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WO2007029551A1 - Transistor à film mince organique, corps de base pour transistor à film mince organique et procédé de fabrication du transistor à film mince organique - Google Patents

Transistor à film mince organique, corps de base pour transistor à film mince organique et procédé de fabrication du transistor à film mince organique Download PDF

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Publication number
WO2007029551A1
WO2007029551A1 PCT/JP2006/316907 JP2006316907W WO2007029551A1 WO 2007029551 A1 WO2007029551 A1 WO 2007029551A1 JP 2006316907 W JP2006316907 W JP 2006316907W WO 2007029551 A1 WO2007029551 A1 WO 2007029551A1
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group
thin film
film transistor
organic thin
surface treatment
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Japanese (ja)
Inventor
Katsura Hirai
Chiyoko Takemura
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Konica Minolta Inc
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Konica Minolta Inc
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    • 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
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • 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]
    • 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]
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom

Definitions

  • Organic thin film transistor, organic thin film transistor substrate, and organic thin film transistor manufacturing method are organic thin film transistors, organic thin film transistor substrate, and organic thin film transistor manufacturing method
  • the present invention relates to an organic thin film transistor substrate for organic thin film transistor and a method for producing an organic thin film transistor.
  • a display medium is formed using elements utilizing liquid crystal, organic EL, electrophoresis or the like.
  • a technique using an active drive element composed of a thin film transistor (TFT) as an image drive element has become mainstream.
  • TFT thin film transistor
  • these TFT elements are formed on a glass substrate, and liquid crystals, organic EL elements, etc. are sealed.
  • a TFT element usually has a semiconductor thin film such as a-Si (amorphous silicon) or p-Si (polysilicon) or a metal thin film such as a source, drain, or gate electrode on a glass substrate. It is manufactured by sequentially forming on the substrate.
  • the production of flat panel displays using TFTs usually requires high-precision photolithographic processes in addition to vacuum equipment such as CVD and sputtering and thin film formation processes that require high-temperature processing processes.
  • the running cost is very heavy. Furthermore, with the recent increase in the screen size of displays, their costs have become enormous.
  • organic semiconductor materials have been energetically studied as organic compounds having high charge transport properties, and application to organic thin film transistors is expected. If these organic semiconductor devices can be realized, solution can be obtained by simplifying the manufacturing process by relatively low temperature, vacuuming at low temperature, and low-pressure deposition, and by appropriately improving the molecular structure. It is thought that there is a possibility of obtaining a semiconductor, and the production by a printing method including an ink jet method can be considered by converting an organic semiconductor solution into an ink. Manufacturing using these low-temperature processes has been considered impossible for conventional Si-based semiconductor materials.
  • a TFT element may be formed on a transparent resin substrate. If a TFT element can be 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. Will be difficult to crack))
  • Patent Document 1 a method using a liquid crystalline material as a solvent of an organic semiconductor material as in Patent Document 1 and a fluorination as in Patent Document 2
  • Patent Document 3 discloses a method of using a mixed solvent for the production of an organic semiconductor thin film.
  • Patent Document 4 discloses surface treatment of a gate insulating film with a surface treatment material containing a phenyl group or the like.
  • a silane coupling agent having an alkyl group or a phenyl group on the surface of the substrate while exerting force When surface treatment is performed by itself, the performance of the organic thin film transistor device (TFT device) in which the organic semiconductor layer is created by the vapor deposition process is improved, but the surface of the substrate created by the solution process repels the organic semiconductor solution. As a result, it was difficult to provide a stable organic semiconductor layer with insufficient coating properties. Therefore, it is desirable for the solution process to achieve both TFT characteristics and coating properties of organic semiconductor materials.
  • Patent Document 1 Japanese Patent Laid-Open No. 2004-31458
  • Patent Document 2 JP 2000-307172 A
  • Patent Document 3 International Publication No. 03Z65409 Pamphlet
  • Patent Document 4 Japanese Patent Laid-Open No. 2005-158765
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide an organic thin film transistor manufactured by a solution process having good TFT characteristics and high production efficiency, and a method for manufacturing the same.
  • An organic thin film transistor having a substrate and an organic semiconductor layer on the surface thereof, and having a surface treatment layer formed of 2 to 5 kinds of surface treatment agents on the substrate surface between the organic semiconductor layer and the substrate.
  • Organic thin-film transistor characterized.
  • the present invention can provide an organic thin film transistor manufactured by a solution process having good TFT characteristics and high production efficiency, and a method for manufacturing the same.
  • FIG. 1 is a conceptual diagram showing an example of a plasma discharge treatment container.
  • FIG. 2 is a schematic view showing another example of a plasma discharge treatment container.
  • FIG. 3 is a schematic perspective view showing an example of a cylindrical roll electrode.
  • FIG. 4 is a schematic perspective view showing an example of a cylindrical fixed electrode.
  • FIG. 5 is a schematic perspective view showing an example of a prismatic fixed electrode.
  • FIG. 6 is a conceptual diagram showing an example of a plasma discharge treatment apparatus.
  • FIG. 7 is a schematic view showing another example of a plasma discharge treatment apparatus.
  • FIG. 8 is a schematic view showing an example of an atmospheric pressure plasma discharge treatment apparatus.
  • FIG. 9 is a schematic view showing another example of an atmospheric pressure plasma discharge treatment apparatus.
  • FIG. 10 is a diagram showing an example of the configuration of an organic thin film transistor element.
  • the present inventors have found that the carrier mobility is improved by increasing the contact angle of the layer in contact with the organic semiconductor layer (substrate surface). Apply at least two types of surface treatment agent to the surface of the surface of the surface of the coating to improve the coating properties.
  • the present inventors have found that an organic thin film transistor can be manufactured by a solution process capable of achieving both TFT device performance and high production efficiency.
  • the surface of the substrate (both substrate !, u) is subjected to surface treatment using 2 to 5 types of surface treatment agents to form a surface treatment layer on the surface of the substrate, and then the surface treatment layer is coated on the surface treatment layer. It is characterized by forming an organic semiconductor layer.
  • the surface treating agent used in the present invention an agent that increases the contact angle of the surface with water when the surface of the substrate is surface treated is used.
  • the contact angle is preferably 50 degrees or more, more preferably 70 to 170 degrees, and even more preferably 90 to 130 degrees. If the contact angle is low, the carrier mobility and onZoff ratio of the transistor element are remarkably lowered, and if it is too high, the coating property of the organic semiconductor material solution is lowered. This contact angle is measured using a contact angle meter (CA-DT, type A: manufactured by Kyowa Interface Science Co., Ltd.) in an environment of 20 ° C 50% RH.
  • CA-DT contact angle meter
  • the surface treatment agent has an alkyl group or an aromatic group.
  • the alkyl group may be a fluoroalkyl group or an alkyl group composed only of carbon and hydrogen.
  • the alkyl group has 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms.
  • the aromatic group include an aromatic hydrocarbon group having 6 to 20 carbon atoms such as a phenyl group which may have a substituent. More preferably, an organosilane compound having both a hydrolyzable group and an alkyl group is used.
  • the hydrolyzable group means a functional group that can be polymerized by adding water and hydrogen, and is not particularly limited in the present invention, but preferably an alkoxy group or an acetyl group. Can be mentioned. More preferably, it is an alkoxy group, and further preferably has an ethoxy group in terms of reactivity and physical properties of the raw material.
  • organosilane compound in addition to the organosilane compound, an organometallic compound in which the metal element is Ti, Ge, Zr or Sn, and a compound having fluorine are also particularly preferred.
  • An organosilane compound, Ti is particularly preferred.
  • a compound having fluorine is particularly preferred.
  • a compound represented by the following general formula (1) is preferable.
  • M represents Si, Ti, Ge, Zr or Sn.
  • R to R are each
  • 1 6 represents a hydrogen atom or a monovalent group
  • At least one of the groups represented by 16 is an organic group having a fluorine atom, such as an alkyl group or alkenyl group having a fluorine atom.
  • an organic group having a fluorine atom such as an alkyl group or alkenyl group having a fluorine atom.
  • alkyl group having a fluorine atom that is preferable for an organic group containing an aryl group include, for example, a trifluoromethyl group, a perfluoroethyl group, and a perfluoropropyl group.
  • the alkenyl group having a fluorine atom for example, 3, 3, 3-Trifluoro-1-propenyl group and the like
  • the aryl group having a fluorine atom includes groups such as a pentafluorophenyl group.
  • an alkyl group having a fluorine atom, an alkyl group, an alkoxy group formed by an aryl group, an alkyl group, an aryloxy group, or the like can also be used.
  • any number of fluorine atoms may be bonded to any position of the carbon atom in the skeleton, such as at least one or more of the alkyl group, alkenyl group, aryl group, and the like. Bonding is preferred.
  • the carbon atom in the skeleton of the alkyl group or alkenyl group includes, for example, other atoms such as oxygen, nitrogen and sulfur, and divalent groups containing oxygen, nitrogen and sulfur, such as a carbonyl group and a thiocarbonyl group. It may be substituted with a group.
  • examples of the monovalent group include a hydroxy group, an amino group, an isocyanate group, a halogen atom, an alkyl group, a cycloalkyl group, a alkenyl group, an aryl group, an alkoxy group, and an alkenyl group.
  • j represents an integer of 0 to 150, preferably 0 to 50, and more preferably j is in the range of 0 to 20.
  • the halogen atom is preferably a chlorine atom, a bromine atom or an iodine atom.
  • the alkyl group, alkyl group, aryl group, alkoxy group, alkoxy group, and aryloxy group are preferably an alkoxy group, an alkoxy group, and an aryloxy group. is there.
  • the monovalent group may be further substituted with another group, but is not particularly limited.
  • Preferred substituents include amino group, hydroxyl group, isocyanate group, fluorine atom, chlorine atom, bromine.
  • Halogen atoms such as atoms, alkyl groups, cycloalkyl groups, alkenyl groups, phenyl groups such as phenyl groups, alkoxy groups, alkoxy groups, aryloxy groups
  • groups such as an acyl group, an acyloxy group, an alkoxycarbonyl group, an alkanamide group, an arylamide group, an alkyl group rubamoyl group, an aryl group rubamoyl group, a silyl group, an alkylsilyl group, and an alkoxysilyl group.
  • RiR 2 R 3 M— represents the metal atom
  • R 3 each represents a monovalent group
  • examples of the monovalent group include the organic group having a fluorine atom or RR.
  • a structure having a plurality of metal atoms further substituted by a group represented by Examples of these metal atoms include Si Ti and the like, and examples thereof include a silyl group, an alkylsilyl group, and an alkoxysilyl group.
  • R R! / An alkyl group which is a group having a fluorine atom
  • Rf represents an alkyl group or an alkenyl group in which at least one of hydrogen is substituted with a fluorine atom, and examples thereof include a trifluoromethyl group, a pentafluoroethyl group, a perfluorooctyl group, and a heptafluoropropyl group.
  • Groups such as perfluoroalkyl groups, 3, 3, 3 trifluoropropyl groups, 4, 4, 3, 3, 2, 2, 1, 1-octafluorobutyl groups, Among those preferred are alkenyl groups substituted by fluorine atoms such as 1, 1, 1 trifluoro-2-chloroprobe group, trifluoromethyl group, pentafluoroethyl group, perfluoro group, etc. Loctyl group, heptafluoropropyl group, etc., and 3, 3, 3 trifluoropropyl group, 4, 4, 3, 3, 2, 2, 1, 1—octafluorobutyl group, etc.
  • X is a simple bond or a divalent group.
  • a divalent group —O— — S
  • [0034] represents a group such as
  • k represents an integer of 0 to 50, preferably 0 to 30.
  • Rf in addition to the fluorine atom, other substituents that may be substituted may be the same groups as those exemplified as the substituents in R to R. Can be mentioned.
  • the skeletal carbon atom in Rf is another atom, for example, O—, — S—, —NR— (R is hydrogen
  • 0 0 represents an atom or a substituted or unsubstituted alkyl group, and may be a group represented by the general formula (F)), a carbo group, one NHCO, one CO—O, one SO NH, etc. of
  • M represents the same metal atom as in general formula (1)
  • Rf and X represent the same groups as Rf and X in general formula (F)
  • k represents the same integer.
  • R is a
  • R represents an alkyl group, an alkenyl group, or R represents an alkyl group, an alkenyl group, or an aryl group.
  • Rf, X, or k has the same meaning as in the general formula (2).
  • R is also synonymous with R in the general formula (2).
  • M is also represented by the general formula (2).
  • Si is the most preferable Si and Ti are preferable.
  • organometallic compounds having a fluorine atom for example, compounds represented by the following general formula (4) are mentioned.
  • At least one of R to R is an organic group having the fluorine atom.
  • R is a hydrogen atom, or substituted or
  • J represents an integer of 0 to: L00, preferably 0 to 50, and most preferably j is in the range of 0 to 20.
  • Another preferred compound having a fluorine atom used in the present invention is an organometallic compound having a fluorine atom represented by the following general formula (5).
  • M represents In, Al, Sb, Y or La.
  • Rf and X represent the same groups as Rf and X in the general formula (F 1), and Y represents a simple bond or oxygen.
  • k also represents an integer of 0 to 50, preferably an integer of 30 or less.
  • R is an alkyl group or
  • R represents an alkyl group, an alkenyl group or an aryl group.
  • n + p 3
  • m is at least 1
  • n 0 to 2
  • Another preferable example of the compound having a fluorine atom used in the present invention is an organometallic compound having a fluorine atom represented by the following general formula (6). [0047] General formula (6)
  • R n represents a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms
  • R 2 represents a hydrolyzable group
  • Z represents —OCONH or —O
  • ml represents an integer of 150
  • nl represents an integer of 0
  • pi represents an integer of 0
  • ql represents an integer of 1 6, and 6 ⁇ nl + p 1> 0.
  • R n is CF CFCF
  • R 11 represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms such as an alkyl group, or an aromatic hydrocarbon group having 6 to 20 carbon atoms such as a phenyl group
  • R 12 represents a carbon number such as a hydrogen atom or an alkyl group
  • 15 represents an aliphatic hydrocarbon of 15
  • R 13 represents a divalent aliphatic hydrocarbon group having 36 carbon atoms such as an alkylidene group.
  • —OCH—OCH—OCH—OCOCOCH and —NH are preferable.
  • ml is 1 30 and more preferably 5 20. More preferably, nl is 1 or 2. More preferably, pi is 1 or 2. Also, ql is more preferred to be 1, 3.
  • Rf is a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms
  • X is an iodine atom or a hydrogen atom
  • Y is a hydrogen atom or a lower alkyl group
  • Z is a fluorine atom or Trifluoromethyl group
  • R 21 represents a hydrolyzable group
  • R 22 represents a hydrogen atom or an inert monovalent organic group
  • a, b, c, d are each an integer of 0 to 200, e Is 0 or 1
  • m and n are integers from 0 to 2
  • p is an integer from 1 to 10.
  • Rf is usually a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, preferably a CF group, a CF group, or a CF group.
  • Y is usually a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, preferably a CF group, a CF group, or a CF group.
  • R 24 O groups, (R 24 ) N groups, and R 23 CONR 24 groups are preferred.
  • R 23 is usually an alkyl group or the like
  • R 24 is usually an alkyl group having 1 to 5 carbon atoms such as a hydrogen atom or an alkyl group.
  • a lower aliphatic hydrocarbon group, R 25 is a divalent aliphatic hydrocarbon group usually having 3 to 6 carbon atoms such as an alkylidene group. More preferably, a chlorine atom, CH 2 O
  • R 22 is a hydrogen atom or an inert monovalent organic group, preferably a monovalent hydrocarbon group usually having 1 to 4 carbon atoms such as an alkyl group.
  • a, b, c and d are integers of 0 to 200, preferably 1 to 50.
  • m and n are integers of 0 to 2, preferably 0.
  • p is an integer of 1 or 2 or more, preferably an integer of 1 to 10, and more preferably an integer of 1 to 5.
  • the number average molecular weight is 5 ⁇ 10 2 to 1 ⁇ 10 5 , preferably 1 ⁇ 10 3 to 1 ⁇ 10 4 .
  • Rf is C
  • F group a is an integer from 1 to 50, b, c and d are 0, e is 1, Z is fluorine
  • the organometallic compound having an organic group having fluorine which is preferably used as the silane compound having a fluorine atom, and the compounds represented by the general formulas (1) to (7) are typical. Specific compounds are listed below, but the present invention is limited to these compounds. Not.
  • Examples thereof include organic titanium compounds having fluorine such as fluorine-containing organic metal compounds as follows.
  • organic silane compounds preferably used include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltripropoxysilane, methyltributoxysilane, Tiltrimethoxysilane, Ethyltriethoxysilane, Vinyltrimethoxysilane, Vinyltriethoxysilane, Vinyltriacetoxysilane, Vinyltrimethoxyethoxysilane, Phenyltrimethoxysilane, Phenyltriethoxysilane, Phenyltriacetoxysilane , ⁇ -black propyltrimethoxysilane , ⁇ -black propyltriethoxysilane, ⁇ -black propyltriacetoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -aminopropyl Trimethoxysilane, ⁇
  • Toxisilane ⁇ -Glycidoxypropylvinyldimethoxysilane, ⁇ -Glycidoxypropylvinyljetoxysilane, ⁇ -Glycidoxypropylphenyldimethoxysilane, ⁇ Dialkoxy silanes such as glycidoxypropyl phenoxy silane, diphenoxy silane, diacinole oxy silane, trimethino ethoxy silane, trimethino methoxy silane, 3, 3, 3-trifluoropropyl trimethoxy silane, dimethoxy methyl 1,3,3-Trifluoroprovir silane, fluoroalkyl silane, hexamethyldisilane, hexamethyldisiloxane, etc., but are not limited to these and may be used alone. Two or more different types can be used simultaneously.
  • methyltriethoxysilane, etyltriethoxysilane, dimethyldiethoxysilane, dimethylenoresimethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, butyltrimethoxysilane, trimethylethoxysilane and the like are preferable.
  • organosilicon compound a compound represented by the following general formula (8) is used.
  • n is 0 to 2000.
  • R to R are a hydrogen atom or each
  • a fluorine compound can be used, and as the organic fluorine compound, a fluorocarbon gas, a fluorinated hydrocarbon gas, or the like can be preferably used.
  • a fluorocarbon gas include tetrafluoromethane, tetrafluoroethylene, hexafluoropropylene, octafluorocyclobutane, and the like.
  • fluorinated hydrocarbon gas include difluoromethane, tetrafluoroethane, tetrafluoropropylene, trifluoropropylene, and the like.
  • halogenated fluoride compounds such as black trifluoromethane, chlorodifluoromethane, dichlorotetrafluorocyclobutane, fluoroalcohols such as trifluoromethanol and pentafluoroethanol, trifluoroacetic acid, etc.
  • Fluorinated fats such as pentafluoropropionic acid
  • organic fluorine compounds such as fluorinated ketones such as fatty acid and hexafluoroacetone is not limited to these. Further, these compounds may have a fluorinated ethylene unsaturated group in the molecule.
  • the silane compound having an alkyl group and the silane compound having an aromatic group according to the present invention can be mixed and used at a mass ratio of 1:99 to 99: 1, and a mass of 10:90 to 90:10. More preferably, the ratio is 20:80 to 80:20.
  • the surface treatment layer according to the present invention is formed on a substrate described later, and an organic semiconductor layer is further formed thereon.
  • the thickness of the surface treatment layer is preferably lOOnm or less from the monomolecular layer, and more preferably lOnm or less from the monomolecular layer.
  • the surface roughness Ra of the surface treatment layer surface is greatly affected by the surface properties of the substrate, the gate electrode, and the gate insulating film when the thin film transistor is a bottom gate type described later.
  • the method for forming the surface treatment layer is not particularly limited, but vacuum deposition, molecular beam epitaxy, ion cluster beam, low energy ion beam, ion plating, CVD, sputtering, atmospheric pressure plasma ( Atmospheric pressure plasma (CV D method), dip coating method, casting method, reel coating method, bar coating method, die coating method, etc., and wet processes such as printing and ink jet patterning methods. Can be used according to.
  • a wet method in which a substrate is immersed in a solution of a surface treatment agent or a solution of a surface treatment agent is applied and dried a plasma CVD method, preferably an atmospheric pressure plasma CVD method is used.
  • a plasma CVD method preferably an atmospheric pressure plasma CVD method is used.
  • the substrate is dipped in a 1% by weight toluene solution of a surface treatment agent for 10 minutes and then dried, or this solution is applied to the substrate and dried.
  • Surface treatment agent in plasma CVD method, surface treatment layer forming material is the raw material
  • a reactive gas is supplied onto a substrate heated in the range of 50 to 500 ° C and a surface treatment layer is formed by a thermal reaction.
  • LOOPa reduced pressure of LOOPa
  • the atmospheric pressure plasma method is most preferable from the viewpoints of the performance, the formation speed of the surface treatment layer, and the efficient production in a non-vacuum system.
  • FIG. 1 is a conceptual diagram showing an example of a plasma discharge treatment container 20 used in the plasma discharge treatment apparatus P.
  • the plasma discharge treatment container 20 shown in FIG. 2 is used.
  • a long film-like substrate F is conveyed while being wound around a portal electrode 21 that rotates in the conveying direction (clockwise in the figure).
  • the fixed electrode 22 is composed of a plurality of cylinders, and is installed facing the roll electrode 21.
  • the substrate F wound around the roll electrode 21 is pressed by the two-up rollers 23a and 23b, is regulated by the guide roller 24, is transported to the discharge treatment space secured by the plasma discharge treatment vessel 20, is subjected to discharge plasma treatment, Then, it is conveyed to the next process via the guide roller 25.
  • the partition plate 26 is disposed in the vicinity of the above-mentioned roller 23b, and suppresses the air accompanying the base F from entering the plasma discharge processing container 20.
  • This entrained air can be achieved by the above-mentioned roller 23b, which is preferably suppressed to 1% by volume or less with respect to the total gas volume in the plasma discharge treatment vessel 20. is there.
  • a mixed gas (discharge gas and reaction gas; the surface treatment agent is included in the reaction gas) used for the discharge plasma treatment is introduced into the plasma discharge treatment vessel 20 from the air supply port 27, and after the treatment, The gas is exhausted from the exhaust port 28.
  • FIG. 2 is a schematic view showing another example of the plasma discharge treatment container 20 as described above, whereas the plasma discharge treatment container 20 of FIG. 1 uses a cylindrical fixed electrode 22.
  • a prismatic fixed electrode 29 is used in the plasma discharge treatment container 20 shown in FIG. 2 .
  • the prismatic fixed electrode 29 shown in FIG. 2 is preferably used in the production method of the present invention.
  • FIGS. 3A and 3B are schematic perspective views showing an example of the cylindrical roll electrode 21 described above, and FIG.
  • FIGS. 5A and 5B are schematic perspective views showing an example of a cylindrical fixed electrode 22, and FIGS. 5A and 5B are schematic perspective views showing an example of a prismatic fixed electrode 29.
  • FIG. 5A and 5B are schematic perspective views showing an example of a cylindrical fixed electrode 22
  • FIGS. 5A and 5B are schematic perspective views showing an example of a prismatic fixed electrode 29.
  • a roll electrode 21 serving as a ground electrode is formed by applying a ceramic-coated dielectric 21b that has been subjected to sealing treatment using an inorganic material after thermal spraying ceramics on a conductive base material 21a such as metal. It consists of a combination of coatings. Ceramic coated dielectric material 21b is covered with lmm with a single wall, manufactured to have a roll diameter of 200mm after coating, and grounded.
  • a roll electrode 21 is formed by a combination of a ceramic-coated dielectric 21B provided with an inorganic material by a conductive base material 21A, such as a metal, and a covering. Also good.
  • a conductive base material 21A such as a metal
  • silicate glass, borate glass, phosphate glass, germanate glass, tellurite glass, aluminate glass, vanadate glass, etc. are preferably used. Among these, borate glass is more preferable because it is easy to process.
  • the conductive base materials 21a and 21A such as metal, stainless steel or titanium is preferable from the viewpoint of force processing including metals such as titanium, silver, platinum, stainless steel, aluminum and iron.
  • a ceramic material used for thermal spraying alumina, silicon nitride, or the like is preferably used. Among these, alumina is more preferable because it is easy to process.
  • the conductive base materials 21a and 21A of the roll electrode are made of a stainless steel jacket roll base material having a constant temperature means using liquid (not shown).
  • FIGS. 4 (a), (b) and FIGS. 5 (a), (b) have a fixed electrode 22 and a fixed electrode 29 as application electrodes, and are in the same combination as the roll electrode 21 described above. It is configured.
  • the power source for applying voltage to the applied electrode is not particularly limited, but Shinko Electric's high frequency power supply (50 kHz), Heiden Laboratory high frequency power supply (continuous mode use, 100 kHz), Pul Kogyo high frequency power supply ( 200kHz), Pearl Industrial High Frequency Power Supply (800kHz), Pearl High Industrial Power Supply (2MHz), JEOL High Frequency Power Supply (13. 56MHz), Pearl Industrial A high-frequency power source (27 MHz), a high-frequency power source (150 MHz) manufactured by Pearl Industry, etc. can be preferably used.
  • a power source that oscillates at 433 MHz, 800 MHz, 1.3 GHz, 1.5 GHz, 1.9 GHz, 2.45 GHz, 5.2 GHz, or 10 GHz may be used.
  • FIG. 6 is a conceptual diagram showing an example of a plasma discharge treatment apparatus P used in the present invention.
  • the portion of the plasma discharge processing vessel 20 has the same force as described in FIG. 2, and further includes a gas generator 40, a power source 50, an electrode constant temperature unit 70, and the like as a device configuration.
  • a thermostat for the electrode thermostat unit 70 an insulating material such as distilled water or oil is used.
  • the electrodes shown in FIG. 6 are the same as those shown in FIGS. 3 and 5, and the gap between the opposing electrodes is set to about 1 mm, for example.
  • the distance between the electrodes is determined in consideration of the thickness of the solid dielectric placed on the electrode base material, the magnitude of the applied voltage, the purpose of using plasma, and the like.
  • the shortest distance between the solid dielectric and the electrode when a solid dielectric is placed on one of the electrodes, and the shortest distance between the solid dielectrics when a solid dielectric is placed on both of the electrodes are uniform in any case From the viewpoint of effective discharge, 0.5 to 20 mm is preferable, and 1 ⁇ 0.5 mm is particularly preferable.
  • a roll electrode 21 and a fixed electrode 29 are arranged at predetermined positions in the plasma discharge treatment vessel 20, the flow rate of the mixed gas generated by the gas generator 40 is controlled, and air is supplied via the gas filling means 41.
  • the plasma discharge treatment vessel 20 is put into the plasma discharge treatment vessel 20 through the port 27, and the inside of the plasma discharge treatment vessel 20 is filled with the mixed gas used for the plasma treatment and exhausted through the exhaust port 28.
  • a voltage is applied to the electrode by the power source 50, and the roll electrode 21 is grounded to the ground, and discharge plasma is generated.
  • the substrate F is supplied from the roll-shaped original winding substrate 60, and the electrodes in the plasma discharge treatment vessel 20 are in a single-sided contact state (in contact with the roll electrode 21) via the guide roller 24.
  • the surface of the substrate F is formed by discharge plasma during conveyance, and after the surface treatment layer containing the inorganic substance derived from the reactive gas (including the surface treatment agent) in the mixed gas is formed on the surface, the guide roller It is conveyed to the next process via 25.
  • the substrate F is in contact with the roll electrode 21, and only the surface is formed.
  • the value of the voltage applied from the power supply 50 to the fixed electrode 29 is determined appropriately.
  • the voltage is about 0.5 to: LOkV
  • the power supply frequency is adjusted to more than 1kHz and less than 150MHz.
  • a continuous sine wave continuous oscillation mode called continuous mode
  • an intermittent oscillation mode called ON / OFF intermittently called pulse mode
  • the discharge power depends force preferably by the shape of the device discharge density of 0. 1 ⁇ 5 OZcm 2 is Yo,.
  • the discharge condition with the two high-frequency voltages is that a high-frequency voltage is applied to the discharge space formed by the opposing electrodes (referred to here as the first electrode and the second electrode), and the high-frequency voltage is the first frequency.
  • a high frequency means a frequency having a frequency of at least 0.5 kHz.
  • the high frequency voltage is higher than the voltage component of the first frequency ⁇ and the first frequency ⁇ .
  • the discharge start voltage the lowest voltage that can cause discharge in the discharge space (electrode configuration, etc.) and reaction conditions (gas conditions, etc.) used in the actual surface treatment layer forming method.
  • the discharge start voltage varies somewhat depending on the type of gas supplied to the discharge space, the dielectric type of the electrode, etc., but may be considered to be substantially the same as the discharge start voltage of the discharge gas alone.
  • the force described above for the superposition of sine waves is not limited to this. Even if it is a Rus wave, it does not work even if one is a sine wave and the other is a pulse wave. Also
  • it may have a third voltage component.
  • the first high-frequency voltage V is applied to the first electrode constituting the counter electrode.
  • the atmospheric pressure plasma discharge treatment apparatus includes gas supply means for supplying a discharge gas and a surface treatment layer forming gas between the counter electrodes. Furthermore, it is preferable to have an electrode temperature control means for controlling the temperature of the electrode.
  • first filter between the electrode and the first power source or between them
  • second filter between the electrode and the second power source or between them.
  • the first filter 1 makes it difficult for current at the frequency of the first power supply to pass through, and more easily passes current at the frequency from the second power supply.
  • being difficult to pass means that it preferably passes only 20% or less, more preferably 10% or less of the current.
  • the phrase “easy to pass” means that 80% or more, more preferably 90% or more of the current is passed.
  • the first power source of the atmospheric pressure plasma discharge treatment apparatus has a capability of applying a higher frequency voltage than the second power source.
  • a high-frequency voltage is applied between the first electrode and the second electrode facing each other, and the high-frequency voltage is applied to the first high-frequency voltage V and the second high-frequency voltage.
  • the definition of the high frequency and the discharge start voltage, and the specific method for applying the high frequency voltage of the present invention between the counter electrodes (same discharge space) are the same as those described above.
  • the high-frequency voltage (applied voltage) and the discharge start voltage are those measured by the following methods.
  • the discharge gas is supplied between the electrodes, the voltage between the electrodes is increased, and the voltage at which discharge starts is defined as the discharge start voltage IV.
  • the measuring instrument is the same as the above high-frequency voltage measurement.
  • the discharge start voltage IV is 3.7 kV.
  • the first high-frequency voltage is V ⁇ 3.7k
  • the nitrogen gas can be excited and put into a plasma state.
  • the frequency of the first power supply is preferably 200 kHz or less.
  • the electric field waveform may be a sine wave or a nors wave.
  • the lower limit is preferably about 1kHz.
  • the frequency of the second power source is preferably 800 kHz or more.
  • the upper limit is preferably about 200MHz.
  • the second frequency ⁇ side is used to increase the plasma density to form a dense and high-quality surface treatment layer.
  • the first filter makes it difficult for a current having a frequency from the first power source to pass through and allows a current having a frequency of the second power source to easily pass.
  • the second filter is difficult to pass a current having a frequency from the second power source. This makes it easier to pass the current of the frequency from the first power source.
  • any filter having such properties can be used without limitation.
  • a capacitor of several tens to several tens of thousands of pF or a coil of about several H can be used depending on the frequency of the second power supply.
  • the second filter can be used as a filter by using a coil of 10 H or more according to the frequency of the first power source and grounding it through these coils or capacitors.
  • the first power supply and the second power supply may not be necessarily used at the same time, but may be used alone. In this case, the same effect as when a single high frequency power supply is applied is obtained.
  • the atmospheric pressure plasma discharge treatment apparatus discharges between the counter electrodes, and at least the discharge gas and the surface treatment layer forming gas (reaction gas) introduced between the counter electrodes are in a plasma state.
  • the surface treatment layer is formed on the substrate by exposing the substrate to be transported to the plasma state gas (see, for example, FIGS. 1 to 7).
  • the atmospheric pressure plasma discharge treatment apparatus discharges between the counter electrodes similar to the above, excites the gas introduced between the counter electrodes, or puts it in a plasma state, and jets the gas outside the counter electrode.
  • a surface treatment layer is formed on the substrate by blowing a gas in an excited or plasma state to the substrate and exposing the substrate in the vicinity of the counter electrode (stationary or transported).
  • There is a jet-type device that forms water see Figure 8 below
  • the discharge gas G is introduced into the discharge spaces formed by the two pairs of counter electrodes 211-221, 212-222, respectively, and excited.
  • the surface treatment layer is formed on the substrate F by contacting or mixing the discharge gas G ′ and the surface treatment layer forming gas (reaction gas) M containing the raw material for the surface treatment layer outside the discharge space. You can also.
  • Reference numeral 213 denotes an insulating layer.
  • the plasma discharge treatment vessel 20 is preferably made of an insulating material such as a Pyrex (registered trademark) glass treatment vessel, but may be made of metal as long as it can be insulated from the electrodes.
  • a Pyrex (registered trademark) glass treatment vessel for example, polyimide resin or the like may be attached to the inner surface of an aluminum or stainless steel frame, and ceramic spraying may be performed on the metal frame to achieve insulation.
  • the temperature of the substrate during the discharge plasma treatment is adjusted to a temperature between room temperature (15-25 ° C) and less than 300 ° C. It is preferable to adjust to room temperature to 200 ° C.
  • these conditions are not limited to this range because the upper limit of the temperature is determined depending on the physical properties of the substrate, particularly the glass transition temperature.
  • the electrode and the substrate are subjected to discharge plasma treatment while being cooled by a cooling means as necessary.
  • the plasma treatment is preferably performed at atmospheric pressure or near atmospheric pressure, but the plasma treatment may be performed under vacuum or high pressure.
  • the vicinity of atmospheric pressure represents a pressure of 20 to L lOkPa, but 93 to 104 kPa is preferable in order to obtain the effect described in the present invention.
  • the surface of at least the surface in contact with the substrate F has a maximum surface roughness (Rmax) specified by JIS B 0601 of 10 m. It is preferable that the surface roughness is adjusted so as to be equal to or less than the maximum value of the surface roughness.
  • the plasma discharge treatment apparatus P shown in FIGS. 1 and 2 described above is a force used when the substrate F is a film.
  • a substrate having a thickness greater than the film for example, If it is a lens or the like, a plasma discharge treatment apparatus P as shown in FIG. 7 is used.
  • FIG. 7 is a schematic view showing another example of the plasma discharge treatment apparatus P.
  • a plate-type electrode 103 is used as an electrode connected to the high-frequency power supply 101, and a base (for example, a lens L) is placed on the electrode 103.
  • a rectangular bar-shaped electrode 104b is provided so as to face the electrode 103.
  • the square rod-shaped electrode 104a is grounded as a ground.
  • the mixed gas is supplied from above the electrodes 104 a and 104 b, and a plasma state is obtained in a range where the force between the electrodes 104 a and 104 b extends over the electrode 103.
  • FIG. 8 is a schematic view showing another example of an atmospheric pressure plasma discharge apparatus useful for the present invention.
  • the plasma discharge treatment apparatus P has a counter electrode composed of a first electrode 111 and a second electrode 112, and the first electrode 111 is connected to the first power supply 121 between the counter electrodes.
  • First A high-frequency voltage V of frequency ⁇ is applied, and the second electrode 112 is connected to the second power source 122.
  • the high frequency voltage V of the second frequency ⁇ is applied.
  • the first frequency ⁇ of the power supply 121 is lower than the second frequency ⁇ of the second power supply 122.
  • a first filter 123 is installed between the first electrode 111 and the first power supply 121 so that the current from the first power supply 121 flows toward the first electrode 111. It is designed to make it difficult to pass current from the second power source 122 and to pass current from the second power source 122 more easily.
  • the second filter 124 is installed between the second electrode 112 and the second power source 122 so that the current from the second power source 122 flows toward the second electrode 112. It is designed to pass the current from the two power sources 122 and to easily pass the current from the first power source 121.
  • Gas G is introduced from the gas supply means 113 between the opposing electrodes of the first electrode 111 and the second electrode 112 (discharge space), and a high-frequency voltage is applied from the first electrode 111 and the second electrode 112. A discharge is generated, and while the gas G is in a plasma state, the gas G is blown out in the form of a jet to the lower side of the counter electrode (the lower side of the paper) to create a plasma G Then, a surface treatment layer is formed on the substrate F in the vicinity of the treatment position 114.
  • FIG. 9 is a schematic diagram showing still another example of an atmospheric pressure plasma discharge treatment apparatus useful for the present invention.
  • the atmospheric pressure plasma discharge treatment apparatus of Fig. 9 mainly includes a counter electrode in which the first electrode 211 and the second electrode 221 and the first electrode 212 and the second electrode 222 are arranged to face each other.
  • the discharge gas G is placed in the discharge space, and the reaction (surface treatment layer formation) gas M is placed outside the discharge space. It comprises gas supply means to be introduced, electrode temperature adjusting means for controlling the electrode temperature, and the like.
  • a region having a dielectric 213 sandwiched between the first electrode 211 and the second electrode 221 or between the first electrode 212 and the second electrode 222 and having a strong diagonal line on the first electrode is a discharge space. .
  • This discharge The discharge gas G is introduced into the space and excited. Further, no discharge occurs in the region sandwiched between the second electrodes 221 and 22, and the surface treatment layer forming gas M is introduced here.
  • the excited discharge gas G ′ and the surface treatment layer forming gas M are brought into contact with each other as an indirect excitation gas. Expose to form a surface treatment layer.
  • the gas used varies depending on the type of surface treatment layer to be provided on the substrate. Basically, it is a mixed gas of discharge gas (inert gas) and reaction gas containing surface treatment agent for forming the surface treatment layer. is there.
  • the reaction gas is preferably contained in an amount of 0.01 to LO volume% with respect to the mixed gas. The content is more preferably 0.1 to 10% by volume, and still more preferably 0.1 to 5% by volume.
  • Examples of the inert gas include Group 18 elements in the periodic table, specifically, helium, neon, argon, krypton, xenon, radon, nitrogen gas, and the like. In order to obtain it, helium, argon, or nitrogen gas is preferably used.
  • reaction is controlled by containing 0.01 to 5% by volume of a component selected from oxygen, ozone, hydrogen peroxide, carbon dioxide, carbon monoxide, hydrogen, and nitrogen in the mixed gas, A good surface treatment layer can be formed.
  • the surface treatment agent of the reactive gas between the electrodes which are the discharge spaces may be in any state of gas, liquid or solid at normal temperature and pressure.
  • gas it can be introduced into the discharge space as it is, but in the case of liquid or solid, it is used after being vaporized by means such as heating, decompression or ultrasonic irradiation.
  • An organic thin film transistor has a source electrode and a drain electrode connected to each other by an organic semiconductor channel (active layer, organic semiconductor layer) on a base, and a top gate type having a gate electrode on the gate electrode via a gate insulating layer.
  • Fig. 10 (a) to (c) and a bottom gate type having a gate electrode on a substrate and a source electrode and a drain electrode connected by an organic semiconductor channel through a gate insulating layer
  • Figure 10 (c!) To (f) The organic thin film transistor of the present invention is Although these top gate type and bottom gate type may be shifted, an organic thin film transistor having a bottom gate type structure, particularly an organic thin film transistor having a bottom gate type structure shown in FIG.
  • organic semiconductor material constituting the organic semiconductor layer various condensed polycyclic aromatic compounds and conjugated compounds can be applied.
  • the organic semiconductor material preferably has an alkyl group in view of solubility and affinity with the thin film formed by the pretreatment agent.
  • the alkyl group has 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms.
  • Examples of the condensed polycyclic aromatic compound include anthracene, tetracene, pentacene, hexacene, heptacene, taricene, picene, fluorene, pyrene, peropyrene, perylene, terylene, ku-terylene, coronene, tal-no-lene.
  • compounds such as musantracene, bisanthene, bisanthene, heptazethrene, pyranslen, violanthene, isoviolanthene, cercobiphenyl, phthalocyanine, porphyrin, and derivatives thereof are listed.
  • Examples of the conjugated compound include polythiophene and its oligomer, polypyrrole and its oligomer, polyaniline, polyphenylene and its oligomer, polyphenylene vinylene and its oligomer, polyphenylene vinylene and its oligomer, polyacetylene, Examples include polydiacetylenes, tetrathiafulvalene compounds, quinone compounds, cyan compounds such as tetracyanoquinodimethane, fullerenes, and derivatives or mixtures thereof.
  • thiophene hexamer ⁇ -secthiophene e, ⁇ -dihexinore a-secciothiophene, e, ⁇ -dihexinore a-quinketiophene, ⁇ , ⁇ Oligomers such as —bis (3-butoxypropyl) -a-secciothiophene can be preferably used.
  • copper phthalocyanine is a metal phthalocyanine such as fluorine-substituted copper phthalocyanine described in JP-A-11-251601, naphthalene 1, 4, 5, 8-tetracarboxylic acid diimide, N, N 'bis (4 trifluoromethylbenzyl) naphthalene 1, 4, 5, 8-tetracarboxylic acid diimide, N, N' -bis (1H, 1H-perfluorooctyl), N, N '-bis (1H, 1H-perfluorobutyl) and N, N '-dioctylnaphthalene 1, 4, 5, 8- tetracarboxylic diimide derivatives, naphthalene 2, 3, 6, 7 naphthalene such as tetracarboxylic diimide Tetracarboxylic acid diimides, and condensed ring tetracarboxylic acid diimides such as anthracene t
  • pigments such as merocyanine pigments and hemicyanine pigments.
  • At least one selected from the group consisting of condensed polycyclic aromatic compounds such as pentacene, fullerenes, condensed ring tetracarboxylic acid diimides, and metal phthalocyanines is included.
  • condensed polycyclic aromatic compounds such as pentacene, fullerenes, condensed ring tetracarboxylic acid diimides, and metal phthalocyanines
  • organic semiconductor materials include tetrathiafulvalene (TTF) -tetracyanoquinodimethane (TCNQ) complex, bisethylenetetrathiafulvalene (BEDTTTF) -perchloric acid complex, BEDTTTF iodine complex, TCNQ iodine complex, etc.
  • TTF tetrathiafulvalene
  • BEDTTTF bisethylenetetrathiafulvalene
  • TCNQ iodine complex etc.
  • Organic molecular complexes of can also be used.
  • ⁇ conjugated polymers such as polysilane and polygermane can also be used organic / inorganic hybrid materials described in JP-A-2000-260999.
  • R represents a substituent
  • the thiophene oligomer represented by the general formula (9) will be described.
  • examples of the substituent represented by R include an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert butyl group, a pentyl group, Xyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (eg, bur group, allyl group, etc.) , Alkyl groups (eg, ethynyl group, propargyl group, etc.), aryl groups (eg, phenol group, p-chlorophenol group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group) Group
  • alkyl group for example,
  • 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.
  • the terminal group of the thiophene oligomer used in the present invention will be described.
  • the terminal group of the thiophene oligomer used in the present invention does not have a chael group.
  • an aryl group for example, a phenyl group, p-Chlorofuryl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulyl group, acenaphthyl group, fluoro group, phenanthryl group, indenyl group, pyrenyl group, biphenyl group Etc.
  • 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.
  • the thiophene oligomer used in the present invention preferably has no head-to-head structure in the structure, more preferably, the structure has a head-to-tail structure, or It preferably has a tail-to-tail structure.
  • Head-to-Head structure For example, " ⁇ -electron organic solid” (1998, published by the Japan Society for Publishing Press, Japan) This can be referred to from pages 27 to 32, Adv. Mater. 1998, 10, No. 2, pages 93 to 116, etc.
  • specific structural features are shown below.
  • R has the same meaning as R in the general formula (9).
  • the organic semiconductor layer may be formed of a material having a functional group such as acrylic acid, acetamide, a dimethylamino group, a cyano group, a carboxyl group, or a nitro group, a benzoquinone derivative, or a tetracyano.
  • a material that serves as an acceptor for accepting electrons such as a material having a functional group such as an amino group, a triphenyl group, an alkyl group, a hydroxyl group, an alkoxy group, or a full group, or a substituted amine such as phenylenediamine.
  • Anthracene benzoanthracene, substituted benzoanthracene, pyrene, substituted pyrene, force rubazole and its derivatives, tetrathiafulvalene and its derivatives, etc. You can do so.
  • the doping means introducing an electron-donating molecule (acceptor) or an electron-donating molecule (donor) into the thin film as a dopant. Therefore, the doped thin film is a thin film containing the condensed polycyclic aromatic compound and the dopant.
  • a well-known thing can be employ
  • these organic semiconductor layers can be formed by a known method, for example, vacuum deposition, MBE (Molecular Beam Epitaxy), ion cluster beam method, low energy ion beam method, ion plate. Coating method, sputtering method, CVD (Chemical Vapor Deposition), laser deposition, electron beam deposition, electrodeposition, spin coating, dip coating, bar coating method, die coating method, spray coating method, LB method, etc., screen printing, Examples thereof include ink jet printing and blade coating.
  • the precursor film formed by coating is heat-treated.
  • a thin film of the target organic semiconductor material may be formed.
  • the film thickness of these organic semiconductor layers is not particularly limited, but the characteristics of the obtained transistor are largely influenced by the film thickness of the organic semiconductor layer. Different forces depending on the conductor Generally 1 ⁇ m or less, particularly 10 to 300 nm is preferred.
  • the source or drain electrode material is not particularly limited as long as it is a conductive material, and is formed of a known electrode material.
  • electrode material There is no particular limitation as long as it is a conductive material, and 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 oxide' tin (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 monopotassium alloy, magnesium, lithium, aluminum, magnesium Z copper mixture, magnesium Z silver mixture, magnesium Z aluminum Mixture, Magnesium Z indium
  • a known conductive polymer whose conductivity has been improved by doping such as conductive polyarlin, conductive polypyrrole, or conductive polythiophene (polyethylenedioxythiophene and polystyrenesulfonic acid complex, etc.) is also preferably used. It is done.
  • materials having low electrical resistance at the contact surface with the semiconductor layer are preferred as materials for forming the source electrode or drain electrode.
  • materials for forming the source electrode or drain electrode are preferred.
  • white gold, gold, silver , ⁇ , conductive polymers and carbon are preferred.
  • the source electrode or the drain electrode is used, it is formed using a fluid electrode material such as a solution, paste, ink, or dispersion liquid containing the above conductive material, in particular, a conductive polymer, Alternatively, a fluid electrode material containing fine metal particles containing platinum, gold, silver and copper is preferred.
  • the solvent or dispersion medium is preferably a solvent or dispersion medium containing 60% or more, preferably 90% or more of water, in order to suppress damage to the organic semiconductor.
  • the fluid electrode material containing fine metal particles for example, a known conductive paste or the like may be used.
  • fine metal particles having a particle diameter of 1 to 50 nm, preferably 1 to: LOnm are used.
  • the material of the metal fine particles is platinum, gold, silver, nickel, chromium, copper, iron, tin, antimony lead, tantalum, indium, palladium, tellurium, rhenium, iridium, aluminum, ru Themes, germanium, molybdenum, tungsten, zinc and the like can be used.
  • a metal phase in a liquid phase such as a physical production method such as a gas evaporation method, a sputtering method, or a metal vapor synthesis method, a colloid method, or a coprecipitation method is used.
  • the chemical production method include reducing metal ions to produce fine metal particles.
  • preferred are JP-A-11-76800, JP-A-11-80647, JP-A-11-319538, and JP-A-2000-239853.
  • An electrode is formed using these metal fine particle dispersions, the solvent is dried, and then heated to a shape in the range of 100 to 300 ° C, preferably 150 to 200 ° C, as necessary. Metal fine particles are thermally fused to form an electrode pattern having a desired shape.
  • a method for forming an electrode a method of forming an electrode using a known photolithographic method or a lift-off method from a conductive thin film formed using a method such as vapor deposition or sputtering using the above as a raw material, aluminum, copper, or the like
  • a method of etching by forming a resist on the metal foil by thermal transfer, ink jet or the like.
  • a conductive polymer solution or dispersion, a dispersion containing metal fine particles, or the like may be directly patterned by an ink-jet method, or may be formed from a coating film by lithography, laser abrasion, or the like.
  • a method of patterning a conductive ink or conductive paste containing a conductive polymer or fine metal particles by a printing method such as relief printing, intaglio printing, planographic printing, or screen printing can also be used.
  • the source electrode and the drain electrode are particularly preferably formed using a photolithographic method.
  • a light-sensitive resin solution is applied to the entire surface of the layer in contact with the protective layer of the organic semiconductor, and light is applied. Form a sensitive resin layer.
  • the same positive and negative photosensitive resins used for patterning the protective layer can be used.
  • an abrasion layer which is another photosensitive resin layer, may be used for electrode formation.
  • the abrasion layer the same ones as those used for patterning the protective layer can be mentioned.
  • Various insulating films can be used as the gate insulating layer of the organic thin film transistor of the present invention, and an inorganic oxide film having a high relative dielectric constant is particularly preferable.
  • inorganic acids include silicon oxide, acid aluminum, acid tantalum, titanium oxide, tin oxide, vanadium oxide, barium strontium titanate, barium zirconate titanate, zirconate zirconate titanate, Examples include lanthanum titanate, strontium titanate, barium titanate, magnesium magnesium titanate, bismuth titanate, strontium bismuth titanate, strontium bismuth tantalate, bismuth tantalate niobate, and trioxide yttrium. Of these, preferable are silicon oxide, acid aluminum, acid tantalum, and acid titanium. Inorganic nitrides such as silicon nitride and aluminum nitride can also be suitably used.
  • Examples of the film formation method include vacuum deposition, molecular beam epitaxy, ion cluster beam, low energy ion beam, ion plating, CVD, sputtering, and atmospheric pressure plasma. Dry process, spray coating method, spin coating method, blade coating method, dip coating method, casting method, roll coating method, bar coating method, die coating method, and other methods by patterning such as printing and inkjet Etc., and can be used depending on the material.
  • the wet process includes 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.
  • a so-called sol-gel method in which a solution of a body, for example, an alkoxide body is applied and dried is used.
  • the above-mentioned atmospheric pressure plasma CVD method is preferable.
  • the gate insulating layer is composed of an anodized film or the anodized film and an insulating film.
  • the anodized film is preferably sealed.
  • Anodized film can be anodized It is formed by anodizing an active metal by a known method.
  • Examples of the metal capable of anodizing treatment include aluminum and tantalum, and a known method with no particular limitation can be used for the method of anodizing treatment.
  • An oxide film is formed by anodizing.
  • Any electrolyte can be used as an electrolytic solution used for anodizing treatment as long as it can form a porous acid film.
  • sulfuric acid, phosphoric acid, oxalic acid, chromic acid, boric acid, sulfamic acid, For benzene sulfonic acid, etc. a mixed acid or a salt thereof in which two or more of these are combined is used.
  • the treatment conditions for anodization vary depending on the electrolyte used, and therefore cannot be specified.
  • the electrolyte concentration is 1 to 80% by mass
  • the electrolyte temperature is 5 to 70 ° C
  • the current is Density 0.5-60AZdm 2
  • electrolysis time 10 seconds to 5 minutes are appropriate.
  • 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 weight. It is preferable to perform electrolytic treatment for 20 to 250 seconds at an electrolyte temperature of 20 to 50 ° C and a current density of 0.5 to 20 A / dm 2. Better!/,.
  • organic compound film polyimide, polyamide, polyester, polyacrylate, photo-radical polymerization system, photo-power thione polymerization system photocurable resin, or copolymer containing acrylonitrile component, polybule Phenolic alcohol, polybutyl alcohol, novolac resin, cyano ethyl pullulan, and the like can also be used.
  • the wet process is preferred as the method of forming the organic compound film.
  • the inorganic oxide film and the organic oxide film can be laminated and used together.
  • the thickness of these insulating films is generally 50 nm to 3 ⁇ m, preferably 100 nm to 1 ⁇ m.
  • an organic semiconductor is formed on the gate insulating layer
  • an arbitrary surface treatment may be performed on the surface of the gate insulating layer.
  • Silane coupling agents such as octadecyltrichlorosilane, trimethylsilazane, and self-organized alignment films such as alkane phosphoric acid, alkanesulfonic acid, and alkanecarboxylic acid are preferably used.
  • the base material constituting the base can be ceramic bases such as glass, quartz, aluminum oxide, sapphire, silicon nitride, silicon carbide, and the like.
  • Power capable of using semiconductor substrates such as recon, germanium, gallium arsenide, gallium phosphide, gallium nitrogen, paper, nonwoven fabric, etc.
  • the substrate is preferably made of resin.
  • a plastic film sheet is used. it can.
  • plastic film examples include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate (PC), Examples of such films include cellulose triacetate (TAC) and cellulose acetate propionate (CAP).
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PES polyethersulfone
  • PES polyetherimide
  • polyetheretherketone polyphenylene sulfide
  • PC polycarbonate
  • TAC cellulose triacetate
  • CAP cellulose acetate propionate
  • a protective layer may be provided on the organic thin film transistor of the present invention.
  • the protective layer include the above-described inorganic acid or inorganic nitride, and the protective layer is preferably formed by the above-mentioned atmospheric plasma method. Thereby, the durability of the organic thin film transistor is improved.
  • a 200-nm-thick thermal oxide film was formed on an n-type Si wafer having a specific resistance of 0.02 ⁇ 'cm as a gate electrode to form a gate insulating layer.
  • the following surface treatment agents A and B are mixed at a molar ratio shown in Table 1 and dissolved in a toluene solution (1% by mass, 55 ° C) for 10 minutes. After crushing, it was rinsed with toluene, dried, and surface-treated with a hot acid film.
  • the evaluation result is shown as an average value of the time when a uniform organic semiconductor layer was formed among the 10 coating trials.
  • the contact angle of water on the surface of the thermally treated oxide film was measured using a contact angle meter (CA—DT'A type: manufactured by Kyowa Interface Science Co., Ltd.) in an environment of 20 ° C. and 50% RH.
  • CA—DT'A type manufactured by Kyowa Interface Science Co., Ltd.
  • the applicability during application of the organic semiconductor material solution was evaluated according to the following criteria.
  • the saturation region force carrier mobility of IV characteristics was calculated, and the onZoff ratio was calculated from the ratio of drain current values when the gate bias was 50 V and 0 V, with a drain bias of 50 V.
  • the organic thin film transistor 11 was unreliable for the average evaluation of the carrier mobility and the onZoff ratio, which had poor applicability.
  • the obtained organic thin film transistor except for the organic thin film transistor 1, operated well as a p-channel enhancement type FET.
  • the organic thin film transistors 12 to 15 of the present invention in which the surface of the substrate is treated with two kinds of surface treatment agents are as follows:
  • the surface treatment agents A and B were changed to the following surface treatment agents C and D, and others were produced in the same manner to produce organic thin film transistors 21 to 26.
  • the obtained organic thin film transistor was evaluated in the same manner as in Example 1. The results are shown in Table 2.
  • a 200-nm-thick thermal oxide film was formed on an n-type Si wafer having a specific resistance of 0.02 ⁇ 'cm as a gate electrode to form a gate insulating layer.
  • Inert gas helium 98.25 volume 0/0
  • Reactive gas Oxygen gas 1. 50% by volume
  • Reactive gas Steam of surface treatment agents E and F in toluene solution 0.25 vol%
  • discharge was performed at a frequency of 13.56 MHz using a high-frequency power source manufactured by Pearl Industries.
  • the electrode is against a stainless steel jacket roll base material that has cooling means with cooling water. Then, lmm is coated with alumina by ceramic spraying, and then a solution obtained by diluting tetramethoxysilane with ethyl acetate is applied and dried, then sealed with UV irradiation, and the surface is smoothed to make the surface Rmax 5 ⁇ m.
  • This is a roll electrode with a relative dielectric constant of 10 and is grounded.
  • the application electrode a hollow rectangular stainless steel pipe was covered with the same dielectric material under the same conditions.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Formation Of Insulating Films (AREA)
  • Thin Film Transistor (AREA)

Abstract

La présente invention concerne un transistor à film mince organique, doté d’excellentes caractéristiques TFT et fabriqué par un processus de solution ayant un haut rendement de production, ainsi qu’un procédé pour fabriquer ce transistor à film mince organique. Le transistor à film mince organique comporte un corps de base et une couche semi-conductrice organique sur la surface du corps de base. Le transistor à film mince organique est caractérisé en ce qu’une couche de finition de surface est formée sur la surface du corps de base entre la couche semi-conductrice organique et le corps de base en utilisant 2 à 5 types d’agents de finition de surface.
PCT/JP2006/316907 2005-09-08 2006-08-29 Transistor à film mince organique, corps de base pour transistor à film mince organique et procédé de fabrication du transistor à film mince organique Ceased WO2007029551A1 (fr)

Priority Applications (1)

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JP2007534344A JPWO2007029551A1 (ja) 2005-09-08 2006-08-29 有機薄膜トランジスタ、有機薄膜トランジスタ用基体及び有機薄膜トランジスタの製造方法

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JP2005-260428 2005-09-08
JP2005260428 2005-09-08

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009176985A (ja) * 2008-01-25 2009-08-06 Asahi Kasei Corp 有機半導体層を有する新規光電界効果トランジスタ

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004001705A1 (fr) * 2002-06-24 2003-12-31 Jinggui Lu Afficheur a guide de lumiere en panneau plat et procede de fabrication

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005109184A (ja) * 2003-09-30 2005-04-21 Seiko Epson Corp 膜パターン形成方法、回路素子、電気光学装置、および電子機器

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004001705A1 (fr) * 2002-06-24 2003-12-31 Jinggui Lu Afficheur a guide de lumiere en panneau plat et procede de fabrication

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009176985A (ja) * 2008-01-25 2009-08-06 Asahi Kasei Corp 有機半導体層を有する新規光電界効果トランジスタ

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