bonded to the mutually, R 7 ⁇ R 12 is closed independently of one another hydrogen atom, a substituent An optionally substituted hydrocarbon group having 1 to 20 carbon atoms, or an aryl group which may have a substituent, and n is a positive number of 1 to 20). It is characterized by.
  • An organic field effect transistor is an organic semiconductor layer forming a current path between a source electrode and a drain electrode on a substrate, and a gate electrode controlling a current in the current path.
  • Is separated by an insulator layer, and the organic semiconductor layer has the following chemical formula (I) (In the formula, Ar 1 and Ar 2 are aryl groups optionally having substituents, R 1 and R 2 are hydrogen atoms independent of each other, alkyl groups optionally having substituents, or substituents; A thienopyrazine compound represented by an aryl group optionally having a ring or a group bonded to each other to form a ring.
  • the organic field effect transistor described in claim 8 is the one described in claim 7, wherein the organic semiconductor layer has ambipolar characteristics.
  • the thienopyrazine compound of the present invention can be used as an organic semiconductor material exhibiting n-type characteristics or p-type characteristics. Further, by appropriately selecting the structure of the thienopyrazine compound, it can be used as an organic semiconductor material exhibiting ambipolar characteristics that bear both n-type characteristics and p-type characteristics.
  • the thienopyrazine compound shows high solubility, it can be easily formed not only by a vapor deposition method but also by a printing method such as a coating method or an ink jet method, and an organic field effect transistor can be manufactured.
  • An organic field effect transistor manufactured with this organic semiconductor material exhibits high carrier mobility and can have a higher current on / off ratio.
  • the organic field effect transistor of the present invention contains a thienopyrazine compound having a quinoid thiophene structure in the organic semiconductor layer, so that the band gap can be reduced and ambipolar characteristics can be exhibited.
  • 1 is an organic semiconductor layer
  • 2 is a source electrode
  • 3 is a drain electrode
  • 5 is an insulating support substrate
  • 6 is a gate electrode
  • 7 is an insulator layer
  • 10, 20 and 30 are organic field effect transistors
  • L is a channel length. is there.
  • the thienopyrazine compound of the present invention is a cis-trans isomer having a thiophene moiety as a quinoid type.
  • This isomer structure is not particularly limited, and two double bonds of quinoid type can be a cis-cis type, cis-trans type, or trans-trans type combined structure.
  • This thienopyrazine compound has a small difference between the highest occupied orbital (HOMO) and the lowest unoccupied orbital (LUMO) and a small band gap.
  • Ar 1 .Ar 2 and R represented by the above chemical formula (I) By appropriately selecting 1 ⁇ R 2 , the LUMO level can be adjusted.
  • the aryl group represented by Ar 1 and Ar 2 is a monocyclic ring or a condensed ring, and may be a carbocyclic compound or a heterocyclic compound.
  • aryl groups for example, thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, phenyl, naphthyl, anthryl, phenanthryl, fluorenyl, carbazolyl, imidazolyl, pyridyl, quinolyl, benzoxa Examples include a zolyl group, a benzimidazolyl group, a benzthiazolyl group, a carbazolyl group, an azepinyl group, and the like, and further includes a multimer composed of any one or more groups of the above aryl groups. Among them, a phenyl group, a naphthyl group, a thienyl group, and a dimer to 20
  • aryl groups may have a substituent.
  • substituents include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, isohexyl group, 2-ethylhexyl group, n-heptyl group, n-octyl group, n-nonyl group, n
  • An alkyl group such as a decyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group; 80 of the hydrogen atoms of the linear, branched, or cycl
  • ambipolar properties include a fluorine atom or a perfluoroalkyl group.
  • the alkyl group represented by R 1 and R 2 has 1 to 20 carbon atoms.
  • cyclic cycloalkyl such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group, etc.
  • cyclic cycloalkyl such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group, etc.
  • alkyl groups may have a substituent.
  • substituents include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group; a pyridyl group, a thienyl group, a furyl group, and a pyrrolyl group.
  • Imidazolyl group pyrazinyl group, oxazolyl group, thiazolyl group, pyrazolyl group, benzothiazolyl group, benzoimidazolyl group and other heteroaromatic ring groups; methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy Group, tert-butoxy group, pentyloxy group, isopentyloxy group, neopentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, etc.
  • Methylchi Group alkylthio group such as ethylthio group, propylthio group and butylthio group; arylthio group such as phenylthio group and naphthylthio group; trisubstituted silyloxy group such as tert-butyldimethylsilyloxy group and tert-butyldiphenylsilyloxy group; acetoxy group; Acyloxy groups such as propanoyloxy group, butanoyloxy group, pivaloyloxy group, benzoyloxy group; methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, isobutoxycarbonyl group, sec-butoxy Alkoxy such as carbonyl group, tert-butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, heptyl
  • Alkylsulfonyl group such as methylsulfinyl group and ethylsulfinyl group; arylsulfinyl group such as phenylsulfinyl group; methylsulfonyloxy group, ethylsulfonyloxy group, phenylsulfonyloxy group, methoxysulfonyl group, ethoxysulfonyl group, phenyloxy A sulfonate group such as a sulfonyl group; a primary or secondary amino group; a cyano group; a nitro group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom;
  • the aryl group represented by R 1 and R 2 is a monocyclic ring or a condensed ring, and may be a carbocyclic compound or a heterocyclic compound.
  • an aryl group for example, phenyl group, naphthyl group, anthryl group, phenanthryl group, pyridyl group, thienyl group, furyl group, pyrrolyl group, imidazolyl group, pyrazinyl group, oxazolyl group, thiazolyl group, pyrazolyl group, benzothiazolyl group, benzoimidazolyl group Etc.
  • These aryl groups may have a substituent, and as such a substituent, the substituents exemplified for the alkyl groups of R 1 and R 2 can be used.
  • alkyl group, alkoxy group and the like exemplified as the substituent have 1 to 30 carbon atoms and may be linear, branched or cyclic.
  • R 1 and R 2 are groups bonded to each other as shown in the following chemical formula (III), and may form a quinoxaline skeleton.
  • R 3 to R 6 are hydrogen atoms have been shown, but the present invention is not limited thereto, and R 3 to R 6 may have an optionally substituted alkyl having 1 to 20 carbon atoms. It may be a group or an aryl group which may have a substituent.
  • alkyl groups those exemplified for the alkyl group represented by R 1 and R 2 can be used, and as the aryl group, those exemplified for the aryl group represented by R 1 and R 2 can be used. These may have a substituent, and as the substituent, those exemplified for the alkyl groups of R 1 and R 2 can be used.
  • examples of the ring formed by bonding R 1 and R 2 include a benzene ring, a furan ring, a thiophene ring, a pyrrole ring, a 2H-pyran ring, and a 4H— Thiopyran ring, pyridine ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, furazane ring, imidazole ring, pyrazole ring, pyrazine ring, pyrimidine ring, pyridazine ring, etc.
  • the thienopyrazine compound of the present invention may be one represented by the above chemical formula (II).
  • examples of the hydrocarbon group represented by R 7 to R 12 include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an alkynyl group having 3 to 20 carbon atoms. .
  • the alkyl group having 1 to 20 carbon atoms may be linear, branched or cyclic, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl. Linear, tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, isohexyl group, 2-ethylhexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, etc.
  • cyclic groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptanyl group, cyclooctanyl group, cyclononanyl group, cyclodecanyl group, cycloundecanyl group, cyclododecanyl group, etc.
  • a cycloalkyl group is mentioned.
  • the alkenyl group having 2 to 20 carbon atoms may be linear, branched or cyclic, for example, vinyl group, allyl group, 1-methylvinyl group, propenyl group, methallyl group, butenyl group, for example.
  • the alkynyl group having 3 to 20 carbon atoms may be linear or branched, for example, for example, propynyl group, butynyl group, pentynyl group, hexynyl group, heptynyl group, octynyl group, noninyl group, dodecynyl group 1-methyl-2-butynyl group, 1-methyl-3-butynyl group, 2-methyl-3-butynyl group, 3-methyl-1-butynyl group, 3-methyl-2-propynyl group, 2-ethynylpropyl Groups and the like.
  • These hydrocarbon groups may have a substituent, and as such a substituent, the substituents exemplified for the alkyl groups of R 1 and R 2 can be used.
  • thienopyrazine compound (1) is obtained by reacting dihydrothienopyrazine compound (2) with aromatic aldehyde compounds (3) and (4) in the presence of a base. It is suitably synthesized.
  • This synthesis reaction is preferably carried out by reacting the dihydrothienopyrazine compound (2) with the aromatic aldehyde compounds (3) and (4) in an inert gas atmosphere such as nitrogen or argon and in the presence of a solvent. .
  • Examples of the base used in the synthesis reaction include hydroxides of alkali metals or alkaline earth metals such as sodium hydroxide, potassium hydroxide, calcium hydroxide, aluminum hydroxide; sodium methoxide, sodium ethoxide, potassium methoxide Metal alkoxides such as lithium methoxide, sodium isopropoxide, sodium tert-butoxide, potassium tert-butoxide, magnesium dimethoxide, calcium dimethoxide; methyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, Organolithium compounds such as phenyl lithium, vinyl lithium, lithium diisopropylamide, lithium bistrimethylsilylamide; trimethylamine, triethylamine, tributylamine Trioctylamine, triethanolamine, pyridine, tertiary amines such as quinoline; and the like.
  • alkali metals or alkaline earth metals such as sodium
  • metal alkoxides or organolithium compounds are preferably used, and potassium tert-butoxide and n-butyllithium are particularly preferable from the viewpoint of reaction selectivity and availability.
  • the amount to be used is preferably in the range of 0.8 to 5 mol, more preferably in the range of 1.0 to 3 mol, per 1 mol of the dihydrothienopyrazine compound (2).
  • the raw material dihydrothienopyridine compound (2) and aromatic aldehyde compounds (3) and (4) are dissolved to such an extent that the reaction rate is not hindered and used even in the presence of a base.
  • a possible solvent is preferred.
  • solvents include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and mesitylene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, nonane, and decane; and alicyclic groups such as cyclohexane and cyclooctane.
  • Hydrocarbons such as diethyl ether, diisopropyl ether, dibutyl ether, anisole, and tetrahydrofuran; and mixed solvents thereof.
  • ethers typified by tetrahydrofuran are preferably used.
  • the amount of the solvent to be used is preferably 1 to 500 parts by mass, more preferably 3 to 100 parts by mass with respect to 1 part by mass of the dihydrothienopyridine compound (2).
  • the reaction temperature is preferably in the range of ⁇ 80 ° C. to 100 ° C., more preferably in the range of ⁇ 20 ° C. to 50 ° C.
  • the reaction time varies depending on the types of the dihydrothienopyrazine compound (2), the base and the solvent, the amount used, and the reaction temperature, but is preferably in the range of 0.5 to 30 hours.
  • the thienopyrazine compound (1) thus obtained can be isolated and purified by a method usually performed in the isolation and purification of organic compounds.
  • the reaction mixture is separated into an organic layer and an aqueous layer using a separatory funnel, and the aqueous layer is extracted with a solvent such as diethyl ether, ethyl acetate, toluene, methylene chloride, 1,2-dichloroethane, and extracted.
  • the crude product obtained by concentrating the liquid and the organic layer after drying over anhydrous sodium sulfate, etc., and concentrating, is purified by sublimation, recrystallization, distillation, silica gel column chromatography, etc. as necessary.
  • a high thienopyrazine compound (1) can be obtained.
  • thienopyrazine compounds can be used as organic semiconductor materials having a high electron transfer and on / off ratio.
  • the isomer structure of the thienopyrazine compound used as the organic semiconductor material is not particularly limited, and a structure in which two double bonds of quinoid type are a combination of cis-cis type, cis-trans type, or trans-trans type is used. Can be mentioned. In addition, these structures may be a single structure or a mixture thereof. Each of these isomeric structures has almost no energy difference in the structure optimization calculation by Gaussian 03.
  • an organic field effect transistor can be manufactured by using the organic semiconductor material containing the thienopyrazine compound of the present invention for the organic semiconductor layer.
  • the thienopyrazine compound represented by the chemical formula (II) is used as an organic semiconductor material, an organic field effect transistor having ambipolar characteristics can be manufactured.
  • the ambipolar characteristic refers to a property that exhibits p-type characteristics when holes are injected and transported as carriers, and exhibits n-type characteristics when electrons are injected and transported as carriers.
  • An organic field effect transistor is a substrate in which a gate electrode layer to which a voltage is applied, an insulator layer, an organic semiconductor layer, and a source-drain electrode layer serving as a current path are laminated.
  • a gate electrode layer to which a voltage is applied an insulator layer, an organic semiconductor layer, and a source-drain electrode layer serving as a current path are laminated.
  • the organic field effect transistor 10 includes a gate electrode 6, an insulator layer 7, an organic semiconductor layer 1 containing a thienopyrazine compound, and a source electrode 2 and a drain electrode 3 on an insulating support substrate 5. Are sequentially stacked to form a bottom gate / top contact type.
  • the gate electrode 6 controls the current flowing in the current path, and is isolated from the organic semiconductor layer 1 and the source-drain electrode layer 2-3 by the insulator layer 7.
  • the source-drain electrode layer 2-3 is deposited on the organic semiconductor layer 1 and forms a channel region that becomes a current path between the source electrode 2 and the drain electrode 3.
  • the organic field effect transistor 10 generates an electric field when a voltage is applied to the gate electrode 6, and forms a channel region serving as a current path between the source electrode 2 and the drain electrode 3 in the source-drain electrode layer 2-3.
  • a current flows by moving carriers that are holes or electrons.
  • the transistor operation is performed by changing the carrier density between the organic semiconductor layer 1 and the insulator layer 7 and changing the amount of current flowing between the source electrode 2 and the drain electrode 3.
  • the organic semiconductor layer 1 is formed by forming a film using the thienopyrazine compound of the present invention or an organic semiconductor material containing the compound.
  • the organic semiconductor layer 1 is a carrier moving layer for moving holes or electrons as carriers from one electrode to the other electrode.
  • the film thickness of the organic semiconductor layer 1 is preferably about 1 nm to 10 ⁇ m, and more preferably about 10 to 500 nm.
  • raw materials for the insulating support substrate 5 include polyethylene terephthalate (PET), glass, quartz, silicon, ceramics, and plastics.
  • the thickness of the insulating support substrate 5 is preferably about 0.05 to 2 mm, and more preferably about 0.1 to 1 mm.
  • the insulator layer 7 preferably has an electric conductivity at room temperature having a leak current of 10 ⁇ 2 A / cm 2 or less under an electric field strength of 1.0 MV / cm. Further, the relative dielectric constant is usually about 4.0, and it is preferable that the relative dielectric constant shows a high value.
  • the raw material for the insulator layer 7 include silicon oxide, silicon nitride, amorphous silicon, aluminum oxide, and tantalum oxide.
  • the group consisting of polystyrene, polyvinylphenol, polycarbonate, polyester, polyvinyl acetate, polyurethane, polysulfone, (meth) acrylic resin, epoxy resin, hydrocarbon resin and phenol resin having cyano group, polyimide resin and polyparaxylylene resin You may form from the resin or resin composition which has 1 type, or 2 or more types of resin selected from these as a main component.
  • the film thickness of the insulator layer 7 is preferably about 50 nm to 2 ⁇ m, more preferably about 100 nm to 1 ⁇ m.
  • the raw materials to be the gate electrode 6, the source electrode 2, and the drain electrode 3 are not particularly limited as long as they exhibit conductivity. Specifically, platinum, gold, silver, nickel, chromium, copper, iron, tin, antimony lead, tantalum, indium, palladium, tellurium, rhenium, iridium, aluminum, ruthenium, germanium, molybdenum, tungsten, tin oxide / antimony, Indium tin oxide (ITO), fluorine-doped zinc oxide, zinc, silicon, carbon, graphite, classy carbon, silver paste and carbon paste, lithium, beryllium, sodium, magnesium, potassium, calcium, scandium, titanium, manganese, zirconium, Gallium, niobium, sodium-potassium alloy, magnesium / silver mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide Mixture, lithium / aluminum mixture, amorphous silicon, and the like.
  • a known conductive polymer whose conductivity is improved by doping or the like for example, conductive polyaniline, conductive polypyrrole, conductive polythiophene, a complex of polyethylenedioxythiophene and polystyrenesulfonic acid, or the like is also preferably used.
  • the film thicknesses of the gate electrode 6, the source electrode 2, and the drain electrode 3 are preferably 0.01 to 2 ⁇ m, and more preferably 0.2 to 1 ⁇ m.
  • the channel length L which is the distance between the source electrode 2 and the drain electrode 3, is usually 100 ⁇ m or less and preferably 50 ⁇ m or less.
  • the channel width W is usually 2000 ⁇ m or less and preferably 500 ⁇ m or less.
  • L / W is usually 0.1 or less and preferably 0.05 or less.
  • the method for forming the organic field effect transistor 10 is not particularly limited, and a conventionally known method can be used.
  • the organic semiconductor layer 1 can be formed by dissolving a thienopyrazine compound in a solvent to form a solution and applying it by a casting method, a dip method, a spin coating method, or a vacuum deposition method.
  • the insulator layer 7 can be formed by, for example, a coating method such as spin coating or blade coating, a vapor deposition method, a sputtering method, a printing method such as screen printing, ink jetting, or an electrostatic charge image developing method.
  • a photo-curing resin that forms an insulator by applying a monomer as a precursor of the insulator and then curing it by irradiation with light may be used.
  • the gate electrode 6, the source electrode 2, and the drain electrode 3 can be formed by, for example, a vacuum deposition method, a sputtering method, a coating method, a printing method, a sol-gel method, or the like.
  • these patterning methods there are a photolithography method, a printing method such as ink jet printing, screen printing, offset printing, letterpress printing, a soft lithography method such as a micro contact printing method, and a method combining a plurality of these methods. Can be mentioned.
  • it can also form by the method of irradiating energy rays, such as a laser and an electron beam, and removing a material.
  • the organic field effect transistor 20 includes a gate electrode 6, an insulator layer 7, a source-drain electrode layer 2-3 that is a source electrode 2 and a drain electrode 3, and an organic semiconductor layer 1 on an insulating substrate 5. It is a bottom gate / bottom contact type formed by sequentially laminating. Except for the difference in the channel region due to the difference in the arrangement of the source-drain electrode layer 2-3 and the organic semiconductor layer 1, it is the same as that shown in FIG.
  • FIG. 3 shows an example of still another organic field effect transistor 30.
  • the organic field effect transistor 30 is a top gate / bottom contact type in which a source-drain electrode layer 2-3, an organic semiconductor layer 1, an insulator layer 7, and a gate electrode 6 are sequentially formed on an insulating substrate 5. It is.
  • the structure of the organic field effect transistor is not particularly limited.
  • a protective film is formed on the organic semiconductor layer 1. It may be.
  • This protective film can minimize the influence of outside air on the organic semiconductor layer 1.
  • the raw material of the protective film include polymers such as epoxy resin, acrylic resin, polyurethane, polyimide, and polyvinyl alcohol, and inorganic oxides and nitrides such as silicon oxide, silicon nitride, and aluminum oxide.
  • the protective film can be formed by a coating method, a vacuum deposition method, or the like.
  • Example 1 The synthesis reaction of 1,3-bis (2-thienylmethylene) -1,3-dihydrothieno [3,4-b] quinoxaline is shown in the following reaction formula (6).
  • Example 2 The synthesis reaction of 1,3-bis (phenylmethylene) -1,3-dihydrothieno [3,4-b] quinoxaline is shown in the following reaction formula (7).
  • Example 2 The same procedure as in Example 1 was carried out except that 6.62 g (59 mmol) of thiophene-2-carbaldehyde was changed to 6.26 g (59 mmol) of benzaldehyde, and 0.328 g (yield: 15) of the target reddish purple solid was obtained. %).
  • Example 2 The same procedure as in Example 1 was carried out except that 6.62 g (59 mmol) of thiophene-2-carbaldehyde was changed to 10.27 g (59 mmol) of 4-trifluoromethylbenzaldehyde, and 0.360 g of the target ocherous solid was obtained. (Yield: 12%) was obtained.
  • Example 4 A synthesis reaction of 1,3-bis (5-hexyl-2-thienylmethylene) -1,3-dihydrothieno [3,4-b] quinoxaline is shown in the following reaction formula (9).
  • Example 2 The same procedure as in Example 1 was carried out except that 6.62 g (59 mmol) of thiophene-2-carbaldehyde was changed to 11.58 g (59 mmol) of 5-hexylthiophene-2-carbaldehyde. 0.523 g (yield: 16%) was obtained.
  • Example 2 The same procedure as in Example 1 was carried out except that 6.62 g (59 mmol) of thiophene-2-carbaldehyde was changed to 11.46 g (59 mmol) of 2,2′-bithiophene-5-carbaldehyde. 1.23 g (yield: 38%) of a purple solid was obtained.
  • Example 2 The same procedure as in Example 1 was carried out except that 6.62 g (59 mmol) of thiophene-2-carbaldehyde was changed to 10.75 g (59 mmol) of 4-phenylbenzaldehyde, and 0.93 g (yield) of the target red solid was obtained. : 30%).
  • Example 2 The same procedure as in Example 1 was carried out except that 6.62 g (59 mmol) of thiophene-2-carbaldehyde was changed to 9.21 g (59 mmol) of 2-naphthaldehyde, and 1.20 g (yield) of the target red solid : 43%).
  • Example 1 6.62 g (59 mmol) of thiophene-2-carbaldehyde was changed to 16.42 g (59 mmol) of 5′-hexyl-2,2′-bithiophene-5-carbaldehyde obtained in Synthesis Example 3. The same procedure was followed except that only the silica gel column chromatography was used to obtain 1.19 g (yield: 28%) of the target purple solid.
  • Example 9 The synthesis reaction of 1,3-bis [5- (4-trifluoromethyl) -2-thienylmethylene] -1,3-dihydrothieno [3,4-b] quinoxaline is shown in the following reaction formula (14).
  • Example 1 6.62 g (59 mmol) of thiophene-2-carbaldehyde was changed to 15.12 g (59 mmol) of 5- (4-trifluoromethylphenyl) thiophene-2-carbaldehyde obtained in Synthesis Example 5. The same procedure was carried out except that 0.52 g (yield: 13%) of the target brown solid was obtained.
  • Example 10 Top Contact Type—Organic Field Effect Transistor
  • a silicon wafer having a thickness of 500 ⁇ m was cut into a size of 3.5 ⁇ 2.5 cm, and this wafer was used as an insulating support substrate.
  • the substrate was treated with ozone, or after treatment with hexamethyldisilazane (HMDS) or octyltrichlorosilane (OTS).
  • HMDS hexamethyldisilazane
  • OTS octyltrichlorosilane
  • An n-type silicon wafer was formed on this processing substrate and used as a gate electrode.
  • a 200 nm silicon oxide (SiO 2 ) insulator layer was formed on the gate electrode by thermal oxidation.
  • 30 nm of the compounds of Examples 1, 5, 6, 7, 8, and 9 were deposited on SiO 2 using a vacuum deposition method to form an organic semiconductor layer.
  • the obtained organic field effect transistor using an electrometer, a voltage of 10 to 60 V was applied between the source electrode and the drain electrode, and the gate voltage was changed in the range of ⁇ 20 to 100 V to obtain a voltage-current curve.
  • the transistor characteristics were evaluated at a temperature of 25 ° C.
  • Carrier mobility (mu) was calculated using the following equation representing the drain current I d of the (A).
  • I d (W / 2L) ⁇ ⁇ ⁇ Ci ⁇ (V g ⁇ V t ) 2 (A)
  • L is the gate length and W is the gate width.
  • Ci is the capacitance per unit area of the insulating layer
  • V g is the gate voltage
  • V t is the threshold voltage.
  • the on / off ratio was calculated from the ratio between the maximum and minimum drain current values (I d ).
  • the obtained transistor characteristic evaluation results are shown in Table 1.
  • the relationship between the drain current (I d ) and the drain voltage (V d ) at a gate voltage (V g ) of ⁇ 100 to 100 V is shown in FIG. 4 and FIG. As shown in FIG. It was confirmed that the p-type characteristics were exhibited when V g ⁇ 0 and the n-type characteristics were exhibited when V g > 0, and the organic field effect transistor using Example 9 was found to have ambipolar characteristics.
  • the thienopyrazine compound of the present invention is used as an organic semiconductor material such as an organic field effect transistor, an organic light emitting diode, a photovoltaic cell, a dye-sensitized solar cell, and an organic electronics device.
  • an organic semiconductor material such as an organic field effect transistor, an organic light emitting diode, a photovoltaic cell, a dye-sensitized solar cell, and an organic electronics device.
  • an ambipolar molecule it is used for making an inverter circuit capable of low power consumption and for application to a light-emitting transistor.

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

Abstract

La présente invention concerne une thiénopyrazine adaptée à un matériau semi-conducteur organique. La présente invention concerne également : un transistor à effet de champ organique, comprenant une couche semi-conductrice organique facilement obtenue à partir d'un matériau semi-conducteur organique contenant la thiénopyrazine par une méthode de revêtement ou une méthode d'impression, et qui présente une forte mobilité des porteurs et un rapport on/off élevé ; et un transistor à effet de champ organique présentant des caractéristiques ambipolaires. La thiénopyrazine est représentée par la formule chimique (I). (Dans la formule, chacun des radicaux Ar1 et Ar2 représente un groupement aryle ; et chacun des radicaux R1 et R2 représente indépendamment un atome d'hydrogène, un groupement alkyle ou un groupement aryle, ou, de façon alternative, R1 et R2 représentent des groupements qui se combinent pour former un cycle.)
PCT/JP2010/071829 2009-12-08 2010-12-06 Thiénopyrazine et transistor à effet de champ l'incluant WO2011071018A1 (fr)

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JP2011514931A JP5650107B2 (ja) 2009-12-08 2010-12-06 チエノピラジン化合物、およびそれを含有した電界効果トランジスタ
CN201080055572XA CN102781945A (zh) 2009-12-08 2010-12-06 噻吩并吡嗪化合物和含有其的场效应晶体管
US13/514,371 US8987447B2 (en) 2009-12-08 2010-12-06 Thienopyrazine compound and field effect transistor containing the same
EP10835938.1A EP2511278B1 (fr) 2009-12-08 2010-12-06 Thiénopyrazine et transistor à effet de champ l'incluant

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See also references of EP2511278A4

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016043233A1 (fr) * 2014-09-16 2016-03-24 国立研究開発法人理化学研究所 Procédé de fabrication de dispositif à semi-conducteur organique, procédé de traitement de surface, composé et dispositif à semi-conducteur organique

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KR20120104280A (ko) 2012-09-20
EP2511278B1 (fr) 2014-08-20
US20120248428A1 (en) 2012-10-04
US8987447B2 (en) 2015-03-24
JPWO2011071018A1 (ja) 2013-04-22
CN102781945A (zh) 2012-11-14
EP2511278A4 (fr) 2013-04-17
JP5650107B2 (ja) 2015-01-07

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