JP2006219550A - Organic semiconductor material, organic thin film transistor (tft), electric field effect transistor and switching element - Google Patents

Organic semiconductor material, organic thin film transistor (tft), electric field effect transistor and switching element Download PDF

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JP2006219550A
JP2006219550A JP2005032739A JP2005032739A JP2006219550A JP 2006219550 A JP2006219550 A JP 2006219550A JP 2005032739 A JP2005032739 A JP 2005032739A JP 2005032739 A JP2005032739 A JP 2005032739A JP 2006219550 A JP2006219550 A JP 2006219550A
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group
organic
semiconductor material
organic semiconductor
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Katsura Hirai
Hiroshi Kita
Kazuaki Nakamura
Chiyoko Takemura
Tatsuo Tanaka
和明 中村
弘志 北
桂 平井
達夫 田中
千代子 竹村
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Konica Minolta Holdings Inc
コニカミノルタホールディングス株式会社
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Abstract

PROBLEM TO BE SOLVED: To molecularly design an organic semiconductor material useful for use in a thin film transistor, and to use the obtained organic semiconductor material, an organic TFT, a field effect transistor having high carrier mobility and high durability. An organic TFT or a switching element having the field effect transistor is provided.
SOLUTION: A repeating unit having regioregularity, wherein the repeating unit contains an aromatic monocyclic ring or a condensed ring having aromaticity in the molecule, and the total of the monocyclic ring or the condensed ring is 10 to 200 oligomers or polymers, and the content of a single molecular weight component in the oligomers or the polymers is 60 mol% or more.
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Description

  The present invention relates to an organic semiconductor material, an organic thin film transistor, a field effect transistor, and a switching element.

  With the widespread use of information terminals, there is an increasing need for flat panel displays as computer displays. In addition, with the progress of computerization, information that has been provided on paper media in the past has become more and more electronically provided. As a mobile display medium that is thin, light, and easy to carry, electronic paper or There is a growing need for digital paper.

  In general, in a flat display device, a display medium is formed using an element utilizing liquid crystal, organic EL, electrophoresis, or the like. In such display media, a technique using an active drive element (TFT element) as an image drive element has become mainstream in order to ensure uniformity of screen brightness, screen rewrite speed, and the like. For example, in a normal computer display, these TFT elements are formed on a glass substrate, and liquid crystal, organic EL elements, etc. are sealed.

  Here, semiconductors such as a-Si (amorphous silicon) and p-Si (polysilicon) can be mainly used for the TFT element, and these Si semiconductors (and metal films as necessary) are formed into a multilayer structure. The TFT element is manufactured by sequentially forming the drain and gate electrodes on the substrate. The manufacture of such a TFT element usually requires sputtering or other vacuum manufacturing processes.

However, in the manufacture of such a TFT element, the vacuum system manufacturing process including the vacuum chamber must be repeated many times to form each layer, and the apparatus cost and running cost have become enormous. For example, in the case of TFT elements, it is usually necessary to repeat processes such as sputtering, CVD, photolithography, etching, and cleaning many times in order to form each layer, and elements are formed on a substrate through tens of processes. is doing. In such a conventional manufacturing method using a Si semiconductor, it is not easy to change the equipment, for example, a design change of a manufacturing apparatus such as a vacuum chamber is required in response to the need for a large display screen.
In addition, since the formation of such a conventional TFT element using a Si material includes a process at a high temperature, the substrate material is restricted to be a material that can withstand the process temperature. Therefore, in practice, glass must be used, and when the above-described thin display such as electronic paper or digital paper is configured using such a conventionally known TFT element, the display is heavy and flexible. Products that may break due to chipping or dropping impact. These characteristics resulting from the formation of TFT elements on a glass substrate are undesirable in satisfying the need for an easy-to-carry-type thin display accompanying the progress of computerization.

  On the other hand, in recent years, organic semiconductor materials have been energetically studied as organic compounds having high charge transport properties. These compounds are expected to be applied to organic laser oscillation elements and organic thin film transistors reported in many papers in addition to charge transport materials for organic EL elements (for example, Non-Patent Document 1, Non-Patent Documents). 2).

  If these organic semiconductor devices can be realized, there is a possibility of obtaining a semiconductor that can be made into a solution by simplifying the manufacturing process by vacuum or low-pressure deposition at a relatively low temperature and further improving the molecular structure appropriately. It is conceivable that the organic semiconductor solution is made into an ink and manufactured by a printing method including an ink jet method. Manufacturing by these low-temperature processes has been considered impossible for conventional Si-based semiconductor materials, but there is a possibility for devices using organic semiconductors, so the above-mentioned restrictions on substrate heat resistance are relaxed. For example, a TFT element may be formed on the transparent resin substrate. If a TFT element is formed on a transparent resin substrate and the display material can be driven by the TFT element, the display is lighter and more flexible than conventional ones, and will not crack even if dropped (or very difficult to break) It could be a display.

  However, organic semiconductors for realizing such TFT elements have been studied so far such as acenes such as pentacene and tetracene (see, for example, Patent Document 1), phthalocyanines including lead phthalocyanine, perylene and its tetra. Low molecular weight compounds such as carboxylic acid derivatives (for example, see Patent Document 2), aromatic oligomers typically represented by thiophene hexamers called α-thienyl or sexithiophene (for example, see Patent Document 3), naphthalene, A compound in which a 5-membered heteroaromatic ring is condensed symmetrically to anthracene (for example, see Patent Document 4), mono, oligo, and polydithienopyridine (for example, see Patent Document 5), and further, polythiophene, polythienylene vinylene, High conjugated content such as poly-p-phenylene vinylene Such as limited number of compounds (e.g., see Non-Patent Documents 1 to 3.) I have only in the development of the semiconductor composition using the novel charge-transporting material showing high carrier mobility has been awaited.

  In addition, in Japanese Patent Application Laid-Open No. 2003-292588, US Patent Application Publication Nos. 2003/136958, 2003/160230, and 2003/164495, “a polymer TFT in an integrated circuit logic element for microelectronics” is disclosed. However, most of the semiconductor polythiophenes are oxidatively doped with ambient oxygen, which increases the electrical conductivity, and thus increases the electrical conductivity. As a result, devices made from these materials have higher off-currents and therefore lower current on / off ratios, so many of these materials are used in material processing and device manufacturing. Eliminate or minimize oxidative doping by eliminating environmental oxygen during Careful attention should be paid to these precautions, which push up manufacturing costs and reduce the appeal of certain polymer TFTs as an economical alternative to amorphous silicon technology, especially for large area devices. These and other disadvantages are avoided or minimized in embodiments of the present invention.

Therefore, an electronic device having a strong resistance to oxygen and a relatively high current on / off ratio is desired. However, the level of improvement is not satisfactory, and further improvement is desired.
JP-A-5-55568 Japanese Patent Laid-Open No. 5-190877 JP-A-8-264805 JP-A-11-195790 JP 2003-155289 A JP 2003-261655 A JP 2003-264327 A JP 2003-268083 A "Science" 289, 599 (2000) "Nature" 403, 521 (2000) Advanced Material, 2002, No. 2, page 99

  The object of the present invention is to molecularly design an organic semiconductor material useful for thin film transistor applications, and to use the obtained organic semiconductor material to exhibit high carrier mobility, a high ON / OFF ratio, and high durability. Another object is to provide an organic TFT, a field effect transistor, and a switching element having the organic TFT or the field effect transistor.

  The above object of the present invention has been achieved by the following constitutions 1-12.

(Claim 1)
Having a repeating unit having regioregularity, and the repeating unit includes an aromatic monocyclic ring or aromatic condensed ring in the molecule, and the total of the monocyclic ring or condensed ring is 10 to 200 An organic semiconductor material characterized in that the content of a single molecular weight component in the oligomer or polymer is 60 mol% or more.

(Claim 2)
The organic semiconductor material according to claim 1, wherein the total number of the single rings or the condensed rings is 40 to 100.

(Claim 3)
The organic semiconductor material according to claim 1, wherein the single molecular weight component is 80 mol% or more.

(Claim 4)
The aromatic single ring is a benzene ring, furan ring, thiophene ring, oxazole ring, pyrrole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, oxadiazole ring, triazole ring, imidazole ring, The organic semiconductor material according to claim 1, wherein the organic semiconductor material is at least one ring selected from the group consisting of a pyrazole ring and a thiazole ring.

(Claim 5)
The aromatic condensed ring is a naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysene ring, naphthacene ring, triphenylene ring, acenaphthene ring, coronene ring, fluorene ring, fluoranthrene ring, naphthacene ring , Tetracene ring, pentacene ring, heptacene ring, hexacene ring, perylene ring, pentaphen ring, picene ring, pyrene ring, pyranthrene ring, anthraanthrene ring, benzimidazole ring, indole ring, benzimidazole ring, benzothiazole ring, thienothiophene A ring, a dithienobenzene ring, a benzoxazole ring, a quinoxaline ring, a quinazoline ring, a phthalazine ring, a carbazole ring, a carboline ring, or at least one ring selected from the group consisting of a diazacarbazole ring. The organic semiconductor material according to any one of to 3.

(Claim 6)
6. At least one of the aromatic single rings or at least one of the condensed rings having aromaticity has an alkyl group as a substituent. Organic semiconductor materials.

(Claim 7)
The organic semiconductor material according to claim 6, wherein the alkyl group is a linear alkyl group having 2 to 20 carbon atoms.

(Claim 8)
The oligomer or polymer includes a thiophene ring repeating unit A having a substituent or an unsubstituted thiophene ring repeating unit B, and the number of thiophene rings included in the total of the repeating unit A and the repeating unit B is It is 10-100, The organic-semiconductor material of any one of Claims 1-7 characterized by the above-mentioned.

(Claim 9)
The organic semiconductor material according to claim 8, wherein the thiophene ring repeating unit A has a head-to-head structure, a head-to-tail structure, or a tail-to-tail structure.

(Claim 10)
An organic thin film transistor, wherein the organic semiconductor material according to claim 1 is used for a semiconductor layer.

(Claim 11)
An organic charge transporting material and a gate electrode directly or indirectly in contact with the organic charge transporting material, and by applying a charge between the gate electrode and the organic charge transporting material, the organic charge transporting property In a field effect transistor that controls the current in a material,
A field effect transistor, wherein the organic charge transporting material is the organic semiconductor material according to any one of claims 1 to 9.

(Claim 12)
A switching element comprising the organic transistor according to claim 10 or the field effect transistor according to claim 11.

  According to the present invention, an organic semiconductor material useful for the production of an organic thin film transistor (hereinafter abbreviated as an organic TFT) is molecularly designed, and the organic semiconductor material is used to exhibit high carrier mobility and a high ON / OFF ratio. Thus, an organic TFT and a field effect transistor having excellent transistor characteristics and high durability were obtained. Moreover, by using them, it was possible to provide a switching element with good switching characteristics.

  In the organic semiconductor material of the present invention, an organic semiconductor material useful for thin film transistor applications can be obtained by using the structure defined in any one of claims 1 to 10. In addition, organic TFTs and field-effect transistors manufactured using the organic semiconductor material exhibit excellent transistor characteristics such as high carrier mobility and good ON / OFF characteristics, and are highly durable. I understood it. Moreover, it turned out that the switching element produced using this organic TFT or this field effect transistor shows a favorable switching characteristic.

  The reason why the present inventors have obtained such an excellent organic thin film transistor is that an oligomer or polymer according to the present invention is used as a repeating unit, and the HH (Head to Head) structure or HT (Head) described below will be described below. to tail), the side chain substituents such as represented by a structure having regularity in a certain direction are adjusted so that the positional relationship with adjacent molecules is regular, and such stereoregularity It is presumed that the use of a compound having a characteristic facilitates the formation of a lamellar structure that is advantageous for exhibiting TFT characteristics.

  It can be expected that the closer the compound having stereoregularity is to a single component, the more easily the above characteristics are exhibited. Therefore, it can be expected that a material capable of exhibiting higher performance TFT characteristics can be provided.

  Hereinafter, details of each component according to the present invention will be sequentially described.

<< Oligomer, polymer >>
The oligomer and polymer according to the present invention will be described.

  The oligomer and polymer according to the present invention have a repeating unit having regioregularity, and the repeating unit contains an aromatic monocyclic ring or a condensed condensed ring having aromaticity in the molecule, It is an oligomer or polymer having a total of 10 to 200 fused rings, and the oligomer or the polymer is characterized in that the content of a single molecular weight component is 60 mol% or more.

  Here, the content of the single molecular weight component according to the present invention can be obtained by commercially available HPLC measurement.

<Stereoscopic characteristics of oligomer and polymer repeat units>
The polymer according to the present invention has a recurring unit having regioregularity. Specifically, the polymer has a head-to-head structure, a head-to-tail structure, or a tail-to-structure in the structure. For example, it has a tail structure.

  Furthermore, in the present invention, the recurring unit having regioregularity means that a specific aromatic monocyclic ring or a condensed ring having a specific aromaticity, the monocyclic ring or the condensed ring is specified in the repeating unit. The case where a plurality of repeating units having a substituent at a specific substitution position is contained in the molecule can be given.

  Specifically, in specific examples of the oligomer or polymer to be described later, the repeating unit represented by [] (however, the total number of aromatic monocyclic or aromatic condensed rings in the repeating unit is 10 to 200). Oligomer or polymer having “repeated unit having regioregularity” is an “oligomer or polymer having repetitive units”.

  Regarding the head-to-head structure, head-to-tail structure, and tail-to-tail structure according to the present invention, for example, “π-electron organic solid” (1998, published by the Japan Society for the Science of Chemistry, edited by Japan Chemical Industry) 27-32, Adv. Mater. 1998, 10, no. Reference can be made to pages 2, 93 to 116, etc. Here, specific structural features of each are shown below.

    Head-to-head structure

    Head-to-tail structure

    Tail-to-Tail structure

<< Aromatic monocycle in repeating unit, condensed ring having aromaticity >>
Examples of aromatic monocycles include furan ring, thiophene ring, oxazole ring, pyrrole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, Examples include a thiazole ring and a benzene ring. Further, as an example having an aromatic single ring, a form having two single rings such as a benzene ring such as a biphenyl ring may be used. These rings may have a substituent described later.

  The aromatic condensed ring includes a quinoxaline ring, a quinazoline ring, a phthalazine ring, a carbazole ring, a carboline ring, and a diazacarbazole ring (one of the carbon atoms of the hydrocarbon ring constituting the carboline ring is further substituted with a nitrogen atom). Naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysene ring, naphthacene ring, triphenylene ring, o-terphenyl ring, m-terphenyl ring, p-terphenyl ring, acenaphthene ring , Coronene ring, fluorene ring, fluoranthrene ring, naphthacene ring, pentacene ring, perylene ring, pentaphen ring, picene ring, pyrene ring, pyranthrene ring, anthraanthrene ring and the like. These condensed rings may have a substituent described later.

<< End group of oligomer or polymer >>
The terminal group of the oligomer or polymer according to the present invention will be described.

  The terminal group of the oligomer or polymer according to the present invention is not particularly limited. For example, an aryl group (for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group) , Acenaphthenyl group, fluorenyl group, phenanthryl group, indenyl group, pyrenyl group, biphenylyl group, etc.), alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group) Group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc.), halogen atoms (for example, fluorine atom, chlorine atom, bromine atom) and the like.

<< Substituent >>
The aromatic monocycle or aromatic condensed ring contained in the repeating unit of the oligomer or polymer according to the present invention may have a substituent as shown below. As, for example, an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc.), A cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), an alkenyl group (eg, vinyl group, allyl group, etc.), an alkynyl group (eg, ethynyl group, propargyl group, etc.), an aryl group (eg, phenyl group, p- Chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthenyl Group, fluorenyl group, phenanthryl group, indenyl group, pyrenyl group, biphenylyl group, etc.), aromatic heterocyclic group (for example, furyl group, thienyl group, pyridyl group, pyridazyl group, pyrimidyl group, pyrazyl group, triazyl group, imidazolyl group) , Pyrazolyl group, thiazolyl group, benzimidazolyl group, benzoxazolyl group, quinazolyl group, phthalazyl group, etc.), heterocyclic group (for example, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group (for example, methoxy Group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, etc.), cycloalkoxy group (for example, cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy group (for example, phenoxy) Group Tiloxy group etc.), alkylthio group (eg methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group etc.), cycloalkylthio group (eg cyclopentylthio group, cyclohexylthio group etc.), arylthio Group (for example, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (for example, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group ( For example, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylamine) Minosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), acyl group (for example, acetyl group, Ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (for example, acetyl) Oxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group ) Group, amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino) Group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylamino) Carbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, Tilaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group, etc.), sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridyl group) Sulfinyl group, etc.), alkylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexyl group) Silsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group (eg, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (eg, amino group, ethylamino group, dimethylamino group, butylamino) Group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.), halogen atom (eg, fluorine atom, chlorine atom, bromine atom), fluorinated hydrocarbon Group (for example, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, pentafluorophenyl group, etc.), cyano group, silyl group (for example, trimethylsilyl group, triisopropylsilyl group, triphenylsilyl group, phenyldiethylsilyl group) Etc.) .

  These substituents may be further substituted with the above substituents, or a plurality thereof may be bonded to each other to form a ring.

  Among these, a preferable substituent is an alkyl group, more preferably an alkyl group having 2 to 20 carbon atoms, and particularly preferably an alkyl group having 6 to 12 carbon atoms.

  Hereinafter, although the specific example of the oligomer or polymer based on this invention is shown, this invention is not limited to these.

<< Organic TFT, field effect transistor and switching element >>
The organic TFT, the field effect transistor and the switching element using them according to the present invention will be described. Here, the switching element is sometimes referred to as an organic TFT element depending on its usage, and is sometimes referred to as a field effect transistor element.

  The organic semiconductor material of the present invention is used for a semiconductor layer of an organic TFT or a field effect transistor (also referred to as an organic semiconductor layer in the case of an organic TFT), thereby providing a switching element (also referred to as a transistor device) that is driven well. be able to. An organic TFT (organic thin film transistor) has a source electrode and a drain electrode connected by an organic semiconductor channel as a channel on a support, a top gate type having a gate electrode on a gate insulating layer thereon, and a support First, it is roughly classified into a bottom gate type having a gate electrode on a body and having a source electrode and a drain electrode connected by an organic semiconductor channel through a gate insulating layer.

  In order to install the organic semiconductor material according to the present invention in a semiconductor layer of a switching element using an organic TFT or a field effect transistor, it can be installed on a substrate by vacuum deposition, but it can be dissolved in an appropriate solvent and used as necessary. A solution prepared by adding an additive is preferably placed on a substrate by cast coating, spin coating, printing, an inkjet method, an ablation method, or the like.

  In this case, the solvent for dissolving the organic semiconductor material of the present invention is not particularly limited as long as the organic semiconductor material can be dissolved to prepare a solution having an appropriate concentration. Specifically, diethyl ether or diisopropyl is used. Chain ether solvents such as ether, cyclic ether solvents such as tetrahydrofuran and dioxane, ketone solvents such as acetone and methyl ethyl ketone, alkyl halide solvents such as chloroform and 1,2-dichloroethane, toluene, o-dichlorobenzene, Aromatic solvents such as nitrobenzene and m-cresol, N-methylpyrrolidone, carbon disulfide and the like can be mentioned.

  In the present invention, the material for forming the source electrode, the drain electrode and the gate electrode is not particularly limited as long as it is a conductive material. Platinum, gold, silver, nickel, chromium, copper, iron, tin, antimony lead, tantalum, indium , Palladium, tellurium, rhenium, iridium, aluminum, ruthenium, germanium, molybdenum, tungsten, tin oxide / antimony, indium tin oxide (ITO), fluorine doped zinc oxide, zinc, carbon, graphite, glassy carbon, silver paste and carbon Paste, lithium, beryllium, sodium, magnesium, potassium, calcium, scandium, titanium, manganese, zirconium, gallium, niobium, sodium, sodium-potassium alloy, magnesium, lithium, aluminum, magnesi A copper / gold mixture, a magnesium / silver mixture, a magnesium / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide mixture, a lithium / aluminum mixture, etc., in particular, platinum, gold, silver, copper, aluminum, indium, ITO and carbon are preferred. Alternatively, known conductive polymers whose conductivity is improved by doping or the like, for example, conductive polyaniline, conductive polypyrrole, conductive polythiophene, a complex of polyethylenedioxythiophene and polystyrenesulfonic acid, and the like are also preferably used. Among them, those having low electrical resistance at the contact surface with the semiconductor layer are preferable.

  As a method for forming an electrode, a method for forming an electrode using a known photolithographic method or a lift-off method, using a conductive thin film formed by a method such as vapor deposition or sputtering using the above as a raw material, a metal foil such as aluminum or copper There is a method of etching using a resist by thermal transfer, ink jet or the like. Alternatively, a conductive polymer solution or dispersion, or a conductive fine particle dispersion may be directly patterned by ink jetting, or may be formed from a coating film by lithography or laser ablation. Furthermore, a method of patterning an ink containing a conductive polymer or conductive fine particles, a conductive paste, or the like by a printing method such as relief printing, intaglio printing, planographic printing, or screen printing can also be used.

  Various insulating films can be used as the gate insulating layer, 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, Examples thereof include barium titanate, barium magnesium fluoride, bismuth titanate, strontium bismuth titanate, strontium bismuth tantalate, bismuth tantalate niobate, and yttrium trioxide. Of these, silicon oxide, aluminum oxide, tantalum oxide, and titanium oxide are preferable. Inorganic nitrides such as silicon nitride and aluminum nitride can also be suitably used.

  Examples of the method for forming the film include a vacuum process, a molecular beam epitaxial growth method, an ion cluster beam method, a low energy ion beam method, an ion plating method, a CVD method, a sputtering method, an atmospheric pressure plasma method, and a spray process. Wet processes such as coating methods, spin coating methods, blade coating methods, dip coating methods, casting methods, roll coating methods, bar coating methods, die coating methods, and other wet processes such as printing and ink jet patterning methods, etc. Can be used depending on the material.

  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. Among these, the atmospheric pressure plasma method and the sol-gel method are preferable.

  The method for forming an insulating film by plasma film formation under atmospheric pressure is a process in which a reactive gas is discharged under atmospheric pressure or a pressure near atmospheric pressure to excite reactive gas to form a thin film on a substrate. The method is described in JP-A-11-61406, JP-A-11-133205, JP-A-2000-121804, JP-A-2000-147209, JP-A-2000-185362 (hereinafter referred to as atmospheric pressure). Also called plasma method). Accordingly, a highly functional thin film can be formed with high productivity.

  In addition, as the organic compound film, polyimide, polyamide, polyester, polyacrylate, photo radical polymerization type, photo cation polymerization type photo curable resin, or a copolymer containing an acrylonitrile component, polyvinyl phenol, polyvinyl alcohol, novolac resin, Also, cyanoethyl pullulan or the like can be used. As the method for forming the organic compound film, the wet process is preferable. An inorganic oxide film and an organic oxide film can be laminated and used together. The thickness of these insulating films is generally 50 nm to 3 μm, preferably 100 nm to 1 μm.

  Moreover, a support body is comprised with glass or a flexible resin-made sheet | seat, for example, a plastic film can be used as a sheet | seat. Examples of the plastic film include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate (PC). And a film made of cellulose triacetate (TAC), cellulose acetate propionate (CAP), or the like. Thus, by using a plastic film, the weight can be reduced as compared with the case of using a glass substrate, the portability can be improved, and the resistance to impact can be improved.

  Below, the field effect transistor using the organic thin film formed using the organic-semiconductor material of this invention is demonstrated.

  FIG. 1 is a diagram showing a configuration example of an organic TFT according to the present invention. In FIG. 2A, a source electrode 2 and a drain electrode 3 are formed on a support 6 by a metal foil or the like, an organic semiconductor layer 1 made of the organic semiconductor material of the present invention is formed between the two electrodes, and a substrate is formed thereon. An insulating layer 5 is formed, and a gate electrode 4 is further formed thereon to form a field effect transistor. FIG. 2B shows the organic semiconductor layer 1 formed between the electrodes in FIG. 1A so as to cover the entire surface of the electrode and the support using a coating method or the like. (C) shows that the organic semiconductor layer 1 is first formed on the support 6 by using a coating method or the like, and then the source electrode 2, the drain electrode 3, the insulating layer 5, and the gate electrode 4 are formed.

  In FIG. 4D, after forming the gate electrode 4 on the support 6 with a metal foil or the like, the insulating layer 5 is formed, and the source electrode 2 and the drain electrode 3 are formed on the metal foil or the like on the insulating layer 5. An organic semiconductor layer 1 made of the organic semiconductor material of the present invention is formed between the electrodes. In addition, the configuration as shown in FIGS.

  FIG. 2 is a diagram showing an example of a schematic equivalent circuit diagram of an organic TFT sheet.

  The organic TFT sheet 10 has a large number of organic TFTs 11 arranged in a matrix. 7 is a gate bus line of each TFT 11, and 8 is a source bus line of each TFT 11. An output element 12 is connected to the source electrode of each TFT 11, and this output 12 is, for example, a liquid crystal, an electrophoretic element or the like, and constitutes a pixel in the display device. The pixel electrode may be used as an input electrode of the photosensor. In the illustrated example, a liquid crystal as an output element is shown by an equivalent circuit composed of a resistor and a capacitor. 13 is a storage capacitor, 14 is a vertical drive circuit, and 15 is a horizontal drive circuit.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these. Moreover, the structure of the comparative compound (2) used for an Example is shown below.

Example 1
<< Synthesis of Compound (1) >>
Compound (1) is prepared according to J. Am. Chem. Soc. Perkin Trans. It was synthesized according to 1,2000, 1211-1216, and it was confirmed by 1 H-NMR that it contained 12 units of thiophene ring and had a Head-to-Tail structure (HT structure). Further, it was confirmed from the HPLC measurement result that the purity was 99% or more (this result indicates that the content of the single molecular weight component is almost 100 mol%).

<< Synthesis of Compounds (2) to (5) and Comparative Compound (2) >>
With reference to the synthesis conditions of compound (1), compounds (2) to (5) and comparative compound (2) (the total number of thiophene rings, which are monocycles of comparative compound (2), is 6) It synthesized similarly.

<< Preparation of Comparative Sample (3) >>
Each of the compounds (1) to (5) synthesized above was mixed in an equimolar amount to prepare a comparative compound (3). (The content of each single molecular weight component is 20 mol%.)
Example 2
<< Production of Organic Thin Film Transistor (Organic TFT) Element 1 >>
A Si oxide having a specific resistance of 0.01 Ω · cm as a gate electrode was formed with a thermal oxide film having a thickness of 2000 mm to form a gate insulating layer, and then surface treatment with octadecyltrichlorosilane was performed. A cast film (thickness 50 nm) was prepared by applying a chloroform solution of the comparative compound (1) (poly (3-hexylthiophene) (regio regular, Aldrich, average molecular weight 89000, PHT)) using an applicator and air-drying. ) And heat-treated at 50 ° C. for 30 minutes in a nitrogen atmosphere. Further, gold was deposited on the surface of this film using a mask to form a source electrode and a drain electrode. An organic thin film transistor element 1 having a width of 100 μm, a thickness of 200 nm, a channel width W = 3 mm, and a channel length L = 20 μm was prepared.

<< Production of Organic Thin Film Transistor Elements 2 and 3 >>
Organic thin-film transistor elements 2 and 3 were produced in the same manner except that the comparative compound (1) was changed to the comparative compound (2) and the comparative sample (3) in the production of the organic thin-film transistor element 1, respectively.

<< Production of Organic Thin Film Transistor Elements 4-7 >>
In the production of the organic thin film transistor 1, organic thin film transistor elements 4 to 7 were produced in the same manner except that the comparative compound (1) was changed to the organic semiconductor material of the present invention shown in Table 1. In addition, the HPLC purity of the exemplary compound of this invention was 99% or more, respectively.

<< Evaluation of Organic Thin Film Transistor Elements 1-7 >>
The organic thin film transistor elements 1 to 7 showed good operating characteristics of the p-channel enhancement type FET. Next, for the organic thin film transistor elements 1 to 7, the carrier mobility is obtained from the saturation region of the IV characteristic, and further the ON / OFF ratio (the drain current value when the drain bias is −50V and the gate bias is −50V and 0V). Ratio). The obtained element was left in the atmosphere for one month, and the carrier mobility and the ON / OFF ratio were obtained again.

  The obtained results are shown in Table 1.

  From the results shown in Table 1, it was found that the organic thin film transistor element of the present invention had better characteristics as a transistor and further suppressed deterioration over time as compared with the comparison.

It is a figure which shows the structural example of the organic TFT which concerns on this invention. It is an example of the schematic equivalent circuit schematic of the organic TFT of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Organic-semiconductor layer 2 Source electrode 3 Drain electrode 4 Gate electrode 5 Insulating layer 6 Support body 7 Gate bus line 8 Source bus line 10 Organic TFT sheet 11 Organic TFT
12 Output element 13 Storage capacitor 14 Vertical drive circuit 15 Horizontal drive circuit

Claims (12)

  1. A repeating unit having regioregularity, the repeating unit comprising an aromatic monocyclic ring or aromatic condensed ring in the molecule, the total of the monocyclic ring or condensed ring being 10 to 200 An organic semiconductor material characterized in that the content of a single molecular weight component in the oligomer or polymer is 60 mol% or more.
  2. The organic semiconductor material according to claim 1, wherein the total number of the single rings or the condensed rings is 40 to 100.
  3. The organic semiconductor material according to claim 1, wherein the single molecular weight component is 80 mol% or more.
  4. The aromatic single ring is a benzene ring, furan ring, thiophene ring, oxazole ring, pyrrole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, oxadiazole ring, triazole ring, imidazole ring, The organic semiconductor material according to any one of claims 1 to 3, wherein the organic semiconductor material is at least one ring selected from the group consisting of a pyrazole ring and a thiazole ring.
  5. The aromatic condensed ring is a naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysene ring, naphthacene ring, triphenylene ring, acenaphthene ring, coronene ring, fluorene ring, fluoranthrene ring, naphthacene ring , Tetracene ring, pentacene ring, heptacene ring, hexacene ring, perylene ring, pentaphen ring, picene ring, pyrene ring, pyranthrene ring, anthraanthrene ring, benzimidazole ring, indole ring, benzimidazole ring, benzothiazole ring, thienothiophene A ring, a dithienobenzene ring, a benzoxazole ring, a quinoxaline ring, a quinazoline ring, a phthalazine ring, a carbazole ring, a carboline ring, or at least one ring selected from the group consisting of a diazacarbazole ring. The organic semiconductor material according to any one of to 3.
  6. 6. At least one of the aromatic single rings or at least one of the condensed rings having aromaticity has an alkyl group as a substituent. Organic semiconductor materials.
  7. The organic semiconductor material according to claim 6, wherein the alkyl group is a linear alkyl group having 2 to 20 carbon atoms.
  8. The oligomer or polymer contains a thiophene ring repeating unit A having a substituent or an unsubstituted thiophene ring repeating unit B, and the number of thiophene rings included in the total of the repeating unit A and the repeating unit B is It is 10-100, The organic-semiconductor material of any one of Claims 1-7 characterized by the above-mentioned.
  9. The organic semiconductor material according to claim 8, wherein the thiophene ring repeating unit A has a head-to-head structure, a head-to-tail structure, or a tail-to-tail structure.
  10. An organic thin film transistor, wherein the organic semiconductor material according to claim 1 is used for a semiconductor layer.
  11. An organic charge transporting material and a gate electrode directly or indirectly in contact with the organic charge transporting material, and by applying a charge between the gate electrode and the organic charge transporting material, the organic charge transporting property In a field effect transistor that controls the current in a material,
    A field effect transistor, wherein the organic charge transporting material is the organic semiconductor material according to any one of claims 1 to 9.
  12. A switching element comprising the organic transistor according to claim 10 or the field effect transistor according to claim 11.
JP2005032739A 2005-02-09 2005-02-09 Organic semiconductor material, organic thin film transistor (tft), electric field effect transistor and switching element Pending JP2006219550A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006232986A (en) * 2005-02-24 2006-09-07 Mitsubishi Chemicals Corp Electroconductive polymer, organic electronic device using the same and field effect transistor
JP2009040857A (en) * 2007-08-08 2009-02-26 Hiroshima Univ Polythiophene and electroluminescent material

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JPH10190001A (en) * 1996-12-20 1998-07-21 Lucent Technol Inc Manufacture of organic thin film transistor
JP2000230040A (en) * 1999-02-10 2000-08-22 Carnegie Mellon Univ Production of poly(3-substituted thiophene)
JP2001196664A (en) * 2000-01-12 2001-07-19 Japan Science & Technology Corp Thin film material for generation and transfer of optical carrier of photoelectric conversion element comprising stereoregularity polythiophene derivative
JP2003261654A (en) * 2002-03-07 2003-09-19 Mitsubishi Chemicals Corp Electroconductive polymer, its preparation process and electro-optical transducer, electric or electronic device, opto-electrical transducer and electrical wiring board containing the electroconductive polymer
JP2003292588A (en) * 2002-01-11 2003-10-15 Xerox Corp Polythiophenes and device using the same
JP2004115695A (en) * 2002-09-27 2004-04-15 Japan Science & Technology Corp Method for producing poly(3-substituted thiophene)
JP2004339193A (en) * 2003-03-07 2004-12-02 Merck Patent Gmbh Monomer, oligomer and polymer containing fluorene and aryl group

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Publication number Priority date Publication date Assignee Title
JPH10190001A (en) * 1996-12-20 1998-07-21 Lucent Technol Inc Manufacture of organic thin film transistor
JP2000230040A (en) * 1999-02-10 2000-08-22 Carnegie Mellon Univ Production of poly(3-substituted thiophene)
JP2001196664A (en) * 2000-01-12 2001-07-19 Japan Science & Technology Corp Thin film material for generation and transfer of optical carrier of photoelectric conversion element comprising stereoregularity polythiophene derivative
JP2003292588A (en) * 2002-01-11 2003-10-15 Xerox Corp Polythiophenes and device using the same
JP2003261654A (en) * 2002-03-07 2003-09-19 Mitsubishi Chemicals Corp Electroconductive polymer, its preparation process and electro-optical transducer, electric or electronic device, opto-electrical transducer and electrical wiring board containing the electroconductive polymer
JP2004115695A (en) * 2002-09-27 2004-04-15 Japan Science & Technology Corp Method for producing poly(3-substituted thiophene)
JP2004339193A (en) * 2003-03-07 2004-12-02 Merck Patent Gmbh Monomer, oligomer and polymer containing fluorene and aryl group

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006232986A (en) * 2005-02-24 2006-09-07 Mitsubishi Chemicals Corp Electroconductive polymer, organic electronic device using the same and field effect transistor
JP2009040857A (en) * 2007-08-08 2009-02-26 Hiroshima Univ Polythiophene and electroluminescent material

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