WO2011074231A1 - Composé polycyclique à cycles fusionnés et transistor organique en couches minces le contenant - Google Patents

Composé polycyclique à cycles fusionnés et transistor organique en couches minces le contenant Download PDF

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WO2011074231A1
WO2011074231A1 PCT/JP2010/007219 JP2010007219W WO2011074231A1 WO 2011074231 A1 WO2011074231 A1 WO 2011074231A1 JP 2010007219 W JP2010007219 W JP 2010007219W WO 2011074231 A1 WO2011074231 A1 WO 2011074231A1
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carbon atoms
compound
organic thin
film transistor
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芦澤美佐
齊藤雅俊
中村浩昭
栗原直樹
近藤浩史
河村昌宏
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出光興産株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • 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
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • 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 a polycyclic fused ring compound and an organic thin film transistor using the same.
  • a thin film transistor (TFT: Thin Film Transistor) is widely used as a switching element for display of a liquid crystal display device or the like.
  • a typical TFT has a gate electrode, an insulator layer, and a semiconductor layer in this order on a substrate, and has a source electrode and a drain electrode formed on the semiconductor layer at 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 apparatus used for manufacturing such a TFT using silicon is very expensive, and a display device using the TFT.
  • Such an increase in size has a problem in that it involves a significant increase in manufacturing costs.
  • 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 thus there is a problem that a lightweight resin substrate cannot be used. there were.
  • a TFT using an organic substance instead of amorphous or polycrystalline silicon (hereinafter sometimes abbreviated as an organic TFT) has been proposed.
  • Vacuum deposition and coating methods are known as film formation methods used when forming TFTs with organic materials.
  • film formation methods it is possible to increase the size of the element while suppressing an increase in manufacturing cost.
  • the process temperature required for film formation can be made relatively low.
  • the organic TFT has an advantage that there are few restrictions when selecting a material to be used for the substrate, and its practical use is expected, and research reports have been actively made.
  • the on / off ratio here refers to the current flowing between the source and drain when the gate voltage is applied (on) divided by the current flowing between the source and drain when the gate voltage is not applied (off).
  • the on-current is a current value (saturation current) when the current flowing between the source and the drain is normally saturated while increasing the gate voltage.
  • organic semiconductor materials used for organic TFTs conjugated polymers, multimers such as thiophene, polycyclic fused ring compounds such as metal phthalocyanine compounds and pentacene, etc. are known. The development of organic semiconductor materials that satisfy all requirements has not been achieved.
  • pentacene which is a polycyclic fused ring compound, has attracted attention as a material that exhibits high carrier mobility similar to amorphous silicon due to its ⁇ -conjugated system, but research has been actively conducted in the atmosphere.
  • the disadvantage of low storage stability is known.
  • a polycyclic fused ring compound obtained by condensing benzothiophene to the naphthalene ring as shown in the following formula (A) is useful as an organic semiconductor material for organic TFTs with a carrier mobility of 10 ⁇ 2 cm 2 / Vs. It has been reported (Patent Document 2). Moreover, although the compound of the following formula (B) and (C) is synthesize
  • An object of the present invention is to provide a novel organic thin film transistor material having high carrier mobility.
  • each X 1 is an oxygen atom, a sulfur atom, or a group represented by N—R 13 .
  • R 1 to R 13 are each a hydrogen atom, a halogen 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.
  • An alkylsilylethynyl group having 5 to 60 carbon atoms, an arylamino group having 3 to 60 carbon atoms, a diarylamino group having 6 to 120 carbon atoms, or a cyano group, Substituent may have.
  • each X 2 represents an oxygen atom, a sulfur atom, or a group represented by N—R 33 .
  • R 21 to R 33 are each a hydrogen atom, a halogen 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.
  • both X 2 are groups represented by N—R 33
  • the two R 33 may be the same or different.
  • R 21 to R 32 are not all hydrogen atoms.
  • R 21 to R 32 are not alkyl groups having 1 carbon atom.
  • the organic thin film transistor in which 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.
  • An organic thin film transistor, wherein the semiconductor layer comprises the compound according to 1 or the compound according to 2. 9.
  • the organic thin film transistor according to any one of 8 to 10 having a buffer layer between the source and drain electrodes and the organic semiconductor layer.
  • An apparatus comprising the organic thin film transistor according to any one of 12.8 to 11.
  • a novel organic thin film transistor material having high carrier mobility can be provided.
  • the organic thin film transistor compound of the present invention is represented by the following formula (1).
  • each X 1 is an oxygen atom, a sulfur atom, or a group represented by N—R 13 .
  • R 1 to R 13 are each a hydrogen atom, a halogen 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.
  • An alkylsilylethynyl group having 5 to 60 carbon atoms, an arylamino group having 3 to 60 carbon atoms, a diarylamino group having 6 to 120 carbon atoms, or a cyano group, Substituent may have.
  • R 13 When X 1 is a group represented by N—R 13 , two R 13 may be the same or different.
  • R 13 is an alkyl group or an aryl group, the stability of the compound is maintained, and at the same time, the overlap of ⁇ electrons between molecules becomes moderate and the carrier mobility may be improved. As preferred.
  • polycyclic fused-ring compound of this invention is represented by following formula (2). This compound is included in the compound of formula (1).
  • each X 2 is an oxygen atom, a sulfur atom, or a group represented by N—R 133 .
  • R 21 to R 32 are each a hydrogen atom, a halogen 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, Haloalkoxy group having 1 to 30 carbon atoms, alkylthio group having 1 to 30 carbon atoms, haloalkylthio group having 1 to 30 carbon atoms, alkylamino group having 1 to 30 carbon atoms, dialkylamino group having 2 to 60 carbon atoms (alkyl The 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
  • R 21 to R 32 are each a hydrogen atom, a halogen 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, Haloalkoxy group having 1 to 30 carbon atoms, alkylthio group having 1 to 30 carbon atoms, haloalkylthio group having 1 to 30 carbon atoms, alkylamino group having 1 to 30 carbon atoms, dialkylamino group having 2 to 60 carbon atoms (alkyl The 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, an aryl group having 3 to 60 carbon atoms, carbon An alkylsilyl group having 3 to 20 carbon
  • R 21 to R 32 are each a hydrogen atom, a halogen atom, an alkyl group having 2 to 30 carbon atoms, a haloalkyl group having 1 to 30 carbon atoms, a carbon number 1-30 alkoxy groups, 1-30 carbon atoms haloalkoxy groups, 1-30 carbon atoms alkylthio groups, 1-30 carbon atoms haloalkylthio groups, 1-30 carbon atoms alkylamino groups, 2-20 carbon atoms 60 dialkylamino groups (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, a carbon number of 3 Aryl group having ⁇ 60, alkylsilyl group having 3 to 20 carbon atoms, alkyls
  • R 33 is a hydrogen atom, a halogen 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, a haloalkoxy group having 1 to 30 carbon atoms, or 1 carbon atom.
  • alkylthio groups 1-30 alkylthio groups, 1-30 haloalkylthio groups, 1-30 alkylamino groups, 2-60 dialkylamino groups (the alkyl groups are bonded to each other to form a ring structure containing a nitrogen atom) May be formed), an alkylsulfonyl group having 1 to 30 carbon atoms, a haloalkylsulfonyl group having 1 to 30 carbon atoms, an aryl group having 3 to 60 carbon atoms, an alkylsilyl group having 3 to 20 carbon atoms, and 5 to 5 carbon atoms An alkylsilylethynyl group having 60 carbon atoms, an arylamino group having 3 to 60 carbon atoms, a diarylamino group having 6 to 120 carbon atoms, or a cyano group, each of which has a substituent. Also good.
  • R 33 is an alkyl group or an aryl group, the stability of the compound is maintained
  • both X 2 are groups represented by N—R 33
  • the two R 33 may be the same or different. Since the compound of the present invention has a phenacene type structure, it is excellent in storage stability as compared with the acene type.
  • X 1 and X 2 are preferably an oxygen atom or a sulfur atom, respectively, from the viewpoint of mobility.
  • the compounds of the formula (1) and the formula (2) are preferably substituents such that R 1 to R 12 and R 21 to R 32 are symmetric at the central point of the central naphthalene skeleton.
  • R 3 and R 9 are the same, or R 2 and R 8 are the same, or R 3 and R 9 are the same, and R 2 and R 8 are the same.
  • Preferred are compounds in which the others are hydrogen.
  • Particularly preferred is a compound in which R 3 and R 9 of R 1 to R 12 in the formula (1) are the same and the others are hydrogen.
  • R 23 and R 29 are the same, or R 22 and R 28 are the same, or R 23 and R 29 are the same, and R 22 and R 28 are Preferable compounds are the same and the others are hydrogen.
  • Particularly preferred is a compound in which, among R 21 to R 32 in formula (2), R 23 and R 29 are the same, and the others are hydrogen.
  • those having a substituent can be applied to a solution process in which the compound of the present invention is dissolved in a solvent to form an organic semiconductor layer, so that the manufacturing method of the organic TFT is diversified.
  • a linear substituent is more preferable.
  • R 21 to R 32 in formula (2) are compounds in which R 23 and R 29 are the same linear substituent, or R 22 and R 28 are the same linear substituent, and the others are hydrogen.
  • a certain compound can be mentioned preferably.
  • R 21 to R 32 in the formula (2) are compounds in which R 23 and R 29 are the same linear substituent, and the others are hydrogen.
  • an alkyl chain such as an alkyl group, a haloalkyl group, an alkoxy group, or an alkylthio group
  • solubility is increased by using a branched alkyl group.
  • an alkyl chain having an appropriate length for example, an alkyl chain having about 4 to 15 carbon atoms is preferable.
  • 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, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group N-octadecyl group, n-nonadecyl group, n-icosane group, n-henicosane group, n-docosane group, n-tricosane group, n-tetracosane group, n-pentacosane group, n-hexacosane group, n-heptacosane group N-octacosane group, n-nonacosane group, n-triacontan
  • 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 —OY 1
  • examples of Y 1 include the same examples as described for the alkyl group
  • the haloalkoxy group is represented by —OY 2.
  • Examples of Y 2 include the same examples as those described for the haloalkyl group.
  • the alkylthio group is a group represented by —SY 1
  • examples of Y 1 include the same examples as described for the alkyl group
  • the haloalkylthio group is represented by —SY 2.
  • Examples of Y 2 include the same examples as those described for the haloalkyl group.
  • the alkylamino group is a group represented by —NHY 1 ; the dialkylamino group is a group represented by —NY 1 Y 3 ; and Y 1 and Y 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 pyrrolidine, piperidine and the like.
  • the alkylsulfonyl group is a group represented by —SO 2 Y 1 , and examples of Y 1 include the same examples as described for the alkyl group, and the haloalkylsulfonyl group includes —SO 2 Y 2 is a group represented by Y 2 , and examples of Y 2 include the same examples as those described for the haloalkyl group.
  • the aryl group is an aromatic hydrocarbon ring and an aromatic heterocycle, and specific examples of the aromatic hydrocarbon ring include benzene, naphthalene, anthracene, chrysene, phenanthrene, tetracene, fluorene, pyrene, fluoranthene, perylene and the like. Is mentioned.
  • aromatic heterocycle examples include pyridine, pyrazine, indole, acridine, pyrrole, imidazole, pyrazole, quinoline, naphthyridine, quinoxaline, phenazine, phenothiazine, phenoxazine, diazaanthracene, pyridoquinoline, pyrimidoquinazoline, pyra Dinoquinoxaline, phenanthroline, carbazole, thiophene, benzothiophene, dibenzothiophene, benzodithiophene, [1] benzothieno [3,2-b] benzothiophene, thienothiophene, dithienothiophene, furan, benzofuran, dibenzofuran, benzodifuran, thiazole, Benzothiazole, dithiaindacene, dithiaindenoindene, dibenzoselenoph
  • aryl group those based on an aromatic hydrocarbon ring are preferable, and a phenyl group is particularly preferable. From the viewpoint of solubility, a phenyl group substituted with a linear alkyl group having 4 to 15 carbon atoms is preferred.
  • the alkylsilyl group is a group represented by —SiY 1 Y 3 Y 4 , and examples of Y 1 , Y 3 and Y 4 are the same as those described for the alkyl group. For example, a trimethylsilyl group etc. are mentioned.
  • the alkylsilylethynyl group is a group in which the group represented by the alkylsilyl group is interposed by an ethynylene group, and examples thereof include a trimethylsilylethynyl group, a triethylsilylethynyl group, and a triisopropylsilylethynyl group.
  • the arylamino group is a group represented by —NHY 5
  • the diarylamino group is a group represented by —NY 5 Y 6
  • Y 5 and Y 6 are those described for the aryl group, respectively. The same example is given.
  • substituents that may be further substituted on the groups represented by R 1 to R 12 in formula (1) and R 21 to R 33 in formula (2) include the aromatic hydrocarbon groups and aromatic heterocycles described above.
  • an alkyl chain such as an alkyl group, a haloalkyl group, an alkoxy group, or an alkylthio group
  • solubility is increased by using a branched alkyl group.
  • an alkyl chain having an appropriate length for example, an alkyl chain having about 4 to 15 carbon atoms is preferable.
  • the organic compound having a specific structure used in the organic thin film transistor of the present invention is basically bipolar with p-type (hole conduction) and n-type (electron conduction), and is combined with the source and drain electrodes described later. Therefore, it can be driven as a p-type element or an n-type element.
  • the lowest unoccupied orbital (LUMO) level is lowered to function as an n-type semiconductor.
  • Preferred as the electron-accepting group are a hydrogen atom, a halogen atom, a cyano group, a haloalkyl group having 1 to 30 carbon atoms, a haloalkoxy group having 1 to 30 carbon atoms, and a haloalkylsulfonyl group having 1 to 30 carbon atoms.
  • the highest occupied orbital (HOMO) level can be increased to function as a p-type semiconductor.
  • Preferred examples of the electron donating group include a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkylamino group having 1 to 30 carbon atoms, and a dialkylamino group having 2 to 60 carbon atoms.
  • the amino groups may be bonded to each other to form a ring structure containing a nitrogen atom).
  • N— such as (C-1) means “N—CH 3 ”.
  • the polycyclic fused ring compound represented by the formula (1) of the present invention can be obtained by a known method, for example, a boronic acid synthesis such as the following reaction (A), a Suzuki coupling using a transition metal such as (B) It can be synthesized by a reaction, a deprotection reaction such as (C), or a cyclization reaction such as (D).
  • a boronic acid synthesis such as the following reaction (A), a Suzuki coupling using a transition metal such as (B)
  • It can be synthesized by a reaction, a deprotection reaction such as (C), or a cyclization reaction such as (D).
  • an electronic device such as a transistor
  • a device with high field-effect mobility and a high on / off ratio can be obtained by using a material with high purity. Therefore, it is desirable to add purification by a technique such as column chromatography, recrystallization, distillation, sublimation, etc. as 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 as a final step of purification. By using these methods, it is preferable to use a material having a purity of 90% or more measured by HPLC, more preferably 95% or more, and particularly preferably 99% or more. In addition, the on / off ratio can be increased and the performance inherent to the material can be extracted.
  • the element configuration of the organic thin film transistor of the present invention is such that 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 applied to the gate electrode. It is a thin film transistor controlled by this. And an organic-semiconductor layer contains the compound for organic thin-film transistors of this invention mentioned above, It is characterized by the above-mentioned.
  • the structure of the transistor is not particularly limited, and components other than the components of the organic semiconductor layer may have a known element configuration.
  • a specific example of the element configuration of the organic thin film transistor will be described with reference to the drawings.
  • 1 to 4 are diagrams showing an example of the element configuration of the organic thin film transistor of the present invention.
  • a gate electrode 15 is formed on the insulator layer 14 and on the gap between the source electrode 11 and the drain electrode 12.
  • the organic thin film transistor 2 in FIG. 2 has a gate electrode 15 and an insulator layer 14 in this order on a substrate 10, and a pair of source electrode 11 and drain formed on the insulator layer 14 with a predetermined interval therebetween.
  • An electrode 12 is provided, and an organic semiconductor layer 13 is formed thereon.
  • the organic semiconductor layer 13 forms a channel region, and is turned on / off by controlling a current flowing between the source electrode 11 and the drain electrode 12 with a voltage applied to the gate electrode 15.
  • the organic thin film transistor 3 in FIG. 3 has a gate electrode 15, an insulator layer 14, and an organic semiconductor layer 13 in this order on a substrate 10.
  • a source electrode 11 and a drain electrode 12 are provided.
  • the insulating layer 14 and the gate electrode 15 are provided in this order.
  • the organic thin film transistor of the present invention has a field effect transistor (FET) structure. As described above, there are several configurations depending on the position of the electrodes, the layer stacking order, and the like.
  • 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.
  • Various configurations of the organic thin film transistor of the present invention have also been proposed as the organic thin film transistor in the above device configuration, and the current flowing between the source electrode and the drain electrode is controlled by the voltage applied to the gate electrode.
  • the device configuration is not limited to the above as long as an effect such as on / off operation and amplification is exhibited.
  • top-and-bottom contact type organic thin film transistor 5 (Fig. 5) proposed by Yoshida et al. Of the National Institute of Advanced Industrial Science and Technology in the 49th Applied Physics Related Conference Lecture Collection 27a-M-3 (March 2002) Or a vertical organic thin film transistor 6 (see FIG. 6) proposed by Kudo et al. Of Chiba University in the IEEJ Transactions 118-A (1998), page 1440.
  • the organic-semiconductor layer in the organic thin-film transistor of this invention contains the compound for organic thin-film transistors of this invention mentioned above.
  • the thickness of the organic semiconductor layer 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.
  • MBE molecular beam deposition
  • vacuum deposition chemical deposition
  • dipping of a solution in which a material is dissolved in a solvent Method spin coating method, casting method, bar coating method, roll coating method, ink jet method printing, coating method and baking
  • electropolymerization molecular beam deposition, self assembly from solution, and a combination of these
  • the above material is used.
  • the solvent used in the case of forming the organic semiconductor by dissolving the organic semiconductor material in the solvent is not particularly limited.
  • examples thereof include alcohol solvents, ketone solvents, hydrocarbon solvents, halogenated hydrocarbon solvents, nitrile solvents, and aprotic polar solvents.
  • 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.
  • one kind of the compound represented by the formula (1) may be used, or a plurality of mixed thin films or stacked layers using a known semiconductor such as pentacene or thiophene oligomer may be used. May be used.
  • 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.
  • PET, PES, PC plastic films
  • metal substrates or composites or laminates thereof 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 a gate electrode / substrate.
  • the surface of Si can be oxidized to form SiO 2 and used as an insulating layer.
  • a metal layer such as Au may be formed on the Si substrate serving as the substrate and gate electrode as an electrode for connecting the 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.
  • Examples of the method for forming the electrode include 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, and ink jet. It 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.
  • the thickness of the electrode formed in this way is not particularly limited as long as current is conducted, but is preferably in the range of 0.2 nm to 10 ⁇ m, more preferably 4 nm to 300 nm. If it is in this preferable range, the resistance is increased due to the thin film thickness, and a voltage drop does not occur. In addition, 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.
  • another source electrode, drain electrode, gate electrode and a method for forming the source electrode are formed using a fluid electrode material such as a solution, paste, ink, or dispersion containing the above conductive material.
  • a fluid electrode material such as a solution, paste, ink, or dispersion containing the above conductive material.
  • a fluid electrode material containing a conductive polymer or metal fine particles containing platinum, gold, silver, or copper is preferable.
  • 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.
  • 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.
  • 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.
  • a method for producing such a dispersion of metal fine particles 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.
  • metal fine particle dispersions may be directly patterned by an ink jet method, or may be formed from a coating film by lithograph or laser ablation. Moreover, the patterning method by printing methods, such as a letterpress, an intaglio, a lithographic plate, and screen printing, can also be used. After the electrode is formed and the solvent is dried, the metal fine particles are heat-fused by heating in a shape within a range of 100 ° C. to 300 ° C., preferably 150 ° C. to 200 ° C., if necessary. An electrode pattern having the following shape can be formed.
  • a known conductive polymer whose conductivity has been improved by doping is also preferable to use as another gate electrode, source electrode, and drain electrode material.
  • conductive polyaniline, conductive polypyrrole, conductive polythiophene, A complex of polyethylene dioxythiophene (PEDOT) and polystyrene sulfonic acid is also preferably used. These materials can reduce the contact resistance between the organic semiconductor layer of the source electrode and the drain electrode.
  • These forming methods may also be patterned by an ink jet method, or may be formed from a coating film by lithography, laser ablation, or the like.
  • the patterning method by printing methods such as a letterpress, an intaglio, a lithographic plate, and screen printing, can also be used.
  • the material for forming the source electrode and the drain electrode is preferably a material having a small electric resistance at the contact surface with the organic semiconductor layer among the examples described above.
  • the electrical resistance at this time corresponds to the field effect mobility when the current control device is manufactured, and the resistance needs to be as small as possible in order to obtain a large mobility. This is generally determined by the magnitude relationship between the work function of the electrode material and the energy level of the organic semiconductor layer.
  • the work function (W) of the electrode material is a
  • the ionization potential (Ip) of the organic semiconductor layer is b
  • the electron affinity (Af) of the organic semiconductor layer is c
  • a, b, and c are all positive values based on the vacuum level.
  • ba ⁇ 1.5 eV (formula (I)) is preferable, and ba ⁇ 1.0 eV is more preferable. If the above relationship can be maintained in relation to the organic semiconductor layer, a high-performance device can be obtained.
  • the electrode material has a work function as large as possible, and the work function is 4.0 eV or more.
  • the work function is preferably 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 higher as described in Chemistry Handbook Fundamentals II-493 (revised 3 edition, published by The Chemical Society of Japan, Maruzen 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, 4.3) , 4.87 eV), Ni (5.04
  • 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.
  • low work function metals have a work function of 4.3 eV or less as described in Chemical Handbook, Basics, pages II-493 (Revised 3rd edition, edited by The Chemical Society of Japan, published by Maruzen Co., Ltd. 1983). What is necessary is just to select from the said list of effective metals, Ag (4.26 eV), Al (4.06, 4.28 eV), Ba (2.52 eV), Ca (2.9 eV), Ce (2.9 eV), Cs (1.95 eV), Er (2.97 eV), Eu (2.5 eV), Gd (3.1 eV), Hf (3.9 eV), In (4.09 eV), K (2.28 eV), La (3.5 eV), Li (2.93 eV), Mg (3.66 eV), Na (2.36 eV), Nd (3.2 eV), Rb (4.25 eV), Sc (3.5 eV), Sm ( 2.7 eV), Ta (4.0, 4.
  • the electrode material contains one or more of these low work function substances, there is no particular limitation as long as the work function satisfies the above formula (II).
  • 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.
  • a buffer layer may be provided between the organic semiconductor layer and the source and drain electrodes for the purpose of improving the injection efficiency.
  • the buffer layer for n-type organic thin film transistors, LiF, Li 2 O, CsF, Na 2 CO 3 , KCl, MgF 2 , CaCO 3 and other alkali metal and alkaline earth metal ion bonds used for the cathode of organic EL A compound having Moreover, you may insert the compound used as an electron injection layer and an electron carrying layer by organic EL, such as Alq.
  • cyano compounds such as FeCl 3 , TCNQ, F 4 -TCNQ, HAT, CFx, GeO 2 , SiO 2 , MoO 3 , V 2 O 5 , VO 2 , V 2 O 3 , MnO, Metal oxides other than alkali metals and alkaline earth metals such as Mn 3 O 4 , ZrO 2 , WO 3 , TiO 2 , In 2 O 3 , ZnO, NiO, HfO 2 , Ta 2 O 5 , ReO 3 , 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 buffer layer has the effect of lowering the threshold voltage by lowering the carrier injection barrier and driving the transistor at a low voltage.
  • a carrier trap exists at the interface between the organic semiconductor and the insulator layer. When carrier injection occurs when a gate voltage is applied, the first injected carrier is used to fill the trap. The trap is filled with voltage and the mobility is improved.
  • the buffer layer only needs to be thin between the electrode and the organic semiconductor layer, and the thickness is 0.1 nm to 30 nm, preferably 0.3 nm to 20 nm.
  • 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, lanthanum oxide, fluorine oxide, magnesium oxide, bismuth oxide, bismuth titanate, niobium oxide, strontium bismuth titanate, strontium bismuth tantalate, tantalum pentoxide, bismuth tantalate niobate, trioxide Examples thereof include 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. Specifically, barium (Ba), strontium (Sr), titanium (Ti), bismuth (Bi), tantalum ( Ta), zircon (Zr), iron (Fe), nickel (Ni), manganese (Mn), lead (Pb), lanthanum (La), lithium (Li), sodium (Na), potassium (K), rubidium ( Rb), cesium (Cs), francium (Fr), beryllium (Be), magnesium (Mg), calcium (Ca), niobium (Nb), thallium (Tl), mercury (Hg), copper (Cu), cobalt ( Co), rhodium (Rh), scandium (Sc), yttrium (Y), and the like.
  • 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. Further, among the above materials, in particular, when an insulator layer is formed of silicon nitride such as Si 3 N 4 , SixNy, or SiONx (x, y> 0), a depletion layer is more easily generated, and the threshold of transistor operation is increased. The voltage can be further reduced.
  • polyimide, polyamide, polyester, polyacrylate, photo radical polymerization system, photo cation polymerization system photo-curable resin, copolymer containing acrylonitrile component, polyvinyl phenol, polyvinyl alcohol, A novolac resin, cyanoethyl pullulan, or the like can also be used.
  • wax polyethylene, polychloropyrene, polyethylene terephthalate, polyoxymethylene, polyvinyl chloride, polyvinylidene fluoride, polysulfone, polyimide cyanoethyl pullulan, poly (vinylphenol) (PVP), poly (methyl methacrylate) (PMMA), polycarbonate (PC ), Polystyrene (PS), polyolefin, polyacrylamide, poly (acrylic acid), novolac resin, resole resin, polyimide, polyxylylene, epoxy resin, and also high molecular materials with high dielectric constant such as pullulan can be used. It is.
  • the organic compound material and polymer material used for the insulator layer are materials having water repellency.
  • water repellency By having water repellency, the interaction between the insulator layer and the organic semiconductor layer can be suppressed, and the crystallinity of the organic semiconductor layer can be improved by utilizing the cohesiveness inherent in the organic semiconductor, thereby improving the device performance.
  • Examples of this include Yasuda et al. Jpn. J. et al. Appl. Phys. Vol. 42 (2003) p. 6614-6618 and Janos Veres et al. Chem. Mater. , Vol. 16 (2004) p. 4543-4555 can be mentioned.
  • the organic semiconductor layer can be formed with less damage. Therefore, it is an effective method.
  • the 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 between the source and gate. Therefore, it is necessary to select an appropriate film thickness, which is normally 10 nm to 5 ⁇ m, preferably 50 nm to 2 ⁇ m, and 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.
  • Silane coupling agents such as hexamethyldisilazane, octadecyltrichlorosilane, trichloromethylsilazane, and self-organized alignment film materials such as alkane phosphoric acid, alkane sulfonic acid, and alkane carboxylic acid are insulated in a liquid phase or gas phase state.
  • An example is a method in which the film is brought into contact with the surface of the film to form a self-assembled film, followed by appropriate drying treatment.
  • 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 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 source electrode is formed. It is preferable to form a series of device manufacturing steps up to the formation of the drain electrode without being exposed to the atmosphere at all, because the device performance can be prevented from being impaired by moisture, oxygen, etc. in the atmosphere due to contact with the atmosphere. If it is unavoidable that the atmosphere must be exposed to the atmosphere once, the steps after the organic semiconductor layer formation are not exposed to the atmosphere at all, and the surface on which the organic semiconductor layer is laminated (for example, FIG. In the case of the organic thin film transistor 2 of FIG.
  • the surface of the insulating layer partially laminated with a source electrode and a drain electrode) is cleaned and activated by ultraviolet irradiation, ultraviolet / ozone irradiation, oxygen plasma, argon plasma, etc. It is preferable to laminate the layers.
  • some p-type TFT materials are exposed to the atmosphere once, and the performance is improved by adsorbing oxygen or the like. Therefore, depending on the material, the materials are appropriately exposed to the atmosphere.
  • a gas barrier layer may be formed on the whole or part of the outer peripheral surface of the organic transistor element.
  • 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.
  • the inorganic substance which has the insulation illustrated in the said insulator layer can also be used.
  • an organic thin film light emitting transistor that emits light using a current flowing between a source electrode and a drain electrode and controls light emission by applying a voltage to the gate electrode. That is, an organic thin film transistor can be used as a light emitting element (organic EL). 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. When used as an organic light emitting transistor, it is necessary to inject holes from one of the source electrode and the drain electrode and electrons from the other, and the following conditions are preferably satisfied in order to improve the light emitting performance.
  • At least one of the source electrode and the drain electrode is a hole injecting electrode in order to improve the hole injecting property.
  • a hole injection electrode is an electrode containing a substance having a work function of 4.2 eV or higher.
  • At least one of the source electrode and the drain electrode is an electron injection electrode.
  • An electron injecting electrode is an electrode containing a substance having a work function of 4.3 eV or less.
  • 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.
  • the hole injection layer In order to improve the hole injection property, it is preferable to insert a hole injection layer between at least one of the source electrode and the drain electrode and the organic semiconductor layer.
  • the hole injection layer include amine-based materials used as a hole injection material and a hole transport material in an organic EL device.
  • an electron injection layer between at least one of the source electrode and the drain electrode and the organic semiconductor layer.
  • the electron injection material used for the organic EL element can be used for the electron injection layer as well as the hole.
  • it is an organic thin film light emitting transistor having a hole injection layer on one electrode and an electron injection layer on the other electrode.
  • the device using the organic thin film transistor of the present invention may be a device using the organic thin film transistor of the present invention, and examples thereof include a circuit, a personal computer, a display, and a mobile phone.
  • Example 3 (Production of organic thin film transistor by vapor deposition process) An organic thin film transistor was produced by the following procedure. The glass substrate was ultrasonically cleaned with a neutral detergent, pure water, acetone and ethanol for 30 minutes each, and then gold (Au) was formed to a thickness of 40 nm by a sputtering method to produce a gate electrode. Next, this substrate was set in a film forming section of a thermal CVD apparatus. On the other hand, 250 mg of polyparaxylene derivative [polyparaxylene chloride (Parylene)] (trade name; diX-C, manufactured by Daisan Kasei Co., Ltd.), which is a raw material for the insulating layer, was placed in a petri dish.
  • Parylene polyparaxylene derivative
  • diX-C manufactured by Daisan Kasei Co., Ltd.
  • the thermal CVD apparatus was evacuated with a vacuum pump and depressurized to 5 Pa, and then the evaporation part was heated to 180 ° C. and the polymerization part was heated to 680 ° C. and left for 2 hours to form an insulating layer having a thickness of 1 ⁇ m on the gate electrode. .
  • the substrate was placed in a vacuum vapor deposition apparatus (ULVAC, EX-400), and the compound (A-8) was deposited on the insulator layer at an organic layer having a thickness of 50 nm at a deposition rate of 0.05 nm / s.
  • a semiconductor layer was formed.
  • gold was deposited to a thickness of 50 nm through a metal mask, so that a source electrode and a drain electrode that were 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 (channel width W) of the source electrode and the drain electrode was 5 mm (see FIG. 3).
  • the source - a current was passed by applying a voltage between the drain.
  • the field effect mobility ⁇ of holes was calculated from the following formula (A), and was 0.5 cm 2 / Vs.
  • I D (W / 2L) ⁇ C ⁇ ⁇ (V G ⁇ V T ) 2 (A)
  • ID is a source-drain current
  • W is a channel width
  • L is a channel length
  • C is a capacitance per unit area of the gate insulator layer
  • V T is a gate threshold voltage
  • V G is a gate voltage.
  • Example 4 Organic thin film transistor by vapor deposition process
  • An organic thin film transistor was produced in the same manner as in Example 3 except that the compound (A-75) was used instead of the compound (A-8) as the material of the organic semiconductor layer.
  • the obtained organic thin film transistor was p-type driven at the gate voltage V G of ⁇ 70 V in the same manner as in Example 3.
  • Table 2 shows the results of measuring the on / off ratio of the current between the source and drain electrodes and calculating the field effect mobility ⁇ of the holes.
  • Comparative Example 1 Organic thin film transistor by vapor deposition process
  • An organic thin film transistor was produced by the following procedure. First, the surface of a Si substrate (also used as a P-type specific resistance 1 ⁇ cm gate electrode) was oxidized by a thermal oxidation method to produce a 300 nm thermal oxide film on the substrate to form an insulator layer. Further, after the SiO 2 film formed on one side of the substrate was completely removed by dry etching, gold (Au) was further formed thereon by 100 nm sputtering to form an extraction 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 deposition apparatus (ULVAC, EX-400), and the following comparative compound (1) was deposited on the insulator layer at a deposition rate of 0.05 nm / s with a thickness of 50 nm. It formed into a film as an organic-semiconductor layer.
  • gold was deposited to a thickness of 50 nm through a metal mask, so that a source electrode and a drain electrode that were 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 (channel width W) of the source electrode and the drain electrode was 5 mm (see FIG. 3).
  • the obtained organic thin film transistor was p-type driven at the gate voltage V G of ⁇ 70 V in the same manner as in Example 3.
  • Table 2 shows the results of measuring the on / off ratio of the current between the source and drain electrodes and calculating the field effect mobility ⁇ of the holes.
  • Example 5 (Synthesis of Compound (A-12)) The corresponding boronic acid was synthesized in the same manner as in Example 1, and compound (A-12) was synthesized in the same manner as in Example 1 using the boronic acid. The target product was confirmed by FD-MS measurement. The measurement results of FD-MS are shown below.
  • Examples 7 and 8 Synthesis of compounds (A-20) and (A-27)
  • the corresponding boronic acids were synthesized in the same manner as in Example 6, and the compounds (A-20) and (A-27) were synthesized in the same manner as in Example 1 using the boronic acids.
  • the target product was confirmed by FD-MS measurement. The measurement results of FD-MS are shown below.
  • Example 9 (Synthesis of Compound (A-50)) (1) Synthesis of compound (p) The reactor was charged with 50.0 g (0.177 mol) of 1-fluoro-4-iodobenzene, 1.0 g (0.86 mmol) of tetrakistriphenylphosphine palladium (0), 0.33 g (1.73 mmol) of copper (I) iodide. ), 350 ml of diisopropylamine was added, and 21.0 g (0.194 mol) of 1-octyne and 350 ml of dehydrated toluene were added thereto, and the mixture was heated and stirred at 60 ° C. for 6 and a half hours. The reaction mixture was filtered, the solvent of the filtrate was removed under reduced pressure, and purified by column chromatography to obtain 51.6 g of a crude product (p).
  • Examples 11, 12, and 13 Synthesis of compounds (B-8), (B-12), and (B-27)
  • the boronic acid corresponding to each was synthesized in the same manner as in Example 1 or Example 6, the intermediate corresponding to compound (e) was synthesized using the boronic acid, and the compound ( B-8), (B-12) and (B-27) were synthesized.
  • the target product was confirmed by FD-MS measurement. The measurement results of FD-MS are shown below.
  • Example 14 Comparison of solubility
  • solubility in a solvent is one of the important characteristics, so the solubility was examined.
  • Table 1 shows compounds (A-8), (A-20), (A-23), (A-27), (A-50), (B--) synthesized in Examples 1, 6 to 10, and 13 23) and solubility results of (B-27) in toluene are shown.
  • concentration of 0.4 mass% in toluene is a standard since the density
  • a structure in which R 3 and R 9 are linear alkyl groups in the formula (1) or a structure in which R 23 and R 29 are linear alkyl groups in the formula (2) is preferable for compatibility with the coating process. I understand that.
  • Example 15 (Production of organic thin film transistor by coating process) In the same manner as in Example 3, the insulating layer was formed. Next, 0.4% by mass of compound (A-20) was dissolved in toluene, and the film was formed on the substrate on which the insulator layer was formed by using a spin coater (Mikasa Co., Ltd .: 1H-D7). It dried at 80 degreeC and formed into a film as an organic-semiconductor layer. Next, gold (Au) was formed in a film thickness of 50 nm through a metal mask with a vacuum deposition apparatus, thereby forming source and drain electrodes that were not in contact with each other, thereby producing an organic thin film transistor.
  • a spin coater Moikasa Co., Ltd .: 1H-D7
  • the obtained organic thin film transistor was p-type driven at the gate voltage V G of ⁇ 70 V in the same manner as in Example 3.
  • Table 2 shows the results of measuring the on / off of the current between the source and drain electrodes and calculating the hole field-effect mobility ⁇ .
  • Example 16 (Production of organic thin film transistor by coating process) An organic thin film transistor was produced in the same manner as in Example 15 except that the compound (A-23) was used instead of the compound (A-20) as the material of the organic semiconductor layer. The obtained organic thin film transistor was p-type driven at the gate voltage V G of ⁇ 70 V in the same manner as in Example 15. Table 2 shows the results of measuring the on / off ratio of the current between the source and drain electrodes and calculating the field effect mobility ⁇ of the holes.
  • Example 17 (Production of organic thin film transistor by coating process) An organic thin film transistor was produced in the same manner as in Example 15 except that the compound (A-27) was used instead of the compound (A-20) as a material for the organic semiconductor layer. The obtained organic thin film transistor was p-type driven at the gate voltage V G of ⁇ 70 V in the same manner as in Example 15. Table 2 shows the results of measuring the on / off ratio of the current between the source and drain electrodes and calculating the field effect mobility ⁇ of the holes.
  • Example 18 (Production of organic thin film transistor by vapor deposition process) An organic thin film transistor was produced in the same manner as in Example 3 except that the compound (A-50) was used instead of the compound (A-8) as the material of the organic semiconductor layer. The obtained organic thin film transistor was p-type driven at the gate voltage V G of ⁇ 70 V in the same manner as in Example 3. Table 2 shows the results of measuring the on / off ratio of the current between the source and drain electrodes and calculating the field effect mobility ⁇ of the holes.
  • Example 19 (Production of organic thin film transistor by coating process) An organic thin film transistor was produced in the same manner as in Example 15 except that the compound (B-27) was used instead of the compound (A-20) as the material of the organic semiconductor layer. The obtained organic thin film transistor was p-type driven at the gate voltage V G of ⁇ 70 V in the same manner as in Example 15. Table 2 shows the results of measuring the on / off ratio of the current between the source and drain electrodes and calculating the field effect mobility ⁇ of the holes.
  • the polycyclic fused ring compound (compound for organic thin film transistor) of the present invention can be used as a material for the organic semiconductor layer of the organic thin film transistor. Since the polycyclic fused ring compound of the present invention has high carrier mobility as a material for the organic semiconductor layer, this organic thin film transistor has a high response speed (driving speed) and high performance as a transistor. It can also be used as an organic thin film light emitting transistor capable of emitting light.

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  • Materials Engineering (AREA)
  • Thin Film Transistor (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Abstract

L'invention concerne un composé de formule (1) destiné à un transistor organique en couches minces.
PCT/JP2010/007219 2009-12-14 2010-12-13 Composé polycyclique à cycles fusionnés et transistor organique en couches minces le contenant WO2011074231A1 (fr)

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JP2013232521A (ja) * 2012-04-27 2013-11-14 Udc Ireland Ltd 有機電界発光素子、有機電界発光素子用材料並びに該有機電界発光素子を用いた発光装置、表示装置及び照明装置
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WO2014136827A1 (fr) 2013-03-05 2014-09-12 Jnc株式会社 Composé organique contenant un chalcogène et son utilisation
TWI588150B (zh) * 2012-08-14 2017-06-21 日本化藥股份有限公司 雜環化合物及其利用
TWI594983B (zh) * 2012-10-15 2017-08-11 富士軟片股份有限公司 有機薄膜電晶體、萘并雙苯并呋喃化合物、非發光性有機半導體元件用塗佈溶液、有機半導體薄膜、有機薄膜電晶體用材料及有機半導體材料
KR20190101897A (ko) * 2018-02-23 2019-09-02 주식회사 엘지화학 헤테로고리 화합물 및 이를 포함하는 유기 발광 소자
JP2020053706A (ja) * 2019-12-19 2020-04-02 純一 竹谷 有機電界効果トランジスタ
US11239426B2 (en) 2016-11-23 2022-02-01 Lg Chem, Ltd. Electroactive compounds
CN114573549A (zh) * 2020-11-30 2022-06-03 江苏和成新材料有限公司 一种二苯并噻吩类化合物的制备方法及其应用

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JP2012169550A (ja) * 2011-02-16 2012-09-06 Tokai Rika Co Ltd 有機半導体材料
TWI571453B (zh) * 2011-11-02 2017-02-21 Ｕｄｃ愛爾蘭有限公司 有機電場發光元件、有機電場發光元件用材料以及使用該有機電場發光元件之發光裝置、顯示裝置及照明裝置
WO2013064881A2 (fr) 2011-11-02 2013-05-10 ユーディーシー アイルランド リミテッド Elément électroluminescent organique, matière pour élément électroluminescent organique et dispositif d'émission de lumière, dispositif d'affichage et dispositif d'éclairage, employant chacun l'élément électroluminescent organique
KR20140094562A (ko) 2011-11-02 2014-07-30 유디씨 아일랜드 리미티드 유기 전계 발광 소자, 유기 전계 발광 소자용 재료 그리고 그 유기 전계 발광 소자를 사용한 발광 장치, 표시 장치 및 조명 장치
US9728726B2 (en) 2011-11-02 2017-08-08 Udc Ireland Limited Organic electroluminescent element, material for organic electroluminescent element and light emitting device, display device, and illumination device, each employing organic electroluminescent element
JP2013232521A (ja) * 2012-04-27 2013-11-14 Udc Ireland Ltd 有機電界発光素子、有機電界発光素子用材料並びに該有機電界発光素子を用いた発光装置、表示装置及び照明装置
TWI588150B (zh) * 2012-08-14 2017-06-21 日本化藥股份有限公司 雜環化合物及其利用
JP2014082248A (ja) * 2012-10-15 2014-05-08 Fujifilm Corp 有機薄膜トランジスタ、有機半導体薄膜および有機半導体材料
TWI594983B (zh) * 2012-10-15 2017-08-11 富士軟片股份有限公司 有機薄膜電晶體、萘并雙苯并呋喃化合物、非發光性有機半導體元件用塗佈溶液、有機半導體薄膜、有機薄膜電晶體用材料及有機半導體材料
WO2014136827A1 (fr) 2013-03-05 2014-09-12 Jnc株式会社 Composé organique contenant un chalcogène et son utilisation
KR102203794B1 (ko) 2013-03-05 2021-01-15 제이엔씨 주식회사 칼코겐 함유 유기 화합물 및 그의 용도
CN105102462A (zh) * 2013-03-05 2015-11-25 捷恩智株式会社 含有氧族元素的有机化合物及其用途
KR20150126898A (ko) 2013-03-05 2015-11-13 제이엔씨 주식회사 칼코겐 함유 유기 화합물 및 그의 용도
US9853225B2 (en) 2013-03-05 2017-12-26 Jnc Corporation Chalcogen-containing organic compound and a use thereof
CN105102462B (zh) * 2013-03-05 2018-02-02 捷恩智株式会社 含有氧族元素的有机化合物、其制造方法以及用途
JP6008158B2 (ja) * 2013-03-05 2016-10-19 Jnc株式会社 カルコゲン含有有機化合物およびその用途
US11239426B2 (en) 2016-11-23 2022-02-01 Lg Chem, Ltd. Electroactive compounds
US12004419B2 (en) 2016-11-23 2024-06-04 Lg Chem, Ltd. Electroactive compounds
KR102187984B1 (ko) 2018-02-23 2020-12-07 주식회사 엘지화학 헤테로고리 화합물 및 이를 포함하는 유기 발광 소자
KR20190101897A (ko) * 2018-02-23 2019-09-02 주식회사 엘지화학 헤테로고리 화합물 및 이를 포함하는 유기 발광 소자
JP2020053706A (ja) * 2019-12-19 2020-04-02 純一 竹谷 有機電界効果トランジスタ
CN114573549A (zh) * 2020-11-30 2022-06-03 江苏和成新材料有限公司 一种二苯并噻吩类化合物的制备方法及其应用
CN114573549B (zh) * 2020-11-30 2024-04-02 江苏和成新材料有限公司 一种二苯并噻吩类化合物的制备方法及其应用

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