WO2011036866A1 - Transistor en film organique mince - Google Patents

Transistor en film organique mince Download PDF

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WO2011036866A1
WO2011036866A1 PCT/JP2010/005706 JP2010005706W WO2011036866A1 WO 2011036866 A1 WO2011036866 A1 WO 2011036866A1 JP 2010005706 W JP2010005706 W JP 2010005706W WO 2011036866 A1 WO2011036866 A1 WO 2011036866A1
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group
carbon atoms
film transistor
thin film
organic thin
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PCT/JP2010/005706
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Japanese (ja)
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中村浩昭
栗原直樹
近藤浩史
齊藤雅俊
中野裕基
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出光興産株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C22/00—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom
    • C07C22/02—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings
    • C07C22/04—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings containing six-membered aromatic rings
    • C07C22/08—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings containing six-membered aromatic rings containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
    • C07C25/18—Polycyclic aromatic halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
    • C07C25/18—Polycyclic aromatic halogenated hydrocarbons
    • C07C25/22—Polycyclic aromatic halogenated hydrocarbons with condensed rings
    • 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
    • H10K10/80—Constructional details
    • H10K10/82—Electrodes
    • H10K10/84—Ohmic electrodes, e.g. source or drain electrodes
    • 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]
    • H10K10/464—Lateral top-gate IGFETs comprising only a single gate
    • 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]
    • H10K10/466—Lateral bottom-gate IGFETs comprising only a single gate

Definitions

  • the present invention relates to an organic thin film transistor. More specifically, the present invention relates to an organic thin film transistor capable of high-speed operation and low-voltage driving because a charge injection layer bonded to a source electrode and a drain electrode contains a compound having a low contact resistance.
  • TFTs Thin film transistors
  • FIG. 1 A cross-sectional structure of a typical TFT is shown in FIG.
  • a TFT has a gate electrode, an insulator layer, and an organic semiconductor layer in this order on a substrate, and has a source electrode and a drain electrode formed on the organic semiconductor layer with a predetermined interval.
  • the organic semiconductor layer forms a channel region, and an on / off operation is performed by controlling a current flowing between the source electrode and the drain electrode with a voltage applied to the gate electrode.
  • this TFT has been manufactured using amorphous or polycrystalline silicon.
  • a CVD (Chemical Vapor Deposition) apparatus used for manufacturing a TFT using silicon is very expensive.
  • the increase in the size of the display device, etc. has been accompanied by a significant increase in manufacturing cost.
  • the process of forming amorphous or polycrystalline silicon is performed at a very high temperature, the types of materials that can be used as a substrate are limited, and a lightweight resin substrate cannot be used. It was.
  • a TFT using an organic substance instead of amorphous or polycrystalline silicon has been proposed.
  • Vacuum deposition and coating methods are known as film formation methods used when forming TFTs with organic materials.
  • an increase in the size of the element can be realized while suppressing an increase in manufacturing cost. Therefore, the process temperature required for film formation can be made relatively low.
  • a TFT using an organic substance has an advantage that there are few restrictions when selecting a material used for a substrate, and its practical use is expected.
  • TFTs using organic substances have been actively reported, and examples thereof include Non-Patent Documents 1 to 16.
  • Organic substances used in the organic compound layer of TFT include p-type polymers such as conjugated polymers and thiophenes (Patent Documents 1 to 5 etc.), metal phthalocyanine compounds (Patent Document 6 etc.), and condensed aromatic hydrocarbons such as pentacene. (Patent Documents 7 and 8, etc.) are used in the form of a simple substance or a mixture with other compounds.
  • Patent Document 9 discloses 1,4,5,8-naphthalenetetracarboxyl dianhydride (NTCDA) and the like
  • Patent Document 10 discloses fluorinated phthalocyanine. Has been.
  • Equation (1) is an expression established in a region called a linear region where the drain voltage is small
  • Equation (2) is an equation established in a region called a saturation region where the drain voltage is large.
  • I D drain current
  • V D drain voltage
  • V G gate voltage
  • V th threshold voltage
  • ⁇ field effect mobility
  • C insulating film capacitance per unit area
  • L channel length
  • W Channel width.
  • an intermediate layer charge injection layer
  • a hole injection material (4,4′-bis [phenyl (3-methylphenyl) amino] biphenyl) (TPD) and electron injection of an organic electroluminescence (EL) element are used.
  • TPD hole injection material
  • EL organic electroluminescence
  • 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole) (PBD) is used.
  • the source electrode and the drain electrode each include a carrier relay film and a carrier conductive film, and the metal constituting the carrier relay film in contact with the organic semiconductor has a work function in the vicinity of the ionization potential of the organic semiconductor.
  • Patent Document 13 discloses an organic thin film transistor in which a charge injection layer made of an inorganic material is inserted between a source electrode and a drain electrode and an organic semiconductor film.
  • a carbon nanotube is provided between the electrode and the organic semiconductor layer.
  • an intermediate layer made of copper phthalocyanine or the like is formed, and in Patent Document 16, an intermediate layer having a permanent dipole moment such as polyvinylidene fluoride is formed.
  • the intermediate layer is formed using a hexaazatriphenylene-based material.
  • Non-Patent Document 17 an attempt is made to improve the charge injection efficiency between the electrode and the organic semiconductor by treating the electrode with pentafluorothiophenol. A combination of the above techniques is also conceivable.
  • Patent Document 18 a layer containing an organic compound having a hole transporting property and a metal oxide, and a layer containing an organic compound having an electron transporting property and an alkali metal or alkaline earth metal, respectively. Is inserted between the electrode and the organic semiconductor.
  • these disclosed materials were used, although the voltage could be slightly lowered, the performance was insufficient practically.
  • Non-Patent Document 18 As another voltage reduction technique, in Non-Patent Document 18, a source electrode, an organic semiconductor layer, and a drain electrode are stacked in a vertical direction, and a gate electrode is inserted between the source electrode and the drain electrode.
  • the vertical transistor structure the same charge transport material as that of the organic EL element can be used (Non-patent Document 18, copper phthalocyanine is used as the charge transport material), so that the contact resistance with the electrode is reduced and charge injection is performed. To lower the voltage.
  • the vertical transistor structure has a problem that if the charge injection from the electrode is improved, the OFF current increases and the ON / OFF ratio decreases.
  • Patent Document 19 discloses that a material used for an organic semiconductor layer of an organic thin film transistor is a phenyl group at both ends, and two or more triple bonds and one or more divalent aromatic hydrocarbon groups or aromatics between them. A compound in which group heterocyclic groups are alternately bonded is disclosed. However, there is no disclosure or suggestion of using this compound in the charge injection layer disposed between the organic semiconductor layer and the source electrode and between the organic semiconductor layer and the drain electrode.
  • the organic semiconductor layer is required to be made of a material having a high mobility because it has a function of moving charges from the source electrode to the drain electrode.
  • required by an organic-semiconductor layer is low.
  • organic compounds are brought into contact with each other, so that smooth charge transfer between the interfaces tends to occur. For this reason, the importance of functions other than mobility is further reduced.
  • the charge injection layer is required to have a function of injecting charges from the electrodes.
  • the mobility of the charge injection layer is also important, but considering the film thickness of the charge injection layer, which is preferably 0.3 nm to 100 nm, which is extremely short compared with the channel length of preferably 5 ⁇ m to 100 ⁇ m, the organic semiconductor Mobility is less important than what is required for a layer. For example, the mobility of TPD and PBD used for the intermediate layer material in Patent Document 11 and copper phthalocyanine used in Patent Document 15 are not high.
  • the charge injection layer is required to have a function of reducing contact resistance with an electrode made of an inorganic material such as metal.
  • the source and drain electrodes repeat oxidation and reduction at the interface with the charge injection layer due to charge transfer. For this reason, the material for the charge injection layer is required to have resistance to oxidation and reduction. Thus, an excellent material for an organic semiconductor layer cannot be easily transferred to a material for a charge injection layer.
  • the present invention has been made in order to solve the above-described problems.
  • An organic thin film transistor that has a high response speed (driving speed), a large on / off ratio, and can be driven at a low voltage, and an organic thin film light emitting device using the organic thin film transistor.
  • An object is to provide a transistor.
  • the present inventors can achieve the above object by using a compound represented by the following general formula (1) in the charge injection layer of the organic thin film transistor. And the present invention has been completed. That is, in the present invention, at least three terminals of a gate electrode, a source electrode, and a drain electrode, an insulator layer, and an organic semiconductor layer are provided on a substrate, and a source-drain current is controlled by applying a voltage to the gate electrode. In the organic thin film transistor, a charge injection layer is provided between the organic semiconductor layer and the source-drain, and the charge injection layer provides an organic thin film transistor containing a compound represented by the following formula (1).
  • Ar 1 is represented by the following formula (2)
  • Ar 3 is represented by the following formula (3).
  • R 1 to R 10 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms, a haloalkyl group having 1 to 30 carbon atoms, or a carbon number of 1
  • Dialkylamino groups (alkyl groups may be bonded to each other to form a ring structure containing a nitrogen atom), alkylsulfonyl groups having 1 to 30 carbon atoms, haloalkylsulfonyl groups having 1 to 30 carbon atoms, 6 to 6 carbon atoms 60 aromatic hydrocarbon group, C1-C60 aromatic
  • R 1 to R 5 and R 6 to R 10 may be adjacent to each other to form a saturated or unsaturated cyclic structure.
  • Ar 2 is a divalent aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or a divalent aromatic heterocyclic group having 2 to 60 carbon atoms which may have a substituent. is there.
  • n is an integer of 1 to 20.
  • the present invention also provides an organic thin-film light emitting transistor that controls light emission by obtaining light emission using a current flowing between a source and a drain in an organic thin film transistor and applying a voltage to a gate electrode.
  • the organic thin film transistor of the present invention has a high response speed (driving speed), a large on / off ratio, a low driving voltage, and has high performance as a transistor, and can emit light. Can also be used.
  • FIG. 1 is a diagram illustrating a configuration of an organic thin film transistor of Example 1.
  • FIG. It is a figure which shows the structure of the organic thin-film transistor of Example 14.
  • FIG. It is a figure which shows the output curve of the organic thin-film transistor of Example 1.
  • FIG. It is a figure which shows the output curve of the organic thin-film transistor of the comparative example 1.
  • the organic thin film transistor of the present invention is provided with at least three terminals of a gate electrode, a source electrode, and a drain electrode, an insulator layer, and an organic semiconductor layer on a substrate, and a source-drain current is controlled by applying a voltage to the gate electrode.
  • a charge injection layer is provided between the organic semiconductor layer and the source-drain, and the charge injection layer contains a compound represented by the following general formula (1).
  • Ar 1 is represented by the following general formula (2)
  • Ar 3 is represented by the following general formula (3).
  • R 1 to R 10 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms, a haloalkyl group having 1 to 30 carbon atoms, or 1 to 30 alkoxy groups, 1-30 haloalkoxy groups, 1-30 alkylthio groups, 1-30 haloalkylthio groups, 1-30 alkylamino groups, 2-30 carbon atoms Dialkylamino group (the alkyl groups may be bonded to each other to form a ring structure containing a nitrogen atom), an alkylsulfonyl group having 1 to 30 carbon atoms, a haloalkylsulfonyl group having 1 to 30 carbon atoms, or 6 to 60 carbon atoms An aromatic hydrocarbon group having 1 to 60 carbon atoms, an alkylsilyl group having 3 to 30 carbon atoms, or a cyano group, each of which may have a substituent.
  • R 1 to R 10 each independently
  • halogen atom examples include fluorine, chlorine, bromine and iodine atoms.
  • alkyl group examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, and n-heptyl group.
  • N-octyl group N-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group and the like.
  • haloalkyl group examples include chloromethyl group, 1-chloroethyl group, 2-chloroethyl group, 2-chloroisobutyl group, 1,2-dichloroethyl group, 1,3-dichloroisopropyl group, 2,3-dichloro- t-butyl group, 1,2,3-trichloropropyl group, bromomethyl group, 1-bromoethyl group, 2-bromoethyl group, 2-bromoisobutyl group, 1,2-dibromoethyl group, 1,3-dibromoisopropyl group, 2,3-dibromo-t-butyl group, 1,2,3-tribromopropyl group, iodomethyl group, 1-iodoethyl group, 2-iodoethyl group, 2-iodoisobutyl group, 1,2-diiodoethyl group, 1, 3-diio
  • the alkoxy group is a group represented by —OX 1
  • examples of X 1 include the same examples as described for the alkyl group
  • the haloalkoxy group is represented by —OX 2.
  • Examples of X 2 include the same examples as described for the haloalkyl group.
  • the alkylthio group is a group represented by —SX 1 and examples of X 1 include the same examples as described for the alkyl group.
  • the haloalkylthio group is represented by —SX 2 Examples of X 2 include the same examples as described for the haloalkyl group.
  • the alkylamino group is a group represented by —NHX 1 ; the dialkylamino group is a group represented by —NX 1 X 3 ; and X 1 and X 3 are the same as those described for the alkyl group, respectively. Similar examples are given.
  • the alkyl group of the dialkylamino group may be bonded to each other to form a ring structure containing a nitrogen atom, and examples of the ring structure include pyrrole, pyrrolidine, piperidine and the like.
  • the alkylsulfonyl group is a group represented by —SO 2 X 1 , and examples of X 1 include the same examples as described for the alkyl group, and the haloalkylsulfonyl group includes —SO 2 a group represented by X 2, examples of X 2 are examples similar to those described in the haloalkyl group.
  • the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a fluorenyl group, a perylenyl group, a tetracenyl group, and a pentacenyl group.
  • Examples of the aromatic heterocyclic group include a thiophenyl group, a dithienophenyl group, a benzofuranyl group, a benzothiophenyl group, a quinolinyl group, a carbazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, and a benzothiadiazonyl group.
  • the alkylsilyl group is a group represented by —SiX 1 X 2 X 3 , and examples of X 1 , X 2 and X 3 are the same as those described for the alkyl group.
  • Examples of the saturated cyclic structure include a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, and a 1,4 dioxane ring.
  • Examples of the unsaturated cyclic structure include the same examples as those described for the aromatic hydrocarbon group.
  • Ar 2 is a divalent aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, and a divalent group having 2 to 60 carbon atoms which may have a substituent.
  • the divalent aromatic hydrocarbon group having 6 to 60 carbon atoms is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and examples thereof include 2 such as benzene, naphthalene, anthracene, phenanthrene, tetracene, chrysene, or pentacene.
  • the divalent aromatic heterocyclic group having 2 to 60 carbon atoms is preferably a condensed polycyclic aromatic heterocyclic ring having 6 to 60 carbon atoms (preferably 8 to 60 carbon atoms), and is preferably a condensed polycyclic aromatic group.
  • the heterocyclic group is preferably a structure containing a benzene ring or a naphthalene ring, and more preferably a structure containing a benzene ring.
  • Examples thereof include divalent residues such as pyrrole, pyridine, pyrimidine, imidazole, thiazole, dithienobenzene, benzothiadiazole, quinoline, benzothiophene, benzodithiophene, dibenzothiophene, benzothienobenzothiophene, benzofuran, or dibenzofuran.
  • the divalent residues of dithienobenzene, benzothiophene, dibenzothiophene, benzofuran and dibenzofuran are preferred.
  • Examples of the substituent for Ar 2 include an alkyl group having 1 to 30 carbon atoms and a haloalkyl group having 1 to 30 carbon atoms.
  • n is an integer of 1 to 20, and may be 1 or a plurality of 2 or more, but is preferably an integer of 1 to 5.
  • R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 9 and R 10 are all hydrogen atoms, and at least one of R 3 and R 8 Is a halogen atom, an alkyl group having 1 to 12 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, a haloalkoxy group having 1 to 8 carbon atoms, or a dialkylamino group having 2 to 16 carbon atoms (the alkyl groups are bonded to each other).
  • a ring structure containing a nitrogen atom may be formed), and when it is not a halogen atom, an alkyl group, a haloalkyl group, a haloalkoxy group, or a dialkylamino group, it is preferably a hydrogen atom. It is also preferred that at least one of R 3 and R 8 is a linear alkyl group having 1 to 12 carbon atoms.
  • the compound represented by the general formula (1) is preferably a compound represented by the following general formula (4).
  • R 1 to R 14 each represent the same group as R 1 to R 10 in the general formula (1), and the same specific examples can be given as examples.
  • R 1 to R 5 , R 6 to R 10 , R 11 to R 12 , and R 13 to R 14 may be adjacent to each other to form a saturated or unsaturated cyclic structure, and specific examples similar to those described above can be given.
  • N is an integer of 1 to 20, and preferably an integer of 1 to 5.
  • R 11 to R 14 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, or an alkoxy having 1 to 8 carbon atoms.
  • an alkylthio group having 1 to 8 carbon atoms, a dialkylamino group having 2 to 8 carbon atoms (the alkyl groups may be bonded to each other to form a ring structure containing a nitrogen atom), alkylsulfonyl having 1 to 8 carbon atoms Group or a cyano group is preferred.
  • R 1 , R 2 , R 4 , R 5 , R 6 , R 7 and R 9 to R 14 are all hydrogen atoms, and at least one of R 3 and R 8 is a halogen atom.
  • any one of R 1 to R 14 is preferably a fluorine atom, a cyano group, a trifluoromethyl group, or a pentafluoroethyl group.
  • the compound represented by the general formula (1) is preferably a compound represented by the following general formula (5).
  • R 1 to R 10 are the same as in formula (1).
  • R 15 to R 22 are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a haloalkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or a haloalkoxy group having 1 to 30 carbon atoms.
  • R 1 ⁇ R 0 include the same specific examples as.
  • R 1 to R 5 and R 6 to R 10 may be adjacent to each other to form a saturated cyclic structure, and specific examples of the cyclic structure include the same specific examples as described above.
  • R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 9 , R 10 and R 15 to R 22 are all hydrogen atoms, and at least R 3 and R 8
  • One is a halogen atom, an alkyl group having 1 to 12 carbon atoms (particularly a linear alkyl group), a haloalkyl group having 1 to 8 carbon atoms, a haloalkoxy group having 1 to 8 carbon atoms, or a dialkyl having 2 to 16 carbon atoms
  • An amino group (the alkyl group may be bonded to each other to form a ring structure containing a nitrogen atom), and if not a halogen atom, an alkyl group, a haloalkyl group, a haloalkoxy group, or a dialkylamino group, It is preferable.
  • any one of R 1 to R 22 is preferably a fluorine atom, a
  • the compound represented by the formula (1) preferably has an ionization potential of 5.2 eV or more, more preferably 5.3 eV or more. Moreover, the upper limit of the ionization potential of the compound represented by Formula (1) is 7.0 eV, for example. When the ionization potential of the compound represented by formula (1) is 5.2 eV or more, it is difficult to oxidize and has high atmospheric stability.
  • the ionization potential can be measured by, for example, photoelectron spectroscopy or cyclic voltammetry.
  • a device having a high field effect mobility and a high on / off ratio can be obtained by using a material having a high purity. Therefore, it is desirable to purify the compound represented by the formula (1) by a technique such as column chromatography, recrystallization, distillation, sublimation, etc., if necessary. Preferably, it is possible to improve the purity by repeatedly using these purification methods or combining a plurality of methods. Furthermore, it is desirable to repeat sublimation purification at least twice or more as the final step of purification as necessary.
  • a material having a purity of 90% or more, more preferably 95% or more, particularly preferably 99% or more of the compound represented by the formula (1) measured by HPLC Accordingly, there is a possibility that the field effect mobility and the on / off ratio of the organic thin film transistor can be increased and the driving voltage can be lowered to bring out the performance inherent to the material.
  • the element structure of the organic thin-film transistor of this invention is demonstrated.
  • As an element configuration of the organic thin film transistor of the present invention at least three terminals of a gate electrode, a source electrode, and a drain electrode, an insulator layer, and an organic semiconductor layer are provided on a substrate, and charge is injected between the organic semiconductor layer and the source-drain.
  • the thin film transistor is not limited as long as it has a layer and controls the source-drain current by applying a voltage to the gate electrode, and may have a known element structure.
  • elements A to D are shown in FIGS. 2 to 5 as typical element configurations of organic thin film transistors.
  • the organic thin film transistor of the present invention has a field effect transistor (FET) structure.
  • the organic thin film transistor is formed with an organic semiconductor layer (organic compound layer), a source electrode and a drain electrode formed to face each other with a predetermined distance, and a predetermined distance from the source electrode and the drain electrode. And a current flowing between the source and drain electrodes is controlled by applying a voltage to the gate electrode.
  • the distance between the source electrode and the drain electrode is determined by the use of the organic thin film transistor of the present invention, and is usually 0.1 ⁇ m to 1 mm, preferably 1 ⁇ m to 100 ⁇ m, and more preferably 5 ⁇ m to 100 ⁇ m.
  • the organic thin film transistor 4 of the element C has a gate electrode 70 and an insulator layer 60 on the substrate 10 in this order.
  • An organic semiconductor layer 50 is formed on 60, and has a pair of a source electrode 20 and a drain electrode 30 formed on the organic semiconductor layer 50 with a predetermined gap therebetween. Further, the source electrode 20, the drain electrode 30, and the organic semiconductor layer 50 are provided.
  • the charge injection layer 40 is inserted between the two.
  • the organic semiconductor layer 50 forms a channel region, and is turned on / off by controlling a current flowing between the source electrode 20 and the drain electrode 30 with a voltage applied to the gate electrode 70.
  • the charge injection layer 40 containing the compound represented by the formula (1) is stacked between the source electrode 20 and the organic semiconductor layer 50 and between the drain electrode 30 and the organic semiconductor layer 50, whereby the source electrode 20, the contact resistance between the drain electrode 30 and the organic semiconductor layer 50 can be reduced, and the drive voltage can be reduced.
  • Organic semiconductor layer The organic semiconductor used in the present invention is not particularly limited. Organic semiconductors used for organic TFTs as generally disclosed can be used. Specific examples are shown below.
  • a crystalline material Since high field effect mobility can be obtained, a crystalline material is usually used. Specifically, the following materials can be exemplified.
  • Acenes which may have a substituent such as naphthalene, anthracene, tetracene, pentacene, hexacene, heptacene, etc., for example, 1,4-bisstyrylbenzene, 1,4-bis (2-methylstyryl) benzene, 1 , 4-bis (3-methylstyryl) benzene (4MSB), 1,4-bis (4-methylstyryl) benzene, polyphenylene vinylene, etc.
  • a styryl structure represented by C 6 H 5 —CH ⁇ CH—C 6 H 5 (2) Compounds containing thiophene rings shown below (a) Substitution of derivatives of ⁇ -4T, ⁇ -5T, ⁇ -6T, ⁇ -7T, ⁇ -8T, etc.
  • TCNQ cyanonaphth-2,6-quinodimethane
  • TCNNQ fullerenes
  • fullerenes such as C60, C70, PCBM, N, N′-diphenyl-3,4,9,10-perylenetetracarboxylic acid diimide, N, N ′
  • tetracarboxylic acids such as dioctyl-3,4,9,10-perylenetetracarboxylic acid diimide (C8-PTCDI), NTCDA, 1,4,5,8-naphthalenetetracarboxyldiimide (NTCDI), and the like.
  • the material used for an organic-semiconductor layer is a material different from the material used for the charge injection layer mentioned later.
  • the substrate in the organic thin film transistor of the present invention plays a role of supporting the structure of the organic thin film transistor.
  • a material in addition to glass, inorganic compounds such as metal oxides and nitrides, plastic films (PET, PES, PC) It is also possible to use metal substrates or composites or laminates thereof. Further, when the structure of the organic thin film transistor can be sufficiently supported by the components other than the substrate, it is possible not to use the substrate.
  • a silicon (Si) wafer is often used as a material for the substrate.
  • Si itself can be used as the gate electrode / substrate 12 shown in FIG. It is also possible to oxidize the surface of Si to form SiO 2 and use it as the insulator layer 62.
  • a metal layer such as Au may be formed on the Si substrate 12 serving as a substrate and gate electrode as an electrode for connecting a lead wire.
  • the material for the gate electrode, the source electrode and the drain electrode is not particularly limited as long as it is a conductive material.
  • the source electrode and the drain electrode those formed using a fluid electrode material such as a solution, paste, ink, or dispersion liquid containing the above conductive material can be used.
  • the solvent or dispersion medium is preferably a solvent or dispersion medium containing 60% by mass or more, preferably 90% by mass or more of water, in order to suppress damage to the organic semiconductor.
  • the dispersion containing the metal fine particles for example, a known conductive paste or the like may be used, but a dispersion containing metal fine particles having a particle size of usually 0.5 nm to 50 nm, 1 nm to 10 nm is preferable. .
  • Examples of the material of the fine metal particles include platinum, gold, silver, nickel, chromium, copper, iron, tin, antimony lead, tantalum, indium, palladium, tellurium, rhenium, iridium, aluminum, ruthenium, germanium, molybdenum, tungsten. Zinc or the like can be used. It is also preferable to form an electrode using a dispersion in which these metal fine particles are dispersed in water or a dispersion medium which is an arbitrary organic solvent using a dispersion stabilizer mainly composed of an organic material.
  • metal ions can be reduced in the liquid phase, such as a physical generation method such as gas evaporation method, sputtering method, metal vapor synthesis method, colloid method, coprecipitation method, etc.
  • a chemical production method for producing metal fine particles preferably disclosed in JP-A-11-76800, JP-A-11-80647, JP-A-11-319538, JP-A-2000-239853, and the like.
  • the shape is heated in the range of 100 ° C. to 300 ° C., preferably 150 ° C. to 200 ° C., if necessary.
  • Metal fine particles are thermally fused to form an electrode pattern having a desired shape.
  • a known conductive polymer whose conductivity has been improved by doping or the like as a material for the gate electrode, the source electrode and the drain electrode.
  • a known conductive polymer whose conductivity has been improved by doping or the like
  • PEDOT polyethylenedioxythiophene
  • a polystyrene sulfonic acid complex or the like is also preferably used.
  • the material for forming the source electrode and the drain electrode is preferably a material having low electrical resistance on the contact surface with the charge injection material.
  • the electrical resistance at this time corresponds to the field effect mobility when the current control device is manufactured as described above, and the resistance needs to be as small as possible in order to obtain a large field effect mobility.
  • contact resistance There are various factors of contact resistance. For example, the adhesion force between the electrode and the organic compound, the adhesion area, the interaction at the interface between the electrode and the organic compound (polarization at the interface, charge transfer, mirror image effect, etc.). Of particular importance is the magnitude relationship between the work function of the electrode material and the energy level of the charge injection layer.
  • the work function (W) of the electrode material is a
  • the ionization potential of the charge injection layer is (Ip)
  • the electron affinity (Af) of the charge injection layer is c
  • a, b, and c are all positive values with reference to the vacuum level.
  • ba ⁇ 1.5 eV (formula (I)) is preferable, and ba ⁇ 1.0 eV is more preferable.
  • the work function of the electrode material is as large as possible, and the work function is preferably 4.0 eV or more. More preferably, the work function is 4.2 eV or more.
  • the value of the work function of a metal is, for example, an effective metal having a work function of 4.0 eV or more described in Chemical Handbook II-493 (revised 3 edition, published by The Chemical Society of Japan, Maruzen Co., Ltd. 1983).
  • the high work function metal is mainly Ag (4.26, 4.52, 4.64, 4.74 eV), Al (4.06, 4.24, 4.41 eV), Au (5.1, 5.37, 5.47 eV), Be (4.98 eV), Bi (4.34 eV), Cd (4.08 eV), Co (5.0 eV), Cu (4.65 eV), Fe (4.5, 4.67, 4.81 eV), Ga (4.3 eV), Hg (4.4 eV), Ir (5.42, 5.76 eV), Mn (4.1 eV), Mo (4 .53, 4.55, 4.95 eV), Nb (4.02, 4.36).
  • noble metals Al, Au, Cu, Pt
  • conductive polymers such as ITO, polyaniline and PEDOT: PSS and carbon are preferred. Even if one or more of these high work function substances are included as the electrode material, there is no particular limitation as long as the work function satisfies the formula (I).
  • the work function of the electrode material is preferably as small as possible, and the work function is preferably 4.3 eV or less. More preferably, the work function is 3.7 eV or less.
  • the low work function metal it has a work function of 4.3 eV or less as described in, for example, Chemical Handbook II-493 (revised 3rd edition, published by Maruzen Co., Ltd., 1983).
  • the electrode material Even if one or more of these low work function substances are included as the electrode material, there is no particular limitation as long as the work function satisfies the above formula (II). However, since the low work function metal easily deteriorates when exposed to moisture and oxygen in the atmosphere, it is desirable to coat with a stable metal in the air such as Ag or Au as necessary.
  • the film thickness necessary for the coating is 10 nm or more, and as the film thickness increases, the film can be protected from oxygen and water. However, for practical reasons, the thickness is preferably 1 ⁇ m or less for the purpose of increasing productivity.
  • the electrode may be formed by means such as vapor deposition, electron beam vapor deposition, sputtering, atmospheric pressure plasma method, ion plating, chemical vapor deposition, electrodeposition, electroless plating, spin coating, printing or ink jet. Is done.
  • a conductive thin film formed using the above method is formed using a known photolithographic method or a lift-off method, on a metal foil such as aluminum or copper.
  • a resist is formed and etched by thermal transfer, ink jet, or the like.
  • a conductive polymer solution or dispersion, a dispersion containing metal fine particles, or the like may be directly patterned by an ink jet method, or may be formed from a coating film by lithography, laser ablation, or the like.
  • a method of patterning a conductive ink or conductive paste containing a conductive polymer or fine metal particles by a printing method such as relief printing, intaglio printing, lithographic printing, or screen printing can also be used.
  • the film thickness of the electrode formed in this way is not particularly limited as long as current conduction is possible, but it is preferably in the range of 0.2 nm to 10 ⁇ m, more preferably 4 nm to 300 nm.
  • the resistance is increased due to the thin film thickness, and a voltage drop does not occur.
  • the film since the film is not too thick, it does not take time to form the film, and when another layer such as a protective layer or an organic semiconductor layer is laminated, the laminated film can be smooth without causing a step.
  • a buffer layer may be provided between the charge injection layer and the source and drain electrodes for the purpose of further improving the charge injection efficiency.
  • the buffer layer has an alkali metal or alkaline earth metal ion bond such as LiF, Li 2 O, CsF, NaCO 3 , KCl, MgF 2 , and CaCO 3 used for an organic EL cathode for an n-type organic thin film transistor.
  • alkali metal or alkaline earth metal ion bond such as LiF, Li 2 O, CsF, NaCO 3 , KCl, MgF 2 , and CaCO 3 used for an organic EL cathode for an n-type organic thin film transistor.
  • organic EL such as Alq.
  • cyano compounds such as FeCl 3 , TCNQ, F4-TCNQ, HAT, CFx, GeO 2 , SiO 2 , MoO 3 , V 2 O 5 , VO 2 , V 2 O 3 , MnO, Mn 3 O 4 , ZrO 2 , WO 3 , TiO 2 , In 2 O 3 , ZnO, NiO, HfO 2 , Ta 2 O 5 , ReO 3 , metal oxides other than alkaline earth metals, such as PbO 2 , Inorganic compounds such as ZnS and ZnSe are desirable. In many cases, these oxides cause oxygen vacancies, which are suitable for hole injection. Further, amine compounds such as TPD and NPD, and compounds used as a hole injection layer and a hole transport layer in an organic EL device such as CuPc may be used. Moreover, what consists of two or more types of said compounds is desirable.
  • the material of the insulator layer in the organic thin film transistor of the present invention is not particularly limited as long as it has electrical insulation and can be formed as a thin film.
  • Metal oxide including silicon oxide
  • metal nitride (Including silicon nitride)
  • polymers low molecular organic molecules, and the like, materials having an electrical resistivity at room temperature of 10 ⁇ cm or more can be used, and an inorganic oxide film having a high relative dielectric constant is particularly preferable.
  • Inorganic oxides include silicon oxide, aluminum oxide, tantalum oxide, titanium oxide, tin oxide, vanadium oxide, barium strontium titanate, barium zirconate titanate, lead zirconate titanate, lead lanthanum titanate, strontium titanate, Barium titanate, barium magnesium fluoride, lanthanum oxide, fluorine oxide, magnesium oxide, bismuth oxide, bismuth titanate, niobium oxide, strontium bismuth titanate, strontium bismuth tantalate, tantalum pentoxide, niobium tantalate Examples thereof include bismuth acid, trioxide yttrium, and combinations thereof, and silicon oxide, aluminum oxide, tantalum oxide, and titanium oxide are preferable.
  • inorganic nitrides such as silicon nitride (Si 3 N 4 , SixNy (x, y> 0)) and aluminum nitride can be suitably used.
  • the insulator layer may be formed of a precursor containing an alkoxide metal, and the insulator layer is formed by coating a solution of the precursor on a substrate, for example, and subjecting the solution to a chemical solution treatment including heat treatment. It is formed.
  • the metal in the alkoxide metal is selected from, for example, a transition metal, a lanthanoid, or a main group element.
  • alkoxide in the alkoxide metal examples include, for example, alcohols including methanol, ethanol, propanol, isopropanol, butanol, isobutanol, methoxyethanol, ethoxyethanol, propoxyethanol, butoxyethanol, pentoxyethanol, heptoxyethanol, Examples thereof include those derived from alkoxy alcohols including methoxypropanol, ethoxypropanol, propoxypropanol, butoxypropanol, pentoxypropanol, heptoxypropanol, and the like.
  • the insulator layer when the insulator layer is made of the above-described material, polarization easily occurs in the insulator layer, and the threshold voltage for transistor operation can be reduced.
  • the insulator layer can be formed of silicon nitride such as Si 3 N 4 , SixNy, and SiONx (x, y> 0).
  • an insulator layer using an organic compound polyimide, polyamide, polyester, polyacrylate, photo radical polymerization system, photo cation polymerization system photo-curing resin, copolymer containing acrylonitrile component, polyvinyl alcohol, novolac resin, Also, cyanoethyl pullulan or the like can be used.
  • wax polyethylene, polychloropyrene, polyethylene terephthalate, polyoxymethylene, polyvinyl chloride, polyvinylidene fluoride, polysulfone, polyimide cyanoethyl pullulan, poly (vinylphenol) (PVP), poly (methyl methacrylate) (PMMA), polycarbonate ( In addition to PC), polystyrene (PS), polyolefin, polyacrylamide, poly (acrylic acid), novolac resin, resole resin, polyimide, polyxylylene, epoxy resin, high molecular materials with high dielectric constant such as pullulan may be used. Is possible.
  • an organic compound having water repellency is particularly preferable.
  • the interaction between the insulator layer and the organic semiconductor layer is suppressed, Utilizing the inherent cohesion, the crystallinity of the organic semiconductor layer can be increased and the device performance can be improved.
  • Examples of such compounds include polyparaxylylene derivatives described in Yasuda et al. Jpn. J. Appl. Phys. Vol. 42 (2003) pp. 6614-6618 and Janos Veres et al. Chem. Mater., Vol. 16 (2004). ) The thing of pp.4543-4555 is mentioned. Further, when such a top gate structure as shown in FIGS. 2 and 5 is used, if such an organic compound is used as a material for the insulator layer, the film can be formed with reduced damage to the organic semiconductor layer. Therefore, it is an effective method.
  • the pre-insulator layer may be a mixed layer using a plurality of inorganic or organic compound materials as described above, or may be a laminated structure of these.
  • the performance of the device can be controlled by mixing or laminating a material having a high dielectric constant and a material having water repellency, if necessary.
  • the insulator layer may include an anodic oxide film or the anodic oxide film as a configuration.
  • the anodized film is preferably sealed.
  • the anodized film is formed by anodizing a metal that can be anodized by a known method. Examples of the metal that can be anodized include aluminum and tantalum, and the anodizing method is not particularly limited, and a known method can be used.
  • An oxide film is formed by anodizing. Any electrolyte solution that can form a porous oxide film can be used as the anodizing treatment.
  • sulfuric acid, phosphoric acid, oxalic acid, chromic acid, boric acid, sulfamic acid, benzenesulfone, and the like can be used.
  • An acid or the like or a mixed acid obtained by combining two or more of these or a salt thereof is used.
  • the treatment conditions for anodization vary depending on the electrolyte used and cannot be specified in general. In general, however, the concentration of the electrolyte is 1 to 80% by mass, the temperature of the electrolyte is 5 to 70 ° C., and the current density. The ranges of 0.5 to 60 A / cm 2 , voltage of 1 to 100 volts, and electrolysis time of 10 seconds to 5 minutes are suitable.
  • a preferred anodizing treatment is a method in which an aqueous solution of sulfuric acid, phosphoric acid or boric acid is used as the electrolytic solution and the treatment is performed with a direct current, but an alternating current can also be used.
  • the concentration of these acids is preferably 5 to 45% by mass, and the electrolytic treatment is preferably performed for 20 to 250 seconds at an electrolyte temperature of 20 to 50 ° C. and a current density of 0.5 to 20 A / cm 2 .
  • the thickness of the insulator layer As the thickness of the insulator layer, if the layer thickness is thin, the effective voltage applied to the organic semiconductor increases, so the drive voltage and threshold voltage of the device itself can be lowered, but conversely the leakage between the source and gate Since the current increases, it is necessary to select an appropriate film thickness, which is usually 1 nm to 5 ⁇ m, preferably 5 nm to 2 ⁇ m, more preferably 100 nm to 1 ⁇ m.
  • any orientation treatment may be performed between the insulator layer and the organic semiconductor layer.
  • a preferable example thereof is a method for improving the crystallinity of the organic semiconductor layer by reducing the interaction between the insulator layer and the organic semiconductor layer by performing a water repellent treatment or the like on the surface of the insulator layer.
  • a silane coupling agent such as octadecyltrichlorosilane, trichloromethylsilazane, or a self-organized alignment film material such as alkane phosphoric acid, alkane sulfonic acid, or alkane carboxylic acid is brought into contact with the insulating film surface in a liquid phase or gas phase.
  • An example is a method of appropriately drying after forming the self-assembled film.
  • a method in which a film made of polyimide or the like is provided on the surface of the insulating film and the surface is rubbed so as to be used for liquid crystal alignment is also preferable.
  • the insulator layer can be formed by vacuum deposition, molecular beam epitaxy, ion cluster beam, low energy ion beam, ion plating, CVD, sputtering, JP-A-11-61406, 11-133205, JP-A 2000-121804, 2000-147209, 2000-185362, etc., dry process such as atmospheric pressure plasma method, spray coating method, spin coating method, blade coating Examples thereof include wet processes such as a method by coating such as a method, a dip coating method, a cast method, a roll coating method, a bar coating method, and a die coating method, and a patterning method such as printing and ink jetting.
  • the wet process is a method of applying and drying a liquid in which fine particles of inorganic oxide are dispersed in an arbitrary organic solvent or water using a dispersion aid such as a surfactant as required, or an oxide precursor, for example,
  • a so-called sol-gel method in which a solution of an alkoxide body is applied and dried is used.
  • the film thickness of the organic semiconductor layer in the organic thin film transistor of the present invention is not particularly limited, but is usually 0.5 nm to 1 ⁇ m, preferably 2 nm to 250 nm.
  • a method for forming the organic semiconductor layer is not particularly limited, and a known method can be applied. For example, molecular beam deposition (MBE), vacuum deposition, chemical deposition, dipping of a solution in which a material is dissolved in a solvent Organic, as described above, by means of printing, spin coating, casting, bar coating, roll coating, etc., coating and baking, electropolymerization, self-assembly from solution, and combinations thereof It is made of a semiconductor layer material.
  • MBE molecular beam deposition
  • vacuum deposition chemical deposition
  • dipping of a solution in which a material is dissolved in a solvent Organic as described above, by means of printing, spin coating, casting, bar coating, roll coating, etc., coating and baking, electropolymerization, self-assembly from solution,
  • the field effect mobility is improved. Therefore, when film formation from a gas phase (evaporation, sputtering, etc.) is used, it is desirable to maintain the substrate temperature during film formation at a high temperature.
  • the temperature is preferably 50 to 250 ° C., more preferably 70 to 150 ° C.
  • the annealing temperature is preferably 50 to 200 ° C., more preferably 70 to 200 ° C., and the time is preferably 10 minutes to 12 hours, more preferably 1 to 10 hours.
  • the charge injection layer for the charge injection layer, one kind of material selected from the general formula (1), (4) or (5) may be used, or a plurality of known materials such as pentacene and thiophene oligomer may be combined. A mixed thin film made of a plurality of materials, a layer made of these materials alone, or a mixed film may be laminated and used. Further, different charge injection layers may be provided for the source electrode and the drain electrode, respectively.
  • the film thickness of the charge injection layer is preferably 0.1 nm to 1 ⁇ m, more preferably 0.3 nm to 100 nm, and the film formation method can be the same as the organic semiconductor layer. Further, as shown in 42 of FIG. 7, the charge injection layer may be disposed between the organic semiconductor layer 52 and the source-drain electrode in a portion where the source-drain electrode is not provided. In this case, the charge injection layer can be installed without using a metal mask, which is advantageous in terms of productivity.
  • a method for forming the organic thin film transistor of the present invention is not particularly limited and may be a known method. According to a desired element configuration, the substrate is charged, the gate electrode is formed, the insulator layer is formed, the organic semiconductor layer is formed, and the charge injection layer is formed. It is preferable to form a series of device manufacturing steps from formation, source electrode formation, and drain electrode formation without exposure to the atmosphere, because the device performance can be prevented from being impaired by moisture, oxygen, etc. in the atmosphere due to contact with the atmosphere. When it is unavoidable that the atmosphere must be exposed to the atmosphere once, the process after the organic semiconductor layer is formed is not exposed to the atmosphere at all.
  • the surface on which the source electrode and the drain electrode are partially stacked on the insulating layer) is cleaned and activated by ultraviolet irradiation, ultraviolet / ozone irradiation, oxygen plasma, argon plasma, etc., and then the organic semiconductor layer is stacked. It is preferable. Further, for example, in consideration of the influence on the organic semiconductor layer such as oxygen and water contained in the atmosphere, a gas barrier layer may be formed on the whole or a part of the outer peripheral surface of the organic thin film transistor element.
  • the gas barrier layer As a material for forming the gas barrier layer, those commonly used in this field can be used, and examples thereof include polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinyl chloride, polyvinylidene chloride, and polychlorotrifluoroethylene. . Furthermore, the inorganic substance which has the insulation illustrated in the said insulator layer can also be used.
  • the present invention also provides an organic thin-film light-emitting transistor that obtains light emission using a current flowing between a source and a drain and controls light emission by applying a voltage to a gate electrode.
  • the organic thin film transistor according to the present invention can also be used as a light emitting element using charges injected from the source and drain electrodes. That is, the organic thin film transistor can be used as an organic thin film light emitting transistor that also functions as a light emitting element (organic EL).
  • the light emission intensity can be controlled by controlling the current flowing between the source and drain electrodes with the gate electrode. Since the transistor for controlling light emission and the light emitting element can be integrated, the aperture ratio of the display can be improved and the cost can be reduced by the simplification of the manufacturing process, which provides a great practical advantage.
  • the contents described in the above detailed description are sufficient, but in order to operate the organic thin-film transistor of the present invention as an organic light-emitting transistor, holes from one of the source and drain and electrons from the other are used. In order to improve the light emission performance, it is preferable to satisfy the following conditions.
  • a hole injection electrode is an electrode containing a substance having a work function of 4.2 eV or higher.
  • An electron injecting electrode is an electrode containing a substance having a work function of 4.3 eV or less. More preferably, it is an organic thin film light-emitting transistor provided with an electrode in which one is hole-injecting and the other is electron-injecting.
  • it is an organic thin film light emitting transistor provided with a hole injection layer under one electrode and an electron injection layer under the other electrode.
  • Synthesis Example 1 Synthesis of Compound (1)
  • the compound (1) was synthesized according to the following synthesis route.
  • Example 1 (Production of organic thin film transistor) A surface of a Si substrate (also used as a P-type specific resistance 1 ⁇ cm gate electrode) was oxidized by a thermal oxidation method, and a 300 nm thermal oxide film was formed on the substrate to form an insulator layer. Further, after the SiO 2 film formed on one side of the substrate is completely removed by dry etching, chromium is deposited to a thickness of 20 nm by sputtering, and further gold (Au) is sputtered by 100 nm by sputtering. A film was formed and taken out as an electrode. This substrate was ultrasonically cleaned with a neutral detergent, pure water, acetone and ethanol for 30 minutes each, and further subjected to ozone cleaning.
  • a neutral detergent, pure water, acetone and ethanol for 30 minutes each, and further subjected to ozone cleaning.
  • the substrate was placed in a vacuum vapor deposition apparatus (ULVAC, EX-400), and 1,4-bis (4-methylstyryl) benzene (4MSB) was vapor-deposited at 0.05 nm / s on the insulator layer.
  • the film was formed as an organic semiconductor layer having a thickness of 50 nm at a speed.
  • a charge injection layer having a thickness of 20 nm was formed from the compound (1) prepared in Synthesis Example 1 through a metal mask at a deposition rate of 0.05 nm / s.
  • a charge injection layer and a source electrode and a drain electrode which are not in contact with each other were formed so that a distance (channel length L) was 75 ⁇ m.
  • an organic thin film transistor was manufactured by forming a film so that the width of the source electrode and the drain electrode (channel width W) was 5 mm (see FIG. 6).
  • a gate voltage of 0 to ⁇ 100 V was applied to the gate electrode of the obtained organic thin film transistor, and a current was applied by applying a voltage between the source and drain.
  • the obtained organic thin film transistor operated as a p-type transistor because electrons were induced in the channel region (between source and drain) of the organic semiconductor layer.
  • the on / off ratio of the current between the source and drain electrodes in the current saturation region was 1 ⁇ 10 6 .
  • the field effect mobility ⁇ S and the threshold voltage V T of the holes of the organic thin film transistor were calculated from the equation (2).
  • the output curve of the obtained organic thin film transistor is shown in FIG. From FIG. 8, it was found that the output curve is a straight line and the contact resistance is reduced in the region where the drain voltage is in the vicinity of 0V (the circled portion).
  • Example 2 An organic thin film transistor was manufactured and evaluated in the same manner as in Example 1 except that the charge injection layer was formed using the compound (42) instead of the compound (1). The results are shown in Table 1.
  • Example 3 An organic thin film transistor was manufactured and evaluated in the same manner as in Example 1 except that the charge injection layer was formed using the compound (162) instead of the compound (1). The results are shown in Table 1.
  • Example 4 An organic thin film transistor was manufactured and evaluated in the same manner as in Example 1 except that the charge injection layer was formed using the compound (9) instead of the compound (1). The results are shown in Table 1.
  • Example 5 An organic thin film transistor was manufactured and evaluated in the same manner as in Example 1 except that the charge injection layer was formed using the compound (43) instead of the compound (1). The results are shown in Table 1.
  • Example 6 An organic thin film transistor was manufactured and evaluated in the same manner as in Example 1 except that the charge injection layer was formed using the compound (60) instead of the compound (1). The results are shown in Table 1.
  • Example 7 An organic thin film transistor was manufactured and evaluated in the same manner as in Example 1 except that the charge injection layer was formed using the compound (70) instead of the compound (1). The results are shown in Table 1.
  • Example 8 An organic thin film transistor was manufactured and evaluated in the same manner as in Example 1 except that the charge injection layer was formed using the compound (110) instead of the compound (1). The results are shown in Table 1.
  • Example 9 An organic thin film transistor was manufactured and evaluated in the same manner as in Example 1 except that the charge injection layer was formed using the compound (171) instead of the compound (1). The results are shown in Table 1.
  • Example 10 An organic semiconductor layer was formed using N, N′-dioxyl-3,4,9,10-perylenedicarboximide (PTCDI-C8) instead of 1,4-bis (4-methylstyryl) benzene. Then, a compound (65) is used instead of the compound (1) to form a charge injection layer, and instead of Au, Ca is vacuum-deposited at a deposition rate of 0.05 nm / s to 20 nm, and then Ag is 0.05 nm / An organic thin film transistor was manufactured in the same manner as in Example 1 except that the source electrode and the drain electrode were formed by depositing 50 nm at a deposition rate of s and covering Ca. Evaluation was performed in the same manner as in Example 1 except that a gate voltage of 0 to +100 V was applied to the gate electrode of the obtained organic thin film transistor to drive n-type. The results are shown in Table 1.
  • PTCDI-C8 N, N′-dioxyl-3,4,9,10-perylenedicarboximi
  • Example 11 Except that MoO 3 was vacuum-deposited by 10 nm at a deposition rate of 0.05 nm / s and inserted as a buffer layer between the source and drain electrodes made of Au and the charge injection layer made of the compound (60), the same as in Example 6. Thus, an organic thin film transistor was manufactured and evaluated. The results are shown in Table 1.
  • Example 12 An organic thin film transistor was manufactured and evaluated in the same manner as in Example 10 except that the charge injection layer was formed using the compound (163) instead of the compound (65). The results are shown in Table 1.
  • Example 13 Instead of depositing the compound (1), 0.5% by mass of the compound (174) is dissolved in toluene, and the solution is used to form a film by a spin coating method, followed by drying at 80 ° C. in a nitrogen atmosphere, thereby injecting charges.
  • An organic thin film transistor was manufactured and evaluated in the same manner as in Example 1 except that the layer was formed. The results are shown in Table 1.
  • Example 14 In the organic thin film transistor manufacturing process of Example 1, when the charge injection layer using the compound (1) was formed, the compound (1) was deposited at a deposition rate of 0.05 nm / s with a thickness of 10 nm without passing through the metal mask. A charge injection layer was formed to manufacture the transistor shown in FIG. The evaluation results of this element are shown in Table 1.
  • Comparative Example 1 An organic thin film transistor was manufactured and evaluated in the same manner as in Example 1 except that the charge injection layer was not formed. The results are shown in Table 1. Moreover, the output curve of the obtained organic thin-film transistor is shown in FIG. From FIG. 9, it was found that in the region where the drain voltage is near 0V (the part surrounded by a circle), the output curve is bent and deviates from the straight line, the contact resistance is large and deviates from the characteristic of the equation (1).
  • Comparative Example 2 An organic thin film transistor was manufactured and evaluated in the same manner as in Example 10 except that the charge injection layer was not formed. The results are shown in Table 1.
  • Example 15 (Production of Organic Thin Film Light-Emitting Transistor)
  • a Si substrate also used as a P-type specific resistance 1 ⁇ cm gate electrode
  • chromium is deposited to a thickness of 20 nm by sputtering
  • gold is sputtered by 100 nm by sputtering.
  • a film was formed and used as an extraction electrode. This substrate was ultrasonically cleaned with a neutral detergent, pure water, acetone and ethanol for 30 minutes each.
  • a vacuum deposition apparatus (ULVAC, EX-900), and 4 MSB is deposited on the insulator layer (SiO 2 ) as an organic semiconductor light emitting layer having a thickness of 100 nm at a deposition rate of 0.05 nm / s. did.
  • a metal mask having a channel length of 75 ⁇ m and a channel width of 5 mm was installed, and a compound (180) was deposited as a charge injection layer to a thickness of 10 nm at a deposition rate of 0.05 nm / s.
  • gold was deposited to a thickness of 50 nm through the mask in a state where the substrate was tilted 45 degrees with respect to the evaporation source.
  • the source electrode and the drain electrode which are not in contact with each other substantially form a hole injecting electrode (Au) and an electron transporting electrode (Mg).
  • An organic thin film light emitting transistor provided was prepared. When -100 V was applied between the source and drain electrodes of the manufactured organic thin film light emitting transistor and -100 V was applied to the gate electrode, blue light emission of 50 cd / m 2 was obtained.
  • Example 16 (Production of top contact type organic thin film transistor) A top contact type organic thin film transistor having the structure shown in FIG. 4 was manufactured as follows. Using a shadow mask, an ITO film having a thickness of 100 nm was formed on a glass substrate by sputtering to form a gate electrode. Further, poly (chloro-p-xylene) (parylene C) was formed thereon to a thickness of 500 nm by thermal chemical vapor deposition to form a gate insulating layer.
  • poly (chloro-p-xylene) parylene C
  • the substrate was placed in a vacuum deposition apparatus (ULVAC, EX-400), and 2,7-diphenyl [1] benzothieno [3,3-b]-[1] -benzothiophene was formed on the insulator layer.
  • DPh-BTBT 2,7-diphenyl [1] benzothieno [3,3-b]-[1] -benzothiophene was formed on the insulator layer.
  • DPh-BTBT 2,7-diphenyl [1] benzothieno [3,3-b]-[1] -benzothiophene was formed on the insulator layer.
  • DPh-BTBT was formed as an organic semiconductor layer having a thickness of 40 nm at a deposition rate of 0.05 nm / s at room temperature.
  • a charge injection layer having a thickness of 10 nm was formed from the compound (60) (2,6-bis (2-phenylethynyl) anthracene;
  • the charge injection layer and the source and drain electrodes which are not in contact with each other were formed so that the interval (channel length L) was 50 ⁇ m.
  • an organic thin film transistor was manufactured by forming a film so that the width (channel width W) of the source electrode and the drain electrode was 1 mm (see FIG. 4).
  • Comparative Examples 3 and 4 An organic thin film transistor was fabricated in the same manner as in Example 16 except that the charge injection layer was replaced with the compound shown in Table 2, and the field effect mobility ⁇ s and the threshold voltage V t were determined. The results are shown in Table 2.
  • Example 16 employing the compound (60) (DPEA) in the charge injection layer is superior to the device of pentacene (Comparative Example 3) or MoO 3 (Comparative Example 4) in field effect migration. Degree and threshold voltage are shown. In particular, when pentacene used as a general organic semiconductor is used for the charge injection layer, good field-effect mobility and threshold voltage are not obtained. It can be seen that the characteristics required for the material constituting the charge injection material layer are different.
  • the organic thin film transistor of the present invention has a high performance as a transistor in which a response speed (driving speed) is increased, an on / off ratio is large, and a driving voltage is lowered by using a compound having a specific structure as a charge injection layer. Yes, it can also be used as an organic thin film light emitting transistor capable of emitting light.
  • the organic thin film transistor of the present invention is used for display electronic devices such as electronic devices for thin film displays, wearable electronic devices such as plastic IC cards and information tags, medical devices such as biosensors, and measuring devices. Can do.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Thin Film Transistor (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Electrodes Of Semiconductors (AREA)

Abstract

L'invention propose un transistor en film organique mince dans lequel un substrat est doté d'une couche semi-conductrice organique, d'une couche d'isolant et d'au moins trois bornes prévues pour une électrode de grille, une électrode de source et une électrode de drain. Le courant entre la source et le drain est régulé en appliquant une tension sur l'électrode de grille. Le transistor en film organique mince proposé présente une couche d'injection de charges entre la couche organique semi-conductrice et l'électrode de source et une autre entre la couche organique semi-conductrice et l'électrode de drain. Lesdites couches d'injection de charges contiennent un composé représenté par la formule (1). (1) Dans la formule, Ar1 est un substituant représenté par la formule (2) ; Ar2 est un hydrocarbure aromatique divalent en C6-60 qui peut présenter un substituant ou un groupe hétérocyclique aromatique divalent en C2-60 qui peut présenter un substituant ; Ar3 est un substituant représenté par la formule (3) et n est un entier compris entre 1 et 20. (2) (3)
PCT/JP2010/005706 2009-09-25 2010-09-21 Transistor en film organique mince WO2011036866A1 (fr)

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JP2013016613A (ja) * 2011-07-04 2013-01-24 Sony Corp 電子デバイス及び半導体装置の製造方法
WO2017159657A1 (fr) * 2016-03-18 2017-09-21 Dic株式会社 Nouveau composé et matériau semi-conducteur organique le contenant
JP2018503985A (ja) * 2015-02-04 2018-02-08 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 低コンタクト抵抗を有する有機電界効果トランジスタ
JP2018100225A (ja) * 2016-12-19 2018-06-28 Dic株式会社 有機化合物およびそれを含有する半導体材料
JP2018177639A (ja) * 2017-04-03 2018-11-15 Dic株式会社 新規化合物およびそれを含有する半導体材料

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CN111128707B (zh) * 2014-08-26 2023-06-16 株式会社尼康 元件制造方法及转印基板
DE102019200810B4 (de) * 2019-01-23 2023-12-07 Technische Universität Dresden Organischer dünnschicht-transistor und verfahren zur herstellung desselben

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JPH10125924A (ja) * 1996-10-17 1998-05-15 Matsushita Electric Ind Co Ltd 有機薄膜トランジスタ及び液晶素子と有機発光素子
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Publication number Priority date Publication date Assignee Title
JP2013016613A (ja) * 2011-07-04 2013-01-24 Sony Corp 電子デバイス及び半導体装置の製造方法
JP2018503985A (ja) * 2015-02-04 2018-02-08 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 低コンタクト抵抗を有する有機電界効果トランジスタ
WO2017159657A1 (fr) * 2016-03-18 2017-09-21 Dic株式会社 Nouveau composé et matériau semi-conducteur organique le contenant
JP2018100225A (ja) * 2016-12-19 2018-06-28 Dic株式会社 有機化合物およびそれを含有する半導体材料
JP2018177639A (ja) * 2017-04-03 2018-11-15 Dic株式会社 新規化合物およびそれを含有する半導体材料

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JPWO2011036866A1 (ja) 2013-02-14
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JP5677306B2 (ja) 2015-02-25

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