WO2008065927A1 - Transistor à film fin organique, élément électronique composite organique, procédé de fabrication d'un tel transistor et d'un tel élément, écran d'affichage et mémoire - Google Patents

Transistor à film fin organique, élément électronique composite organique, procédé de fabrication d'un tel transistor et d'un tel élément, écran d'affichage et mémoire Download PDF

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Publication number
WO2008065927A1
WO2008065927A1 PCT/JP2007/072424 JP2007072424W WO2008065927A1 WO 2008065927 A1 WO2008065927 A1 WO 2008065927A1 JP 2007072424 W JP2007072424 W JP 2007072424W WO 2008065927 A1 WO2008065927 A1 WO 2008065927A1
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WIPO (PCT)
Prior art keywords
film
transistor
organic
low dielectric
forming
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PCT/JP2007/072424
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English (en)
Japanese (ja)
Inventor
Mamoru Baba
Rongbin Ye
Takeyoshi Katoh
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Zeon Corporation
Iwate University
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Priority claimed from JP2006319186A external-priority patent/JP2010034092A/ja
Priority claimed from JP2006319184A external-priority patent/JP2010034090A/ja
Priority claimed from JP2006319185A external-priority patent/JP2010034091A/ja
Application filed by Zeon Corporation, Iwate University filed Critical Zeon Corporation
Publication of WO2008065927A1 publication Critical patent/WO2008065927A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/40—Electrodes ; Multistep manufacturing processes therefor
    • H01L29/401—Multistep manufacturing processes
    • H01L29/4011—Multistep manufacturing processes for data storage electrodes
    • H01L29/40111—Multistep manufacturing processes for data storage electrodes the electrodes comprising a layer which is used for its ferroelectric properties
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10B—ELECTRONIC MEMORY DEVICES
    • H10B51/00—Ferroelectric RAM [FeRAM] devices comprising ferroelectric memory transistors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10B—ELECTRONIC MEMORY DEVICES
    • H10B51/00—Ferroelectric RAM [FeRAM] devices comprising ferroelectric memory transistors
    • H10B51/30—Ferroelectric RAM [FeRAM] devices comprising ferroelectric memory transistors characterised by the memory core region
    • 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]
    • H10K10/468—Insulated gate field-effect transistors [IGFETs] characterised by the gate dielectrics
    • H10K10/474—Insulated gate field-effect transistors [IGFETs] characterised by the gate dielectrics the gate dielectric comprising a multilayered structure

Definitions

  • Organic thin film transistor organic composite electronic device, manufacturing method thereof, display device, and memory
  • the present invention relates to an organic thin film transistor, a method for producing the organic thin film transistor, and a display device such as an organic EL display device including the organic thin film transistor.
  • the present invention also relates to an organic composite electronic device including an organic thin film transistor and a high dielectric capacitor, a method for manufacturing the organic composite electronic device, and an organic semiconductor memory using the organic composite electronic device.
  • the present invention relates to an organic composite electronic device comprising two or more organic thin film transistors having different performances, a method for producing the organic composite electronic device, and a strong dielectric memory using the organic composite electronic device.
  • An organic thin film transistor has, for example, a structure in which a substrate, a gate electrode, a gate insulating film, a source electrode, a drain electrode, an organic semiconductor film, and a protective film are stacked.
  • Organic thin-film transistors can be obtained by a low-cost manufacturing process under normal temperature and normal pressure, such as printing, and have good strength and compatibility with flexible substrates.
  • organic thin film transistors can be applied to image drive elements of flat panel displays such as liquid crystal display devices and organic electoluminescence (EU display devices, electrophoretic display devices, sheet displays, electronic It is expected to be applied to integrated circuit technology for electronic devices such as paper, electronic price tags and electronic tags, and biosensors.
  • EU display devices organic electoluminescence
  • electrophoretic display devices electrophoretic display devices
  • sheet displays electronic It is expected to be applied to integrated circuit technology for electronic devices such as paper, electronic price tags and electronic tags, and biosensors.
  • a high dielectric constant for example, in the organic thin film transistor disclosed in Japanese Patent Publication No. 5-508745 and US Pat. No. 5,347,144, in order to increase the drain current, Since it is better to have a larger electric capacity per unit area, a high dielectric constant, a dielectric constant of at least 5 and a high insulating polymer (such as cyanoethyl pullulan) are used for the gate insulating film.
  • This cyanoethyl pullulan has a dielectric constant of 18.5.
  • polyacrylonitrile which is a polymer having a cyano group
  • the relative dielectric constant of polyatrylonitrile is 4.5.
  • polyimide, polystyrene, polymethylmetatalylate, polybuluchloride, polybulualcohol, polyparaxylene, polyvinylidene fluoride, polybutanol, Polymers such as pullulan and norylene and their derivatives have been proposed.
  • Japanese Patent Publication No. 8-191162 it is further proposed to use a composite material mixed with a material for increasing the dielectric constant in order to obtain a more effective electric field effect.
  • a first object of the present invention is to provide an organic thin film transistor capable of suppressing leakage current in a gate insulating film, obtaining a high insulating film capacity, and operating at a low gate voltage, a method for producing the same, and the organic thin film transistor. It is to provide a display device to be used.
  • a second object of the present invention is to simplify the manufacturing process of an organic composite electronic device including an organic thin film transistor and a high dielectric capacitor.
  • a third object of the present invention is to simplify a manufacturing process of an organic composite electronic device including two or more organic thin film transistors having different performances.
  • the present inventors have studied various organic gate insulating film materials conventionally used for organic thin film transistors, and as a result, have found that there is a sensory function present in the molecular structure. As a result of further investigation, it was found that there was no functional group with an unshared electron pair and a ⁇ -electron bond in the molecular structure.
  • a low dielectric film is formed using an organic polymer compound that does not have a layer, and this low dielectric film and a ferroelectric film are laminated to form a gate insulating film.
  • an organic thin film transistor comprising a gate electrode, a gate insulating film, an organic semiconductor film, a source electrode, and a drain electrode on a substrate.
  • the gate insulating film includes a ferroelectric film, and a low dielectric film having a low dielectric constant compared to the ferroelectric film interposed between the ferroelectric film and the organic semiconductor film.
  • the low-dielectric film includes an organic thin film transistor including an organic polymer compound that does not have a functional group having an unshared electron pair and does not have 71 electronic bonds in the molecular structure.
  • a first step of forming a gate electrode on the substrate a second step of forming a ferroelectric film on the substrate including the gate electrode, and a ferroelectric film on the ferroelectric film
  • a third step of forming a low dielectric film having a low dielectric constant compared to the fourth step a fourth step of forming an organic semiconductor film on the low dielectric film, and a source electrode and a drain on the organic semiconductor film.
  • a method for producing an organic thin film transistor which comprises a step of obtaining a solution, and a step of casting the solution and then removing the solvent.
  • a display device comprising the organic thin film transistor is also provided.
  • the organic thin film transistor of the present invention is capable of suppressing leakage current in the gate insulating film, realizing stable and excellent performance, and operating at a low gate voltage.
  • the method for producing an organic thin film transistor of the present invention can produce an organic thin film transistor that has stable characteristics, has a high insulating film capacity, and can operate at a low gate voltage.
  • the organic thin film transistor of the present invention can be used as an image driving element for a flat panel display such as a liquid crystal display device, an organic EL (electrical luminance) display device, and an electrophoretic display device. It can also be applied to integrated circuit technology for electronic devices such as sheet displays, electronic paper, electronic price tags and electronic tags, and biosensors, gas sensors, and memory elements. In particular, since the organic thin film transistor of the present invention can be operated at a low voltage, it is suitable for an image driving element of an organic EL display device, for example.
  • a method for producing an organic composite electronic device is a method for producing an organic composite electronic device comprising a transistor and a capacitor on a substrate.
  • a second electrode group for the transistor is formed in a predetermined positional relationship with the first electrode group, and a second electrode group for the capacitor is formed corresponding to the first electrode group for the capacitor at least across the ferroelectric film.
  • the electrode group refers to one or more electrodes.
  • the predetermined positional relationship refers to a positional relationship in which each electrode is arranged so as to constitute a transistor.
  • the transistor ferroelectric film and the capacitor ferroelectric film are formed in the same formation process, and the transistor electrode group and the capacitor electrode group are formed in the same formation process. Therefore, it is possible to manufacture organic composite electronic devices having transistors and capacitors with less man-hours compared to the conventional technology, which are formed by different forming processes! Manufacturing cost can be reduced.
  • the insulating film (gate insulating film) of the transistor is formed by laminating a ferroelectric film and a low dielectric film, the dielectric constant of the low dielectric film should be appropriately selected.
  • the present invention it is possible to facilitate the manufacture of an organic composite electronic device including an organic thin film transistor and a high dielectric capacitor.
  • the organic composite electronic device manufactured according to the present invention can be suitably used for manufacturing, for example, a signal circuit for a wireless transmission tag.
  • an organic composite electronic device manufacturing method includes an organic composite electronic device including a first transistor and a second transistor on a substrate.
  • a second electrode group forming step of forming the second electrode group for the second transistor in a predetermined positional relationship with the first electrode group for the second transistor refers to one or more electrodes.
  • the predetermined positional relationship means a positional relationship in which each electrode is arranged so as to constitute a transistor.
  • the ferroelectric film for the first transistor and the ferroelectric film for the second transistor are formed in the same formation process, and the first transistor electrode group and the second transistor electrode group are formed. Therefore, it is possible to manufacture organic composite electronic devices with two types of transistors with a small amount and a small number compared to the conventional technology formed by different forming processes. Manufacturing cost can be reduced.
  • the first transistor is formed with a two-layer gate insulating film having a ferroelectric film and a low dielectric film, the dielectric constant of the low dielectric film can be selected appropriately.
  • An organic thin film transistor having a good characteristic with low hysteresis capable of setting a dielectric constant of an insulating film composed of a dielectric film and a low dielectric film to a desired value, being operable at a low gate voltage.
  • a gate insulating film made of a ferroelectric film is formed, an organic thin film transistor suitable for use in, for example, a ferroelectric memory can be obtained.
  • FIG. La is a diagram showing a configuration example of a top gate staggered organic thin film transistor of the first embodiment.
  • FIG. Lb is a diagram showing a configuration example of a top gate coplanar type organic thin film transistor of the first embodiment.
  • FIG. 2a is a diagram showing a configuration example of a bottom-gate staggered organic thin film transistor of the first embodiment.
  • FIG. 2b Configuration example of bottom gate 'coplanar type organic thin film transistor of the first embodiment
  • FIG. 4 is a diagram illustrating a configuration example of one pixel of the organic EL display device according to the first embodiment.
  • FIG. 6a is a diagram showing a manufacturing process (part 1) of an organic composite electronic device including a bottom-gate staggered organic thin film transistor and a capacitor according to a second embodiment.
  • FIG. 6b A diagram showing a manufacturing process (part 2) of the organic composite electronic device including the bottom gate staggered organic thin film transistor and the capacitor according to the second embodiment.
  • 6c] is a diagram showing a manufacturing process (No. 3) of the organic composite electronic device including the bottom gate staggered organic thin film transistor and the capacitor according to the second embodiment.
  • 6d is a diagram showing a manufacturing process (No. 4) of the organic composite electronic device including the bottom gate staggered organic thin film transistor and the capacitor according to the second embodiment.
  • 6e is a view showing a manufacturing process (No. 5) of the organic composite electronic device including the bottom gate staggered organic thin film transistor and the capacitor according to the second embodiment.
  • 6f is a diagram showing a manufacturing process (No. 6) of the organic composite electronic device including the bottom gate staggered organic thin film transistor and the capacitor of the second embodiment.
  • FIG. 7a] is a diagram showing a manufacturing process (No. 1) of an organic composite electronic device including a bottom gate coplanar type organic thin film transistor and a capacitor according to a second embodiment.
  • FIG. 7b] is a diagram showing a manufacturing process (No. 2) of the organic composite electronic device including the bottom gate 'coplanar type organic thin film transistor and the capacitor of the second embodiment.
  • FIG. 7c] is a diagram showing a manufacturing process (No. 3) of the organic composite electronic device including the bottom gate coplanar type organic thin film transistor and the capacitor according to the second embodiment.
  • FIG. 7d] is a diagram showing a manufacturing process (No. 4) of the organic composite electronic device including the bottom gate and coplanar type organic thin film transistor and capacitor of the second embodiment.
  • FIG. 7e] is a diagram showing a manufacturing process (No. 5) of an organic composite electronic device including a bottom-gate coplanar type organic thin film transistor and a capacitor according to a second embodiment.
  • FIG. 11 is a diagram showing a manufacturing process (No. 6) of an organic composite electronic device including a shita.
  • FIG. 8a] is a diagram showing a manufacturing process (No. 1) of an organic composite electronic device including a top gate stagger type organic thin film transistor and a capacitor according to a second embodiment.
  • FIG. 8b] is a diagram showing a manufacturing process (No. 2) of the organic composite electronic device including the top gate stagger type organic thin film transistor and the capacitor of the second embodiment.
  • FIG. 8c] is a diagram showing a manufacturing process (No. 3) of the organic composite electronic device including the top gate staggered organic thin film transistor and the capacitor according to the second embodiment.
  • FIG. 8d] is a diagram showing a manufacturing process (No. 4) of the organic composite electronic device including the top gate staggered organic thin film transistor and the capacitor according to the second embodiment.
  • FIG. 8e] is a diagram showing a manufacturing process (No. 5) of the organic composite electronic device including the top gate stagger-type organic thin film transistor and capacitor of the second embodiment.
  • FIG. 8f] is a diagram showing a manufacturing process (No. 6) of the organic composite electronic device including the top gate stagger type organic thin film transistor and capacitor of the second embodiment.
  • FIG. 9a] is a diagram showing a manufacturing process (No. 1) of an organic composite electronic device including a top-gate coplanar type organic thin film transistor and a capacitor according to a second embodiment.
  • FIG. 9b] is a diagram showing a manufacturing process (No. 2) of an organic composite electronic device including a top gate coplanar type organic thin film transistor and a capacitor according to a second embodiment.
  • FIG. 9c] is a diagram showing a manufacturing process (No. 3) of the organic composite electronic device including the top gate coplanar type organic thin film transistor and the capacitor according to the second embodiment.
  • FIG. 9d] is a diagram showing a manufacturing process (No. 4) of an organic composite electronic device including a top gate coplanar type organic thin film transistor and a capacitor according to a second embodiment.
  • FIG. 9e] is a diagram showing a manufacturing process (No. 5) of an organic composite electronic device including a top gate coplanar type organic thin film transistor and a capacitor according to a second embodiment.
  • FIG. 9f] is a diagram showing a manufacturing process (No. 6) of an organic composite electronic device including the top gate coplanar type organic thin film transistor and capacitor of the second embodiment.
  • FIG. 10 A diagram showing a configuration example of the high dielectric memory cell of the second embodiment.
  • FIG. 1 la] is a diagram showing a manufacturing process (No. 1) of an organic composite electronic device including the bottom gate stagger type organic thin film transistor of the third embodiment.
  • FIG. 1 lb is a diagram showing a manufacturing process (No. 2) of an organic composite electronic device including a bottom-gate staggered organic thin film transistor according to a third embodiment.
  • FIG. 11c is a diagram showing a manufacturing process (No. 3) of the organic composite electronic device including the bottom-gate staggered organic thin film transistor of the third embodiment.
  • FIG. 1 Id is a diagram showing a manufacturing process (No. 4) of an organic composite electronic device including a bottom-gate staggered organic thin film transistor according to a third embodiment.
  • FIG. 1 is a diagram showing a manufacturing process (No. 5) of an organic composite electronic device including a bottom-gate staggered organic thin film transistor according to a third embodiment.
  • FIG. 1 If is a diagram showing a manufacturing process (No. 6) of an organic composite electronic device including a bottom-gate staggered organic thin film transistor according to a third embodiment.
  • FIG. 12a is a view showing a manufacturing process (No. 1) of an organic composite electronic device including a bottom-gate coplanar type organic thin film transistor according to a third embodiment.
  • FIG. 12 b is a diagram showing a manufacturing process (No. 2) of the organic composite electronic device including the bottom gate coplanar type organic thin film transistor of the third embodiment.
  • FIG. 12c is a diagram showing a manufacturing process (No. 3) of the organic composite electronic device including the bottom-gate coplanar type organic thin film transistor of the third embodiment.
  • FIG. 12d is a diagram showing a manufacturing step (No. 4) of the organic composite electronic device including the bottom gate ′ coplanar type organic thin film transistor of the third embodiment.
  • FIG. 12e is a diagram showing a manufacturing process (No. 5) of the organic composite electronic device including the bottom gate ′ coplanar type organic thin film transistor of the third embodiment.
  • FIG. 12f is a diagram showing a manufacturing step (No. 6) of the organic composite electronic device including the bottom gate ′ coplanar type organic thin film transistor of the third embodiment.
  • FIG. 13a is a diagram showing a manufacturing process (No. 1) of an organic composite electronic device including a top-gate staggered organic thin film transistor according to a third embodiment.
  • FIG. 13b is a diagram showing a manufacturing process (No. 2) of the organic composite electronic device including the top gate stagger type organic thin film transistor of the third embodiment.
  • FIG. 13c is a diagram showing a manufacturing process (No. 3) of the organic composite electronic device including the top-gate staggered organic thin film transistor of the third embodiment.
  • FIG. 13d is a diagram showing a manufacturing process (No. 4) of the organic composite electronic device including the top-gate staggered organic thin film transistor of the third embodiment.
  • FIG. 13e is a diagram showing a manufacturing process (No. 5) of an organic composite electronic device including a top-gate staggered organic thin film transistor according to a third embodiment.
  • FIG. 13f is a diagram showing a manufacturing process (No. 6) of an organic composite electronic device including the top-gate staggered organic thin film transistor of the third embodiment.
  • FIG. 14a is a diagram showing a manufacturing process (No. 1) of an organic composite electronic device including a top gate coplanar type organic thin film transistor of a third embodiment.
  • FIG. 14b is a diagram showing a manufacturing process (No. 2) of the organic composite electronic device including the top gate coplanar type organic thin film transistor of the third embodiment.
  • FIG. 14c is a view showing a manufacturing process (No. 3) of the organic composite electronic device including the top gate coplanar type organic thin film transistor of the third embodiment.
  • FIG. 14d is a diagram showing a manufacturing step (No. 4) of the organic composite electronic device including the top gate coplanar type organic thin film transistor of the third embodiment.
  • FIG. 14e is a diagram showing a manufacturing process (No. 5) of the organic composite electronic device including the top gate coplanar type organic thin film transistor of the third embodiment.
  • FIG. 14f is a diagram showing a manufacturing process (No. 6) of the organic composite electronic device including the top gate coplanar type organic thin film transistor of the third embodiment.
  • FIG. 15 is a diagram showing a configuration example of a ferroelectric memory cell according to a third embodiment.
  • FIG. 16 is a VD-ID diagram of the transistor or the first transistor in the example.
  • FIG. 17 is a VG-ID diagram of the transistor or the first transistor in the example.
  • FIG. 18 is a VG-ID diagram of the second transistor in the example.
  • the organic thin film transistor of this embodiment has an organic semiconductor film, a gate electrode, and a soot on a substrate.
  • the gate insulating film has a two-layer structure in which a low dielectric constant low dielectric film and a ferroelectric film having a higher dielectric constant than the low dielectric film are stacked.
  • An organic thin film transistor has a source electrode and a drain electrode in contact with an organic semiconductor film, and has a top gate type having a gate electrode via a gate insulating film thereon, a gate electrode, and a gate insulating film thereon It is roughly classified into a bottom gate type having a source electrode and a drain electrode connected by an organic semiconductor film through a via.
  • the organic thin film transistor to which the present invention can be applied may be a top gate type or a bottom gate type. However, damage to the organic semiconductor film due to the formation of the source electrode and the drain electrode is prevented. From the viewpoint of avoidance, the bottom gate type is preferable.
  • FIG. La is a diagram showing a configuration of a top gate stagger type organic thin film transistor.
  • the organic thin film transistor shown in FIG. La has an undercoat layer 12 on a substrate 11.
  • the undercoat layer 12 contains a polymer or a compound selected from inorganic oxides and inorganic nitrides.
  • An organic semiconductor film 16, a drain electrode 14, and a source electrode 15 are provided in contact with the undercoat layer 12.
  • a gate electrode 18 is provided on the organic semiconductor film 16 via a gate insulating film 17.
  • the gate insulating film 17 is formed by laminating a low dielectric film 17a and a ferroelectric film 17b.
  • the low dielectric film 17a is disposed between the organic semiconductor film 16 and the ferroelectric film 17b.
  • a protective film (sealing film) 23 is provided as the outermost layer.
  • Figure lb shows the configuration of the top gate coplanar type with the drain electrode and the stacking order of the source electrode and the organic semiconductor film changed.
  • FIG. 2a is a diagram showing a configuration of an organic thin film transistor of a bottom gate stagger type (Bottom Gate Stagger type).
  • the organic thin film transistor shown in FIG. 2 a has an undercoat layer 12 on a substrate 11.
  • the undercoat layer 12 contains a polymer or a compound selected from inorganic oxides and inorganic nitrides.
  • An organic semiconductor film 16 is provided in contact with the undercoat layer 12 via a gate electrode 18 and a gate insulating film 17.
  • the gate insulating film 17 is formed by laminating a low dielectric film 17a and a ferroelectric film 17b.
  • the low dielectric film 17a is interposed between the organic semiconductor film 16 and the ferroelectric film 17b.
  • Further organic semiconductor film A drain electrode 14 and a source electrode 15 are provided in contact with 16.
  • Figure 2b shows the configuration of the bottom gate coplanar type with the drain electrode and the stacking order of the source electrode and the organic semiconductor film changed.
  • Organic semiconductor materials include ⁇ -conjugated materials.
  • ⁇ -conjugated materials include polypyrrole, poly ( ⁇ substituted pyrrole), poly (3-substituted pyrrole), poly (3,4-disubstituted pyrrole), and the like; polythiophene, poly (3-substituted thiophene) Polythiophenes such as poly (3,4-disubstituted thiophene) and polybenzothiophene; Polyisothianaphthenes such as polyisothianaphthene; Polyethylene vinylenes such as polyphenylene vinylene; Poly ( ⁇ vinylene) such as poly (.rho. phenylene vinylene) s; Poria diphosphate, poly (Nyu- substituted Ayurin), poly (3 - substituent Ayurin), poly (2, 3 - substituted Ayurin) Polya diphosphate,
  • Poly rubazoles such as Nole and poly ( ⁇ -substituted carbazole); Polyselenophenes such as polyselenophene; Polyfurans such as polyfuran and polybenzofuran; Poly ( ⁇ -phenol) such as poly ( ⁇ -phenol) Polyindoles such as polypyridazine; polypyridazines such as polypyridazine; naphthacene, pentacene, hexacene, heptacene, dibenzopentacene, tetrabenzopentacene, pyrene, dibenzopyrene, taricene, perylene, coronene, terylene, Derivatives (triphenodioxazines) in which a part of carbon of polyacene is substituted with an atom such as N, S, or O, or a functional group such as carbonyl group.
  • Triphenodioxazines in which a part of carbon
  • these polymers have the same repeating unit, for example, thiophene hexamer.
  • ⁇ -seccithiophene ⁇ , ⁇ -dihexinole ⁇ -seccithiophene, ⁇ , ⁇ -dihexoxyl ⁇ -kinchethiophene, ⁇ , ⁇ -bis (3-butoxypropyl) ⁇ -sexuality
  • examples include oligomers such as ophene and styrylbenzene derivatives.
  • metal phthalocyanines such as copper phthalocyanine and fluorine-substituted copper phthalocyanine described in Japanese Patent Application Laid-Open No. 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, 1 bis (1H, 1H-perfluorooctyl) naphthalene 1, 4, 5, 8— Tetracarboxylic acid diimide, N, N, monobis (1H, 1H-perfluorobutyl) naphthalene 1, 4, 5, 8-tetracarboxylic acid diimide and N, N'-dioctylnaphthalene 1, 4, 5, 8 tetracarboxylic acid Naphthalene tetracarboxylic acid diimides such as diimide, na
  • thiophene, chelenylene vinylene, phenylene vinylene, ⁇ -phenylene, and at least one of these substituents are repeating units, and the number of repeating units ⁇ is 4 to; an oligomer having 10 to 10 and a polymer having ⁇ of 20 or more; a condensed polycyclic aromatic compound such as pentacene; fullerenes; a condensed ring tetracarboxylic diimide; and a group consisting of metal phthalocyanines At least one selected from is preferred.
  • organic semiconductor materials include tetrathiafunolevalene (TTF) -tetracyanoquinodimethane (TCNQ) complex, bisethylenetetrathiafulvalene (BEDTTTF) -perchloric acid complex, BEDTTTF iodine complex, TCNQ iodine complex
  • TTF tetrathiafunolevalene
  • BEDTTTF bisethylenetetrathiafulvalene
  • TCNQ iodine complex TCNQ iodine complex
  • Organic molecular complex such as Further examples include ⁇ -conjugated polymers such as polysilane and polygermane, and organic / inorganic hybrid materials described in Japanese Unexamined Patent Publication No. 2000-260999.
  • a material having a functional group such as acrylic acid, acetamido, dimethylamino group, cyano group, carboxyl group, nitro group; benzoquinone derivative, tetracyanethylene, tetracyanoquinodimethane and derivatives thereof Materials that accept electrons, such as amino groups, triphenyl groups, alkyl groups, hydroxyl groups, Materials having functional groups such as alkoxy groups and phenyl groups; substituted amines such as phenylenediamine, substituted amines, anthracene, benzoanthracene, substituted benzoanthracenes, pyrene, substituted pyrene, force rubazole and derivatives thereof, tetrathiafulvalene and its A material which becomes a donor which is an electron donor such as a derivative may be contained.
  • a functional group such as acrylic acid, acetamido, dimethylamino group, cyano group, carboxyl group, nitro group
  • Organic semiconductor film formation (formation) methods include vacuum deposition, molecular beam epitaxy, ion cluster beam, low energy ion beam, ion plating, CVD, sputtering, plasma Examples include a polymerization method, an electrolytic polymerization method, a chemical polymerization method, a spray coating method, a spin coating method, a blade coating method, a dip coating method, a casting method, a Rhino recording method, a bar coating method, a die coating method, and an LB method.
  • the thickness of the organic semiconductor film varies depending on the organic semiconductor material to be used, but is usually 1 ⁇ m or less, preferably from a monolayer thickness to 400 nm.
  • Each electrode (gate electrode, source electrode and drain electrode) constituting the organic thin film transistor is formed of a conductive material.
  • conductive materials include platinum, gold, silver, nickel, chromium, copper, iron, tin, antimony lead, tantalum, indium, palladium, tellurium, rhenium, iridium, aluminum, ruthenium, germanium, and 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, magnesium, potassium, calcium, scandium, Titanium, manganese, zirconium oxide, gallium, niobium, sodium, sodium-potassium alloy, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide Compound, and lithium / aluminum mixed compounds and the like.
  • ITO indium tin oxide
  • conductive polymers whose conductivity has been improved by doping or the like, for example, conductive polyaniline, conductive polypyrrole, or conductive polythiophene (polyethylene dioxythiophene and polystyrene sulfonic acid complex, etc.) can be mentioned.
  • the material for forming the source electrode and the drain electrode is preferably a p-type semiconductor having a low electrical resistance at the contact surface with the organic semiconductor film among the materials listed above. Platinum, gold, silver, ITO, conductive polymer and carbon are preferred.
  • the gate electrode, the source electrode, and the drain electrode are formed using a fluid electrode material such as a solution, paste, ink, or dispersion liquid containing the above-described conductive material. It is preferable to use a conductive polymer or a fluid electrode material containing fine metal particles containing platinum, gold, silver and copper!
  • the fluid electrode material containing fine metal particles for example, a known conductive paste may be used.
  • the average particle size is 1 to 50 nm, preferably 1 to;
  • a material in which fine particles are dispersed in water or a dispersion medium that is an arbitrary organic solvent using a dispersion stabilizer as required is used.
  • the average particle size can be measured by a photon correlation method.
  • 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.
  • a chemical production method in which metal fine particles are produced by reducing ON. After forming an electrode using these metal fine particle dispersions and drying the solvent, the metal fine particles are formed by heating in the range of 100 to 300 ° C, preferably 150 to 200 ° C as necessary. An electrode pattern having a desired shape is formed by heat fusion.
  • a conductive thin film is formed by sputtering or vapor deposition using the conductive material as a raw material, and then a pattern is formed with a photoresist, and then an unnecessary thin film is removed by etching to form an electrode pattern.
  • Photolithographic method to form an electrode metal mask method on which a metal mask is placed on a substrate, and sputtering or vapor deposition is performed as it is to form an electrode pattern; a photoresist film is formed on a metal foil such as aluminum or copper by thermal transfer or ink jet
  • a method of forming an electrode pattern by removing an unnecessary thin film by etching after forming a pattern There are known methods such as a method of forming an electrode pattern by removing an unnecessary thin film by etching after forming a pattern.
  • a solution or dispersion of a conductive polymer, 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 lithograph or laser abrasion. You may make it.
  • a method of patterning conductive inks or conductive pastes containing conductive polymers and metal fine particles by printing methods such as relief printing, intaglio printing, lithographic printing, and screen printing.
  • the thickness of the electrode is not particularly limited, but is usually 20 to 500 nm, preferably 50 to 200.
  • the gate insulating film is a film having a two-layer structure in which a low dielectric film having a relatively low dielectric constant and a ferroelectric film (high dielectric film) having a relatively high dielectric constant are stacked.
  • the power to explain the gate insulating film having a two-layer structure may be a film having a multilayer structure of two or more layers within a range not impairing the object of the present invention.
  • the low dielectric film is formed in contact with the organic semiconductor film, and the ferroelectric film is formed in contact with the gate electrode.
  • the relative dielectric constant of the low dielectric film is normally set to a value of 4 or less, and is preferably set to a value of 3.5 or less. Force S is preferable, and is more preferably set to a value of 3 or less. .
  • the lower limit of the dielectric constant is usually around 2.
  • the film thickness of the low dielectric film is preferably set to 5 nm to 500 nm, more preferably 10 nm to 300 nm.
  • the relative dielectric constant of the ferroelectric film is normally set to a value of 5 or more, and is preferably set to a value of 7 or more, and is preferably set to a value of 10 or more.
  • the upper limit of the relative dielectric constant is usually about 50.
  • the film thickness of the ferroelectric film is preferably set to 5 nm to 500 nm, more preferably 10 nm to 300 nm.
  • the effective dielectric constant of the entire gate insulating film can be adjusted by appropriately setting the relative dielectric constant and film thickness of the low dielectric film and the relative dielectric constant and film thickness of the ferroelectric film.
  • the total thickness of the gate insulating film formed by laminating the low dielectric film and the ferroelectric film may be any thickness as long as the insulating property is maintained. 10 to 500 nm, more preferably 10 to 300 nm. It is desirable to make it as thin as possible as the size of organic thin-film transistor elements becomes smaller.
  • the low dielectric film constituting the gate insulating film is a film containing an organic polymer compound that does not have a functional group having an unshared electron pair and does not have a negative electron bond in the molecular structure.
  • the “functional group” is not involved in the formation of the skeleton structure of the main chain of the organic polymer compound.
  • the unshared electron pair is an electron that is paired with two of the outermost electrons of the atom without involving a bond with another atom. It is also called a lone pair or a non-bonded pair.
  • the functional group having an unshared electron pair is a group bonded to the main chain and branched from the main chain, and does not include those based on the main chain itself.
  • an imino group in the case where the main chain itself exists in the main chain itself such as polyamine has an unshared electron pair. Not included in the functional group.
  • a nitrile group having a nitrile group bonded to the main chain such as polyacrylonitrile or a fluorine group having a fluorine group bonded to the main chain such as polytetrafluoroethylene has an unshared electron pair. Included in functional group.
  • a ⁇ -electron bond is a bond formed by electrons belonging to a ⁇ orbit.
  • a ⁇ orbital is a type of orbit that accommodates electrons in a molecule, and orbitals that are distributed in a direction perpendicular to the axis connecting the nuclei of one bond (bonding axis) are above and below the molecular plane. It is an electron orbit created by overlapping in the horizontal direction.
  • bonds having a ⁇ -electron bond include carbon-carbon double bonds and triple bonds, nitrogen-carbon triple bonds, carbon-oxygen double bonds, and benzene and naphthalene double bonds. It is done.
  • the organic polymer compound contained in the low dielectric film is a compound that does not have a functional group having an unshared electron pair and does not have a negative electron bond in the molecular structure as described above. Any of these compounds can achieve the desired effects of the present invention.
  • the organic high molecular compound used in this embodiment has a small relative dielectric constant and is usually 3 or less. In this embodiment, the relative dielectric constant can be measured by a capacitance method using an LCR meter (manufactured by Agilent Technologies, part number 4284 ⁇ ).
  • organic polymer compounds examples include polyolefins such as polyethylene, polypropylene, and polybutene; alicyclic polyolefin polymers; polyamines; polyethers; Of these, alicyclic polyolefin polymers are preferred from the viewpoint that the frequency dependence of the dielectric constant is small.
  • the alicyclic olefin polymer is a polymer having a cycloalkane structure in the main chain and / or side chain. From the viewpoint of mechanical strength and heat resistance, a polymer containing a cycloalkane structure in the main chain is preferred. Cycloalkane structures can be monocyclic or polycyclic (condensed). Multi-rings, bridge rings, etc.). The number of carbon atoms constituting one unit of the cycloalkane structure is not particularly limited, but is usually 4 to 30, preferably 5 to 20, more preferably 5 to 15; Various characteristics such as mechanical strength, heat resistance, and moldability are highly known and suitable. In addition, the alicyclic olefin polymer used in the present embodiment is usually a thermoplastic resin.
  • the repeating unit having a cycloalkane structure is usually 30 to 100% by weight in all the repeating units in the main chain of the alicyclic olefin polymer, preferably 50 to 50%. 100 weight. / 0 , more preferably from 70 to 100% by weight. If the ratio of the repeating unit having a cycloalkane structure is within these ranges, the heat resistance is excellent.
  • the alicyclic olefin polymer is usually obtained by addition polymerization or ring-opening polymerization of olefin having a ring structure, and hydrogenating the unsaturated bond portion and the aromatic ring portion as necessary. .
  • Olefins having a ring structure used to obtain an alicyclic olefin polymer include norbornene, dicyclopentagen, tetracyclododecene, ethyltetracyclododecene, and ethylidenetetracyclodone. Decene, tetracyclo [7 ⁇ 4.0.110, 13.
  • Polymerization of olefin having a ring structure can be carried out according to a known method.
  • the polymerization temperature, pressure and the like are not particularly limited, but the polymerization is usually carried out at a polymerization temperature of 50 ° C to 100 ° C and a polymerization pressure of 0 to 5 MPa.
  • the hydrogenation reaction is carried out by blowing hydrogen in the presence of a known hydrogenation catalyst.
  • alicyclic olefin polymer examples include a hydride of a ring-opening polymer of a norbornene monomer, an addition polymer of a norbornene monomer and a hydride thereof, and a norbornene monomer.
  • hydrides of ring-opening polymers of norbornene monomers are preferred, addition polymers of norbornene monomers, addition weights of norbornene monomers and bur compounds (such as ethylene and a 1-year-old refin).
  • aromatic ring hydrides of polymers and aromatic olefin polymers particularly hydrides of ring-opening polymers of norbornene monomers.
  • the above alicyclic olefin polymers can be used singly or in combination of two or more.
  • the norbornene monomer is a monomer having a norbornene structure as shown in Chemical Formula 1.
  • the norbornene monomer is ring-opening polymerized, a polymer having a repeating unit as shown in Chemical Formula 2 is obtained, and when this is hydrogenated, a polymer having a repeating unit as shown in Chemical Formula 3 is obtained.
  • Rl and R2 in Chemical Formula 3 represent a substituent having no unshared electron pair and having no ⁇ -electron bond, and R1 and R2 may be bonded to form a ring.
  • R1 and R2 in Chemical Formula 1 and Chemical Formula 2 are subjected to various production processes, and the finally obtained alicyclic olefin polymer does not have a functional group having an unshared electron pair and has a ⁇ -electron bond. Is not particularly limited, but preferably represents a substituent having no unshared electron pair and no ⁇ -electron bond, and R1 and R2 may be bonded to form a ring. Good.
  • the alicyclic olefin polymer used in the present embodiment is not particularly limited by the molecular weight.
  • the molecular weight of an alicyclic olefin polymer is a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) using cyclohexane as a solvent, and is usually 1,000— 1, 000,000, preferably ⁇ is in the range of 5,000-500,000, more preferably in the range of 10,000-250,000.
  • the molecular weight distribution of the alicyclic olefin polymer is the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by GPC using cyclohexane as a solvent. Usually, it is 5 or less, preferably 4 or less, more preferably 3 or less.
  • the glass transition temperature of the alicyclic olefin polymer is preferably 70 ° C or higher, more preferably 120 ° C or higher, and most preferably 140 ° C or higher. The glass transition temperature can be measured with a differential scanning calorimeter.
  • the low dielectric film has no functional group having an unshared electron pair and has 71 electronic bonds in the molecular structure as long as expression of the desired effect of the present invention is not inhibited.
  • organic polymer compounds other known organic polymer compounds are included!
  • the content of the organic polymer compound in the gate insulating film that does not have a functional group having an unshared electron pair and has 71 electronic bonds in the molecular structure is preferably 70 to 100% by weight
  • colorants such as pigments and dyes, optical brighteners, dispersants, heat stabilizers, light stabilizers, UV absorbers, antistatic agents, antioxidants, lubricants, solvents, and other compounding agents are used as appropriate. You may mix
  • Low dielectric film formation (formation) methods include vacuum deposition, molecular beam epitaxy, ion cluster beam, low energy ion beam, ion plating, CVD, sputtering, Examples include plasma polymerization method, electrolytic polymerization method, chemical polymerization method, spray coating method, spin coating method, blade coating method, dip coating method, casting method, Rhino recording method, bar coating method, die coating method and LB method. .
  • the wet method is preferred.
  • the organic polymer compound constituting the low dielectric film and the compounding agent are dissolved in a solvent as desired to obtain a solution, and after casting the solution, the solvent is removed to form a film. Is the method.
  • the solvent to be used may be appropriately selected from known solvents according to the organic polymer compound to be used.
  • the wet method include spin coating, blade coating, dip coating, roll coating, bar coating, die coating, screen printing, and ink jet printing. It is also possible to apply a printing method called soft lithography such as microcontact printing and micromolding. Of these wet methods, the spin coating method is particularly preferable.
  • the material of the ferroelectric film constituting the gate insulating film is not particularly limited. Usually, the insulating organic polymer alone, or the insulating organic polymer and the inorganic metal oxide or high dielectric insulator nanoparticles are used. Can be used. The dielectric constant can be adjusted by selecting an insulating organic polymer and adjusting the mass ratio between the insulating organic polymer and the nanoparticles. Using such a material, a ferroelectric film can be formed according to the same formation method as that of the low dielectric film described above. Also in the formation of the ferroelectric film, among the above-described forming methods, the spin coating method is particularly preferable, which is preferable to the wet method.
  • Examples of the insulating organic polymer include polyester, polycarbonate, polyvinyl alcohol, polyvinyl butyral, polyacetal, polyarylate, polyamide, polyamidoimide, polyetherimide, polyphenylene ether, polyphenylene sulfide, Polyethersulfone, polyetherketone, polyphthalanolamide, polyethernitrile, polyethersulfone, polybenzimidazole, polycarpositimide, polysiloxane, polymethylmethacrylate, polymethacrylamide, nitrile rubber, acrylic rubber , Polyethylene tetrafluoride, epoxy resin, phenol resin, melamine resin, urea resin, polybutene, polypentene, ethylene-propylene copolymer, ethylene-butene copolymer Polymer, polybutadiene, polyisoprene, ethylene propylene copolymer, butyl rubber, polymethylpentene, polystyrene, styren
  • the inorganic metal oxide nanoparticles are not particularly limited, and examples thereof include Ta 2 O 3, Y 2 O 3,
  • Nanoparticles such as TiO 2, CeO and ZrO can be mentioned. High dielectric insulator nanoparticles and
  • Ba Sr TiO (where d is 0 and d satisfies 1); d 1 d 3
  • Nanoparticles such as BZT), BaTiO 3, SrTiO 2 and Bi Ti 2 O 3
  • Ba Sr TiO is called Barium Strontium Titanate d 1 d 3
  • the weight ratio of BaTiO and SrTiO is 1: 9 to 9: 1
  • nanoparticles may be used alone or in combination of two or more. It can be used together.
  • the nanoparticles those having a dielectric constant of 5 or more are preferable. From the viewpoint of achieving this, normally, nanoparticles of a high dielectric insulator are preferably used.
  • the average particle size of the nanoparticles is usually 50 nm or less, preferably !!-50 nm, more preferably !!-30 nm.
  • the dielectric constant is measured according to JIS K 6911, and the average particle size is measured by the dynamic light scattering method.
  • the material of the ferroelectric film at least one selected from the group consisting of a titanium compound, a zirconium compound, a hafnium compound, and an aluminum compound, instead of the nanoparticle, instead of the insulating organic polymer as described above.
  • a mixture of these organometallic compounds may also be used. Also in this case, it is preferable to use an organometallic compound having a relative dielectric constant of 5 or more.
  • the organic thin film transistor of this embodiment may have a protective film (for example, the protective film 23 in FIGS. La, lb, 2a, and 2b) as the outermost layer.
  • the protective film is formed by, for example, a silicon oxide film, a silicon nitride film, or a silicon oxynitride film formed by a CVD method or a sputtering method; a polyparaxylene film formed by a thermal CVD method; or a wet method as described above
  • Preferred are a polyimide film, an alicyclic olefin polymer film, an ultraviolet curable epoxy resin film, an acrylic resin film, and the like.
  • the thickness of the protective film is usually preferably from lOOnm to ⁇ .
  • the substrate 11 is used to support the thin film organic thin film transistor.
  • the substrate is not particularly limited, and any material may be used.
  • polycarbonate, polyimide, polyethylene terephthalate (PET), and flexible plastic substrates such as alicyclic olefin polymers are used as substrates, such as glass, quartz, soda glass, and inorganic alkali. Glass substrates such as glass and silicon wafers can also be used.
  • the substrate and / or the protective film is made of the above-described alicyclic polyolefin polymer. Since the alicyclic olefin polymer has low moisture permeability and gas permeability! /, If the substrate and / or the protective film is made of the above alicyclic olefin polymer, the organic semiconductor film is not deteriorated. High effect to prevent Yes.
  • an undercoat layer 12 containing a compound selected from a polymer or an inorganic oxide and an inorganic nitride is provided.
  • Examples of the inorganic oxide contained in the undercoat layer include silicon oxide, aluminum oxide, and tantalum oxide.
  • Examples of the inorganic nitride include silicon nitride and aluminum nitride. Of these, preferred are silicon oxide and nitride nitride.
  • Polymers used for the undercoat layer containing the polymer include polyester resin, polycarbonate resin, cellulose resin, acrylic resin, polyurethane resin, polyethylene resin, polypropylene resin, polystyrene resin, phenoxy resin, norbornene resin, epoxy resin.
  • the undercoat layer is not particularly limited by the formation method.
  • the method for forming the undercoat layer include vacuum deposition, molecular beam epitaxy, ion cluster beam, low energy ion beam, ion plating, CVD, sputtering, and atmospheric pressure plasma.
  • the display device of this embodiment includes the organic thin film transistor.
  • This table In order to describe the display device more specifically, an organic EL display device will be described as an example.
  • This organic EL display device has at least one organic EL element with each pixel force formed in a matrix arrangement on a substrate, and at least two organic thin film transistors for driving the organic EL element. is there. At least one of the organic thin film transistors is the aforementioned organic thin film transistor.
  • the organic EL element is not particularly limited.
  • a structure in which a hole transport layer and a light emitting material layer are formed between a hole injection electrode serving as an anode and an electron injection electrode serving as a cathode SH--
  • a structure), a structure in which a light emitting material layer and an electron transport layer are formed between a hole injection electrode and an electron injection electrode (SH-B structure), or a hole injection electrode and an electron injection electrode a structure in which a hole transport layer, a light emitting material layer, and an electron transport layer are formed (DH structure) is included.
  • the organic EL element has a light emitting material layer and a hole (or electron) transport layer formed by the holes injected from the hole injection electrode (anode) and the electrons injected from the electron injection electrode (cathode). It operates on the principle that light is emitted by recombination within the interface and the light emitting material layer.
  • FIG. 3 shows a configuration example of a typical organic EL element.
  • the organic EL element shown in FIG. 3 includes a transparent substrate 1, a lower electrode layer (anode) 54, a light emitting material layer 62, and an upper electrode layer (cathode) 55.
  • a protective film 23 is provided as the outermost layer.
  • the transparent substrate 11 ′ has a visible light transmittance of 400 to 700 nm of 50% or more, is smooth, and does not change its characteristics when forming each layer of electrodes and organic EL elements! /, I prefer to be a thing!
  • the transparent substrate 11 ' can be formed of a material selected from the group consisting of plastic, glass, quartz, silicon, and ceramic.
  • a flexible and lightweight organic EL display can be obtained.
  • the plastic is preferably selected from the group consisting of polycarbonate resin, polyethersulfone resin, polyethylene terephthalate resin, polyimide resin, polymethyl methacrylate resin, and alicyclic olefin polymer.
  • the average thickness of the substrate is usually 30 111 to 3111111, preferably 50 to 300 mm 111.
  • Examples of the material constituting the lower electrode layer 54 include materials for emitting light from the lower electrode layer. Specifically, a conductive metal oxide, a translucent metal, or a laminate thereof is used. Can be mentioned. Specifically, indium oxide, zinc oxide, tin oxide, and composites thereof Conductive glass (NESA, etc.) made of indium oxide (tin) (ITO), indium oxide, zinc, etc., gold, platinum, silver, copper, etc. are used. Among them, ITO, indium oxide (zinc oxide, tin oxide) are used. preferable. As the lower electrode layer, an organic transparent conductive film such as polyaniline or a derivative thereof or polythiophene may be used.
  • the average thickness of the lower electrode layer can be selected as appropriate in consideration of light transmittance and electrical conductivity. Usually, lOnm to lO ⁇ m, preferably 100 to 500 nm. It is convenient that the lower electrode layer is transparent or translucent because the emission efficiency of light emission is good. Examples of the method for producing the lower electrode layer include a vacuum deposition method, a sputtering method, and a laminating method in which a metal thin film is thermocompression bonded.
  • the material constituting the light emitting material layer 62 a known material can be used as a light emitting material in the organic EL element without particular limitation.
  • Specific examples of such light-emitting materials include fluorescent brighteners such as benzothiazole, benzimidazole, and benzoxazole, metal chelated oxinoid compounds, styrylbenzene compounds, distyrylpyrazine derivatives, and aromatic dimethylidine. Compound etc. are mentioned.
  • Two or more kinds of light emitting materials may be mixed and used in the light emitting material layer. Two or more light emitting material layers may be laminated. Examples of a method for manufacturing the light emitting material layer include a vacuum deposition method and a casting method.
  • the average thickness of the light-emitting material layer varies depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are moderate values, but is usually 11 111 to 1 111, preferably 2 nm. ⁇ 500nm.
  • the material constituting the upper electrode layer 55 is preferably a material having a small work function! /, Which reflects light emitted from the light emitting material layer toward the upper electrode layer and is directed toward the lower electrode layer. Therefore, a mirror body is more preferable.
  • the alloy include magnesium silver alloy, magnesium indium alloy, magnesium aluminum alloy, indium silver alloy, lithium aluminum alloy, lithium magnesium alloy, lithium indium alloy, and calcium aluminum alloy.
  • the upper electrode layer may have a laminated structure of two or more layers. Examples of the method for producing the upper electrode layer include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method.
  • the average thickness of the upper electrode layer can be appropriately selected in consideration of electric conductivity and durability, but is usually 10 nm to 10111, preferably 100 to 500 nm.
  • the organic EL element includes a transparent substrate 11 ', a lower electrode layer 54, a light emitting material layer 62, an upper electrode layer.
  • another layer may be provided.
  • the other layer include a hole injection layer, a hole transport layer, an electron transport layer, and an electron injection layer.
  • the hole injection layer is a layer provided adjacent to the anode, and is a layer having a function of improving the hole injection efficiency from the anode.
  • the average thickness of the hole injection layer is usually 1 nm to 100 nm, preferably 2 nm to 50 nm.
  • the hole transport layer refers to a layer having a function of transporting holes.
  • the thickness of the hole transport layer differs depending on the material used, and it may be selected so that the drive voltage and luminous efficiency are appropriate. If it is too thick, the drive voltage of the element increases, which is not preferable. Therefore, the average thickness of the hole transport layer is usually 11 111 to 1111, preferably 2 nm to 500 nm. Examples of materials used for the hole injection layer and the hole transport layer include those known as hole transport compounds in organic EL devices.
  • the electron transport layer is a layer having a function of transporting electrons.
  • the thickness of the electron transport layer differs depending on the material used and may be selected so that the drive voltage and light emission efficiency are appropriate. However, the thickness should be at least sufficient to prevent pinholes. If it is too thick, the driving voltage of the organic EL element increases, which is not preferable. Therefore, the average thickness of the electron transport layer is usually 11 111 to 1111, preferably 2 nm to 500 nm.
  • the electron injection layer is a layer provided adjacent to the cathode and has a function of improving the electron injection efficiency from the cathode and has an effect of lowering the driving voltage of the element. The average thickness of the electron injection layer is usually In m ⁇ ;! OOnm, preferably 2 nm ⁇ 50 nm.
  • Examples of the material include those known as electron transfer compounds in organic EL devices. Examples of other methods for producing the layers include spin coating, casting, and vacuum deposition.
  • FIG. 4 is a circuit configuration example for one pixel of the organic EL display device of the present embodiment.
  • a configuration for one pixel of an organic EL display device usually, at least two organic thin film transistors for driving the EL element are required for at least one organic EL element, that is, a driving transistor and a writing transistor.
  • a driving transistor and a writing transistor In the configuration example in Fig. 4, only the drive transistor is shown, and the write transistor is omitted. At least one of the drive transistor and the write transistor is constituted by the organic thin film transistor of this embodiment.
  • the anode 54 of the organic EL element 6 and the drain electrode 14 of the organic thin film transistor 5 are connected. Then, for example, the organic thin film transistor 2 (write transistor) is turned on by the voltage applied in sequence to the scan electrode 1 connected to the horizontal drive circuit, as compared with an active matrix circuit as shown in FIG. Thus, the charge amount corresponding to the display signal from the data electrode 3 connected to the vertical drive circuit is accumulated in the capacitor 4.
  • the drive transistor 5 operates according to the amount of charge accumulated in the capacitor 4, current is supplied to the organic EL element 6, and the organic EL element is turned on. This lighting state is maintained until the voltage is applied to the scan electrode 1.
  • FIGS. 6a to 6f are diagrams showing a manufacturing process of an organic composite electronic device including a bottom gate stagger type transistor and a capacitor.
  • a first electrode group forming process is performed in which one of the transistor gate electrode Ga and the capacitor counter electrode CE1 is formed on the substrate 11 in the same process (FIG. 6a).
  • an undercoat layer (not shown) may be formed on the substrate 11, and these electrodes Ga and CE1 may be formed on the undercoat layer.
  • an insulating film forming step is performed in which an insulating film 17 is formed on the substrate 11 including these electrodes Ga and CEl (on the underlayer when the undercoat layer is formed) (FIG. 6b).
  • the insulating film forming step includes a ferroelectric film forming step for forming the ferroelectric film 17b, and a low dielectric film having a low dielectric constant on the ferroelectric film 17b as compared with the ferroelectric film 17b.
  • a low dielectric film forming step of forming 17a is included.
  • an organic semiconductor film forming step of forming the organic semiconductor film 16 on the low dielectric film 17a is performed (FIG. 6c).
  • a film removal step is performed to remove portions of the low dielectric film 17a and the organic semiconductor film 16 corresponding to the capacitor counter electrode CE1 (including the vicinity thereof! /).
  • a mask formation process (FIG. 6d) for forming or placing a mask MS on the organic semiconductor film 16, an etching process for removing a portion corresponding to the capacitor counter electrode CE1 by etching or the like, And a mask removing step for removing the mask MS.
  • removal portions are formed in portions of the low dielectric film 17a and the organic semiconductor film 16 corresponding to the capacitor counter electrode CE1 (FIG. 6e).
  • the transistor source electrode So is configured so that the transistor is configured in a predetermined positional relationship with the transistor gate electrode Ga across the ferroelectric film 17b, the low dielectric film 17a, and the organic semiconductor film 16.
  • a protective film is formed by forming a protective film.
  • an organic composite electronic device including an organic thin film transistor Tr having the ferroelectric film 17b and the low dielectric film 17a as the gate insulating film 17 and a high dielectric capacitor Ca having the ferroelectric film 17b as the insulating film is manufactured. Is done.
  • the low dielectric film 17a and the organic semiconductor film 16 are formed.
  • the force S that removes the capacitor forming part S the low dielectric film 17a is formed except the capacitor forming part in the low dielectric film forming process, and then the capacitor is formed in the organic semiconductor film forming process.
  • the organic semiconductor film 16 may be formed except for the portion to be formed.
  • the film removal step only the organic semiconductor film 16 is removed without removing the low dielectric film 17a. You may make it leave.
  • the organic thin film transistor Tr having the ferroelectric film 17b and the low dielectric film 17a as the gate insulating film 17 and the high dielectric capacitor Ca having the ferroelectric film 17b and the low dielectric film 17a as the insulating film 17 are formed.
  • An organic composite electronic device is provided.
  • the portion of the low dielectric film 17a corresponding to the capacitor counter electrode CE1 may be removed by removing only a portion of the low dielectric film 17a in the thickness direction.
  • FIG. 7a to FIG. 7f are diagrams illustrating a manufacturing process of an organic composite electronic device including a bottom gate coplanar type transistor and a capacitor.
  • a first electrode group forming process is performed in which one of the transistor gate electrode Ga and the capacitor counter electrode CE1 is formed on the substrate 11 in the same process (FIG. 7a).
  • An undercoat layer (not shown) may be formed on the substrate 11, and these electrodes Ga and CE1 may be formed on the undercoat layer.
  • an insulating film forming step is performed in which an insulating film 17 is formed on the substrate 11 including these electrodes Ga and CE1 (on the undercoat layer when the undercoat layer is formed) (FIG. 7b).
  • the insulating film forming process includes a ferroelectric film forming process for forming the ferroelectric film 17b, and a low dielectric film 17a having a low dielectric constant on the ferroelectric film 17b as compared with the dielectric film 17b. Forming a low dielectric film.
  • a low dielectric film removal step is performed to remove a portion of the low dielectric film 17a corresponding to the capacitor counter electrode CE1 (including the vicinity thereof! /).
  • This low dielectric film removal process includes a mask formation process (FIG. 7b) in which a mask MS1 is formed or placed on the low dielectric film 17a, and an etching process that removes a portion corresponding to the capacitor counter electrode CE1 by etching or the like. And a mask removing step for removing the mask MS1. As a result, a removal portion is formed in the portion of the low dielectric film 17a corresponding to the capacitor counter electrode CE1 (FIG. 7).
  • the transistor source electrode So and the drain electrode Dr are formed so as to form a transistor in a predetermined positional relationship with the transistor gate electrode Ga across the ferroelectric film 17b and the low dielectric film 17a.
  • a second electrode group forming step of forming a capacitor counter electrode CE2 corresponding to the capacitor counter electrode CE1 so as to constitute a capacitor with the ferroelectric film 17b interposed therebetween, and the organic semiconductor film 16 is formed thereon The organic semiconductor film formation process to be formed is performed (Fig. 7 d) 0
  • an organic semiconductor film removal step is performed to remove a portion of the organic semiconductor film 16 corresponding to the capacitor counter electrode CE1 (which may include the vicinity thereof).
  • This film removing step includes a mask forming step (FIG. 7e) for forming or placing a mask MS2 on the organic semiconductor film 16, an etching step for removing a portion corresponding to the capacitor counter electrode CE1 by etching or the like, And a mask removing process for removing the mask MS2.
  • a removal portion is formed in the portion of the organic semiconductor film 16 corresponding to the capacitor counter electrode CE1 (FIG. 7f).
  • a protective film formation process is performed and a protective film is formed.
  • an organic composite electronic device including an organic thin film transistor Tr having the ferroelectric film 17b and the low dielectric film 17a as the gate insulating film 17 and a high dielectric capacitor Ca having the ferroelectric film 17b as the insulating film is obtained. Manufactured.
  • the portion of the low dielectric film 17a in which the capacitor is formed is removed in the low dielectric film removal process.
  • the low dielectric film 17a may be formed except for the part where the capacitor is formed in the low dielectric film forming step.
  • the portion of the organic semiconductor film 16 in which the capacitor is formed is removed in the organic semiconductor film removing process, but the capacitor is removed in the organic semiconductor film forming process.
  • the organic semiconductor film 16 may be formed except for the portion to be formed.
  • the portion of the low dielectric film 17a corresponding to the capacitor counter electrode CE1 may be removed by removing only a part of the thickness in the thickness direction! /.
  • FIGS. 8a to 8f are diagrams showing a manufacturing process of an organic composite electronic device including a top gate stagger type transistor and a capacitor.
  • a first electrode group forming step is performed in which one of the transistor source electrode So, drain Dr, and capacitor counter electrode CE 1 is formed in the same step on the substrate 11, and the organic semiconductor film 16 is formed thereon.
  • An organic semiconductor film forming step is performed (FIG. 8a).
  • An undercoat layer (not shown) may be formed on the substrate 11, and these electrodes So, Dr, and CE1 may be formed on the undercoat layer.
  • An organic semiconductor film removing step is performed to remove the surrounding portion of the substrate.
  • This organic semiconductor film removing step includes a mask forming step (FIG. 8a) for forming or placing a mask MS1 on the organic semiconductor film 16, and an etching step for removing a portion corresponding to the capacitor counter electrode CE1 by etching or the like. And a mask removing process for removing the mask MS1. As a result, a removal portion is formed in the portion corresponding to the counter electrode CE1 for the capacitor of the organic semiconductor film 16 and its surrounding portion (FIG. 8b).
  • a low dielectric film forming step is performed to form a low dielectric film 17a having a lower dielectric constant than that of a ferroelectric film 17b described later (FIG. 8c.
  • a low dielectric film removal step is performed to remove the portion corresponding to the capacitor counter electrode CE1 (may include the vicinity thereof! /), Which is performed on the low dielectric film 17a.
  • a removal portion is formed in the portion of the low dielectric film 17a corresponding to the capacitor counter electrode CE1 (FIG. 8d).
  • a ferroelectric film forming step for forming the ferroelectric film 17b is performed (FIG. 8e). Thereafter, a transistor gate electrode is formed so that the transistor is configured in a predetermined positional relationship with the transistor source electrode So and the drain electrode Dr across the organic semiconductor film 16, the low dielectric film 17a, and the ferroelectric film 17b.
  • a second electrode group forming step is performed in which the capacitor counter electrode CE2 is formed in the same process corresponding to the capacitor counter electrode CE1 so as to constitute a capacitor with Ga and the ferroelectric film 17b interposed therebetween (FIG. 8f). ). After that, although not shown, a protective film is formed by performing a protective film forming step.
  • an organic composite electronic device including an organic thin film transistor Tr having the low dielectric film 17a and the ferroelectric film 17b as the gate insulating film 17 and a high dielectric capacitor Ca having the ferroelectric film 17b as the insulating film is manufactured.
  • the portion of the organic semiconductor film 16 in which the capacitor is formed is removed in the organic semiconductor film removing step.
  • the organic semiconductor film 16 may be formed except for the part where the capacitor is formed in the forming process.
  • the capacitor of the low dielectric film 17a is formed in the low dielectric film removal step.
  • the low dielectric film 17a may be formed by removing the portion where the capacitor is formed in the low dielectric film forming step.
  • the portion of the low dielectric film 17a corresponding to the capacitor counter electrode CE1 may be removed by removing only a portion of the thickness direction! / ,.
  • FIG. 9a to FIG. 9f are diagrams showing a manufacturing process of an organic composite electronic device including a transistor and a capacitor of a top gate coplanar type.
  • an organic semiconductor film forming step for forming the organic semiconductor film 16 on the substrate 11 is performed (FIG. 9a).
  • An undercoat layer (not shown) may be formed on the substrate 11 and the organic semiconductor film 16 may be formed on the undercoat layer.
  • an organic semiconductor film removing step is performed to remove the portion of the organic semiconductor film 16 corresponding to the capacitor counter electrode CE1 and the surrounding portion thereof.
  • This organic semiconductor film removal step includes a mask formation step (FIG.
  • a low dielectric film forming step for forming a low dielectric film 17a having a lower dielectric constant than that of a ferroelectric film 17b described later is performed (FIG. 9c).
  • a low dielectric film removal step is performed to remove a portion of the low dielectric film 17a corresponding to the counter electrode CE1 for the capacitor (including the vicinity thereof! /).
  • This low dielectric film removal process includes a mask formation process (FIG. 9c) for forming or placing a mask MS2 on the low dielectric film 17a, and an etching process for removing a portion corresponding to the capacitor counter electrode CE1 by etching or the like.
  • a removal portion is formed in the portion of the low dielectric film 17a corresponding to the capacitor counter electrode CE1 (FIG. 9d).
  • a ferroelectric film forming step for forming the ferroelectric film 17b is performed (FIG. 1).
  • the transistor source electrode So and drain are sandwiched between the low dielectric film 17a and the ferroelectric film 17b.
  • the transistor gate electrode Ga is configured so as to configure the transistor in a predetermined positional relationship with the transistor electrode Dr, and the capacitor corresponding to the capacitor counter electrode CE1 so as to configure the capacitor sandwiching the ferroelectric film 17b.
  • a second electrode group forming process is performed in which the counter electrode CE2 is formed in the same process (FIG. 9f).
  • a protective film is formed by performing a protective film forming step.
  • an organic composite electronic device including an organic thin film transistor Tr having a low dielectric film 17a and a ferroelectric film 17b as a gate insulating film 17 and a high dielectric capacitor Ca having a ferroelectric film 17b as an insulating film is manufactured. Is done.
  • the portion of the organic semiconductor film 16 in which the capacitor is formed is removed in the organic semiconductor film removing step.
  • the organic semiconductor film 16 may be formed excluding the portion where the capacitor is formed and the surrounding portion in the forming step.
  • the low dielectric film 17a removes the capacitor forming portion of the low dielectric film 17a.
  • the low dielectric film 17a may be formed except for the part where the capacitor is formed in the film forming process.
  • the portion of the low dielectric film 17a corresponding to the capacitor counter electrode CE1 may be removed by removing only a portion of the thickness in the thickness direction.
  • the material for forming the organic semiconductor film constituting the thin film transistor of the organic composite electronic device of the second embodiment, the method of forming (forming) the same, and the like are the same as those of the first embodiment described above.
  • the material for forming the gate electrode, the source electrode and the drain electrode constituting the thin film transistor of the organic composite electronic device of the second embodiment, and the pair of counter electrodes constituting the high dielectric capacitor, and the film formation (formation) method thereof are as follows: This is the same as the first embodiment described above.
  • a single-layer film having a ferroelectric film force is used as an insulating film for a capacitor.
  • the low dielectric film and the ferroelectric film are the same as the transistor. You can also use a two-layered film with body layers stacked! /.
  • the relative dielectric constant of the low dielectric film and the ferroelectric film, the forming material, the film formation (formation) method, and the like are the same as those in the first embodiment described above.
  • a uniform film is formed by using the spin coating method described above, and then a photoresist is formed thereon.
  • a method can be used in which a mask pattern is formed or a mask such as a metal mask is provided and unnecessary portions are removed by etching.
  • etching method either dry etching or wet etching may be used, but dry etching is preferable. Examples of dry etching methods include gas etching, ion etching, plasma etching, ICP (Inductively Coupled Plasma Inductive Coupling), radical ion etching (RIE), and the like.
  • a method of forming a film by removing the removal portion may be used.
  • a solution or a dispersion liquid of a low dielectric material may be formed only on a necessary portion by a direct ink jet method or the like, or after unnecessary portions are masked and formed using a printing method or the like, the mask is formed. You may make it remove.
  • the protective film and substrate forming material of the organic composite electronic device of the second embodiment, and the film forming (forming) method or manufacturing method thereof are the same as those of the first embodiment described above.
  • an undercoat layer containing a compound selected from a polymer or an inorganic oxide and an inorganic nitride may be provided on the substrate.
  • the material for forming the undercoat layer, the film formation (formation) method, and the like are the same as in the first embodiment described above.
  • the inorganic oxide contained in the undercoat layer includes titanium oxide, tin oxide, vanadium oxide, as well as the silicon oxide, aluminum oxide, and tantalum oxide exemplified in the first embodiment.
  • the organic composite electronic device manufactured as described above has a signal writing characteristic and a charge storing characteristic. Therefore, for example, it is suitable for manufacturing a memory, particularly a signal circuit for a wireless transmission tag. It can be used suitably.
  • a capacitor type organic semiconductor memory can be configured by arranging the organic composite electronic elements manufactured as described above in a matrix on a substrate.
  • FIG. 10 is a diagram showing a circuit of an organic semiconductor memory cell of 1T1C (1 transistor ⁇ 1 capacitor) type. The sense amplifier is not shown. Writing is performed by activating the WL (lead line) of the corresponding cell, turning on the FET (Tr), and applying a voltage between BL (bit line) and PL (plate line). .
  • BL Vcc PL is GND (OV)
  • the upper part of the capacitor Ca is + (plus) and the lower part is (minus) polarization, and "1" is written.
  • BL is GND PL and Vcc, the upper part of the capacitor is at the bottom.
  • the organic composite electronic device according to the present embodiment can be applied to a 2T2C (2-transistor / 2-capacitor) type high-dielectric memory cell in addition to such a 1T1C-type high-dielectric memory cell. .
  • FIGS. 11a to l lf are diagrams illustrating a manufacturing process of an organic composite electronic device including a bottom gate stagger type transistor.
  • a first electrode group forming step is performed in which the first transistor gate electrode Gal and the second transistor gate electrode Ga2 are formed on the substrate 11 in the same step (FIG. 11a).
  • An undercoat layer (not shown) may be formed on the substrate 11, and these electrodes GalGa2 may be formed on the undercoat layer.
  • the undercoat An insulating film forming step for forming an insulating film 17 on the layer is performed (FIG. 1 lb).
  • a ferroelectric film forming step for forming the ferroelectric film 17b, and a low dielectric film formation for forming the low dielectric film 17a having a low dielectric constant on the ferroelectric film 17b are performed.
  • a process is included.
  • a low dielectric film removal step is performed to remove a part of the low dielectric film 17a in order to form a later-described source / drain electrode in a predetermined positional relationship with the second transistor gate electrode Ga2.
  • This low dielectric film removal process includes a mask formation process (FIG. 11c) for forming or placing a mask MS on the low dielectric film 17a, and an etching process for removing a part of the low dielectric film 17a by etching or the like. A step and a mask removing step of removing the mask MS.
  • a transistor is configured in a predetermined positional relationship with the gate electrode Gal for the first transistor across the ferroelectric film 17b, the low dielectric film 17a, and the organic semiconductor film 16.
  • Source electrode Sol, drain electrode Drl, and second transistor source electrode so that the transistor is configured in a predetermined positional relationship with second transistor gate electrode Ga2 across ferroelectric film 17b and organic semiconductor film 16
  • a second electrode group forming process is performed in which So2 and drain electrode Dr2 are formed in the same process (FIG. 1, If).
  • a protective film is formed by performing a protective film forming step.
  • an organic composite electronic device including an organic thin film transistor Trl using the ferroelectric film 17b and the low dielectric film 17a as the gate insulating film 17 and an organic thin film transistor Tr2 using the ferroelectric film 17b as the gate insulating film is manufactured.
  • the portion of the low dielectric film 17a where the second transistor is formed (part of the low dielectric film 17a)
  • the low dielectric film 17a may be formed except for the portion where the second transistor is formed in the low dielectric film formation step.
  • a part of the low dielectric film 17a may be removed not only in the thickness direction.
  • FIGS. 12a to 12f are diagrams illustrating a manufacturing process of an organic composite electronic device including a bottom gate coplanar type transistor.
  • a first electrode group forming process is performed in which the first transistor gate electrode Gal and the second transistor gate electrode Ga2 are formed on the substrate 11 in the same process (FIG. 12a).
  • An undercoat layer (not shown) may be formed on the substrate 11, and these electrodes Gal and Ga2 may be formed on the undercoat layer.
  • an insulating film forming step is performed in which an insulating film 17 is formed on the substrate 11 including these electrodes Gal and Ga2 (on the undercoat layer when the undercoat layer is formed) (FIG. 12b).
  • the insulating film forming process includes a ferroelectric film forming process for forming the ferroelectric film 17b and a low dielectric film forming process for forming the low dielectric film 17a having a low dielectric constant on the ferroelectric film 17b. Is included
  • a low dielectric film removal step is performed to remove a part of the low dielectric film 17a in order to form a later-described source / drain electrode in a predetermined positional relationship with the second transistor gate electrode Ga2.
  • This low dielectric film removal process includes a mask formation process (FIG. 12c) for forming or placing a mask MS on the low dielectric film 17a, and an etching process for removing a part of the low dielectric film 17a by etching or the like.
  • a step and a mask removing step of removing the mask MS As a result, a removed portion of the low dielectric film 17a for forming a later-described source / drain electrode in a predetermined positional relationship with the second transistor gate electrode Ga2 is formed (FIG. 12d).
  • the first transistor source electrode Sol and the drain electrode are formed so as to form a transistor in a predetermined positional relationship with the first transistor gate electrode Gal across the ferroelectric film 17b and the low dielectric film 17a.
  • the second transistor source electrode So2 and the drain electrode Dr2 are formed in the same process so that the transistor is configured in a predetermined positional relationship with the second transistor gate electrode Ga2 across the Drl and the ferroelectric film 17b.
  • performing two electrodes forming step (Fig. 12e) 0
  • each electrode Sol, Drl, So2 performs the organic semiconductor film forming step of forming an organic semiconductor film 16 on the low dielectric film 17a containing Dr2 ( Figure 12f ).
  • a protective film is formed by performing a protective film forming step.
  • an organic composite electronic device including the organic thin film transistor Trl having the ferroelectric film 17b and the low dielectric film 17a as the gate insulating film 17 and the organic thin film transistor Tr2 having the ferroelectric film 17b as the gate insulating film is manufactured.
  • the low dielectric film 17a after forming the low dielectric film 17a in the low dielectric film formation step, the portion of the low dielectric film 17a where the second transistor is formed (part of the low dielectric film 17a)
  • the low dielectric film 17a may be formed except for the portion where the second transistor is formed in the low dielectric film formation step.
  • the low dielectric film removal step a part of the low dielectric film 17a may be removed not only in the thickness direction.
  • FIG. 13a to FIG. 13f are diagrams illustrating a manufacturing process of an organic composite electronic device including a top gate stagger type transistor.
  • a first electrode group forming process is performed in which the first transistor source electrode Sol, the drain electrode Drl, the second transistor source electrode So2, and the drain electrode Dr2 are formed on the substrate 11 in the same process (FIG. 13a).
  • An undercoat layer (not shown) may be formed on the substrate 11, and these electrodes Sol, Dr1, So2, and Dr2 may be formed on the undercoat layer.
  • the low dielectric film removal is performed to remove a part of the low dielectric film 17a in order to form the gate electrode described later in a predetermined positional relationship with the source electrode So2 and the drain electrode Dr2 for the second transistor. Perform the process.
  • This low dielectric film removal step includes a mask formation step (FIG. 13c) for forming or placing a mask MS on the low dielectric film 17a, and an etching for removing a part of the low dielectric film 17a by etching or the like. And a mask removing step for removing the mask MS.
  • a removal portion of the low dielectric film 17a for forming a gate electrode described later in a predetermined positional relationship with the source electrode So2 and the drain electrode Dr2 for the second transistor is formed (FIG. 13d).
  • a ferroelectric film forming step of forming a ferroelectric film 17b on the low dielectric film 17a including the removed portion is performed (FIG. 13e).
  • a transistor is configured in a predetermined positional relationship with the source electrode Sol and the drain electrode Drl for the first transistor across the organic semiconductor film 16, the low dielectric film 17a, and the ferroelectric film 17b.
  • First transistor gate electrode Gal, ferroelectric film 17b and organic semiconductor Second electrode group forming step in which the second transistor gate electrode Ga2 is formed in the same process so as to form a transistor with a predetermined positional relationship with the second transistor source electrode So2 and drain electrode Dr2 across the film 16.
  • a protective film is formed by performing a protective film forming step.
  • an organic composite electronic device including an organic thin film transistor Trl using the ferroelectric film 17b and the low dielectric film 17a as the gate insulating film 17 and an organic thin film transistor Tr2 using the ferroelectric film 17b as the gate insulating film is manufactured.
  • the portion of the low dielectric film 17a where the second transistor is formed (part of the low dielectric film 17a)
  • the low dielectric film 17a may be formed except for the portion where the second transistor is formed in the low dielectric film formation step.
  • a part of the low dielectric film 17a may be removed not only in the thickness direction.
  • FIG. 14a to FIG. 14f are diagrams illustrating a manufacturing process of an organic composite electronic device including a transistor of a top gate coplanar type.
  • the organic semiconductor film forming process for forming the organic semiconductor film 16 is performed on the substrate 11, and then the source electrode Sol for the first transistor, the drain electrode Drl, the source electrode So2 for the second transistor, the drain electrode Dr2
  • a first electrode group forming step is performed in which the steps are formed in the same step (FIG. 14a).
  • An undercoat layer (not shown) may be formed on the substrate 11 and the organic semiconductor film 16 may be formed on the undercoat layer.
  • a low dielectric film forming step for forming a low dielectric film 17a on the organic semiconductor film 16 containing these electrodes Sol, Drl, So2, and Dr2 is performed (FIG. 14b).
  • the low dielectric film removal is performed to remove a part of the low dielectric film 17a in order to form the gate electrode described later in a predetermined positional relationship with the source electrode So2 and the drain electrode Dr2 for the second transistor. Perform the process.
  • This low dielectric film removal process includes a mask formation process (FIG. 14c) for forming or placing a mask MS on the low dielectric film 17a, and an etching process for removing a part of the low dielectric film 17a by etching or the like. And a mask removing step for removing the mask MS.
  • the second transistor source electrode So2 and drain electrode Dr2 Due to the arrangement, a removed portion of the low dielectric film 17a for forming a gate electrode described later is formed (FIG. 14d). Thereafter, a ferroelectric film forming step of forming a ferroelectric film 17b on the low dielectric film 17a including the removed portion is performed (FIG. 14e).
  • the first transistor gate electrode is configured so that the transistor is configured in a predetermined positional relationship with the first transistor source electrode Sol and the drain electrode Drl with the low dielectric film 17a and the ferroelectric film 17b interposed therebetween.
  • the second transistor gate electrode Ga2 is formed in the same process so that the transistor is configured in a predetermined positional relationship with the source electrode So2 and drain electrode Dr2 of the second transistor across Gal and the ferroelectric film 17b.
  • the second electrode group forming step is performed (FIG. 14f). Then, although illustration is abbreviate
  • an organic composite electronic device including an organic thin film transistor Trl having the ferroelectric film 17b and the low dielectric film 17a as the gate insulating film 17 and an organic thin film transistor Tr2 having the ferroelectric film 17b as the gate insulating film is obtained. Manufactured.
  • the low dielectric film 17a after forming the low dielectric film 17a in the low dielectric film formation step, a portion of the low dielectric film 17a for forming the second transistor (a part of the low dielectric film 17a) is formed. Although removed, the low dielectric film 17a may be formed in the low dielectric film forming step except for the portion constituting the second transistor. In the low dielectric film removal step, a part of the low dielectric film 17a may be removed not only in the thickness direction.
  • the material for forming the organic semiconductor film constituting the organic thin film transistor of the organic composite electronic device of the third embodiment, the film formation (formation) method, and the like are the same as those in the first or second embodiment described above.
  • the material for forming the gate electrode, the source electrode and the drain electrode, and the method for forming (forming) the first and second organic thin film transistors constituting the first and second organic thin film transistors of the organic composite electronic device of the third embodiment are the same as those described in the first or second embodiment. It is the same as the form.
  • a gate insulating film for the first transistor As a gate insulating film for the first transistor, A two-layered film in which a low dielectric constant film having a low dielectric constant and a ferroelectric film are stacked is used, and a single layer film having a ferroelectric film force is used as a gate insulating film for the second transistor.
  • the relative dielectric constant, the forming material, the film forming (forming) method, and the like of the low dielectric film and the ferroelectric film are the same as those in the first or second embodiment described above.
  • a method for forming the low dielectric film when forming the removal portion described above the same method as described in the second embodiment may be used.
  • the material for forming the protective film and substrate of the organic composite electronic device of the third embodiment, the film forming (forming) method, the manufacturing method, and the like are the same as those in the first or second embodiment described above.
  • an undercoat layer containing a compound selected from a polymer or an inorganic oxide and an inorganic nitride may be provided on the substrate.
  • the material for forming the undercoat layer, the film formation (formation) method, and the like are the same as those in the first or second embodiment described above.
  • the second transistor of the organic composite electronic device manufactured as described above can be used as a 1T (1 transistor) type ferroelectric memory device, and the organic composite electronic device is arranged in a matrix on the substrate.
  • a ferroelectric memory FeRAM: Ferroelectric Random Access Memory
  • FIG. 15 is a diagram showing a circuit of an IT type ferroelectric memory element.
  • BL is a bit line
  • WL is a word line
  • Tr2 is a second organic thin film transistor.
  • the sense amplifier is not shown.
  • Examples of the present invention will be specifically described below.
  • the present invention was applied to manufacture an organic electronic device including a bottom-gate staggered organic thin film transistor (TFT) as shown in FIG. 2a.
  • bottom gate staggered organic thin film as shown in Figure 6f
  • An organic composite electronic device with a transistor (Tr) and a high dielectric capacitor (Ca) was manufactured.
  • an organic composite electronic device having two bottom gate / stagger type organic thin film transistors (Trl, Tr2) as shown in FIG. 1 If was manufactured.
  • a polyethylene terephthalate film substrate 25 mm x 10 mm x O. 5 mm in size
  • the gate electrode (and capacitor electrode) was formed by vapor-depositing aluminum on the substrate.
  • the aluminum was deposited so that the degree of vacuum was less than 1 ⁇ 10-2 Pa, the substrate temperature was RT (room temperature), and the film thickness was about 200 nm.
  • the ferroelectric film which is the first layer of the insulating film having a two-layer structure, is prepared by dissolving cyanoethylated cellulose (manufactured by Shin-Etsu Chemical Co., Ltd .: Cyanoresin CR—S (trade name)) in cyclopentanone Solutions with a concentration of 3-7% by weight were produced. This solution was formed by applying the spin coat method at a rotational speed of 3000 rpm for 30 seconds and drying at 100 ° C. for 2 minutes. This ferroelectric film had a thickness of about 300 nm and a relative dielectric constant of 17.
  • the low dielectric film which is the second layer of the insulating film is a 5% cyclohexane solution of alicyclic olefin polymer (manufactured by Nippon Zeon Co., Ltd .: ZEONEX (registered trademark) 480R) at a rotational speed of 5000 rpm. It was formed by applying for 30 seconds using a spin coating method and drying at 60 ° C. for 2 minutes. The thickness of this low dielectric film was about 300 nm and the relative dielectric constant was 2.2.
  • the organic semiconductor film was formed by vapor-depositing pentacene on the insulating film. Pentacene deposition is performed so that the degree of vacuum is less than 2 X 10-3 Pa, the substrate temperature is RT (room temperature), the deposition temperature is 185 ° C, the deposition rate is 0.06 nm / s, and the film thickness is about 50 nm. It was.
  • Fig. 16 is a VD ID fountain diagram when VD is changed between + 10V and 30V with VG kept constant
  • Fig. 17 shows VG with + 10V when VD is kept constant (30V). Change between 30V It is a VG-ID diagram when it is made to be.
  • the organic transistor (Tr, Trl) in which the two-layer insulating film of the ferroelectric film and the low dielectric film of this example is used as a gate insulating film can be operated at a low V and a driving voltage. It can be seen that it has good characteristics with very little hysteresis.
  • the second transistor (Tr2) of the organic composite electronic device having two transistors manufactured as described above that is, an organic thin film transistor (organic TFT) having a single-layer ferroelectric film as a gate insulating film.
  • organic TFT organic thin film transistor
  • the electrical characteristics were evaluated by measuring the current-voltage curve, and the results are shown in Fig.18. It can be seen that the second transistor (Tr2) can be operated with a low driving voltage and has a large hysteresis, so that it is suitable for use in a ferroelectric memory.

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Abstract

La présente invention concerne un transistor à film fin organique accompagné d'une électrode grille (18), d'un film d'isolation de grille (17), d'un film semi-conducteur organique (16), d'une électrode drain (14) et d'une électrode source (15) sur un substrat (11). Le film d'isolation de grille (17) comporte une structure à double couche d'un film à constante diélectrique faible (17a) et un film ferroélectrique (17b). Le film à constante diélectrique faible (17a) est placé entre le film ferroélectrique (17b) et le film semi-conducteur organique (16) et le film à constante diélectrique faible (17a) comprend un composé polymère organique qui n'a pas de groupe fonctionnel à paire d'électrons non partagée ni de couplage d'électron π au sein de la structure moléculaire.
PCT/JP2007/072424 2006-11-27 2007-11-20 Transistor à film fin organique, élément électronique composite organique, procédé de fabrication d'un tel transistor et d'un tel élément, écran d'affichage et mémoire WO2008065927A1 (fr)

Applications Claiming Priority (6)

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JP2006319186A JP2010034092A (ja) 2006-11-27 2006-11-27 有機複合電子素子及びその製造方法、及び該有機複合電子素子を用いる強誘電体メモリ
JP2006-319184 2006-11-27
JP2006-319186 2006-11-27
JP2006319184A JP2010034090A (ja) 2006-11-27 2006-11-27 有機薄膜トランジスタ、ゲート絶縁膜、有機薄膜トランジスタの製造方法、及び表示装置
JP2006-319185 2006-11-27
JP2006319185A JP2010034091A (ja) 2006-11-27 2006-11-27 有機複合電子素子及びその製造方法、及び該有機複合電子素子を用いる有機半導体メモリ

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JP2011049537A (ja) * 2009-08-25 2011-03-10 Korea Electronics Telecommun 不揮発性メモリセル及びその製造方法
JP2011517504A (ja) * 2008-03-20 2011-06-09 ファクルダージ デ シエンシアス イ テクノロジア ダ ユニベルシダデ ノバ デ リスボア 能動半導体酸化物を用いるメモリを備える自立可能な接合電界効果型トランジスタにおける物理的支持体及び電荷蓄積媒体としての、天然セルロース系繊維、合成セルロース系繊維、又はそれらの組合せの使用及び製造方法
WO2013000501A1 (fr) * 2011-06-27 2013-01-03 Thin Film Electronics Asa Réduction de court-circuit dans une cellule de mémoire ferroélectrique comprenant une pile de couches disposées sur un substrat flexible
WO2013000825A1 (fr) * 2011-06-27 2013-01-03 Thin Film Electronics Asa Réduction de court-circuit dans un composant électronique comprenant une pile de couches disposées sur un substrat flexible
US9018704B2 (en) 2011-10-20 2015-04-28 Panasonic Corporation Thin-film transistor and method of manufacturing the same
JP2018011074A (ja) * 2011-01-26 2018-01-18 株式会社半導体エネルギー研究所 半導体装置

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TWI500160B (zh) * 2008-08-08 2015-09-11 Semiconductor Energy Lab 半導體裝置及其製造方法
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JP2011049537A (ja) * 2009-08-25 2011-03-10 Korea Electronics Telecommun 不揮発性メモリセル及びその製造方法
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US10497419B2 (en) 2011-01-26 2019-12-03 Semiconductor Energy Laboratory Co., Ltd. Memory device and semiconductor device
JP2018011074A (ja) * 2011-01-26 2018-01-18 株式会社半導体エネルギー研究所 半導体装置
CN103650046A (zh) * 2011-06-27 2014-03-19 薄膜电子有限公司 包括布置在柔性衬底上的堆叠层的铁电存储单元中的短路减少
CN103620681A (zh) * 2011-06-27 2014-03-05 薄膜电子有限公司 包括布置在柔性衬底上的堆叠层的电子部件中的短路减少
US9412705B2 (en) 2011-06-27 2016-08-09 Thin Film Electronics Asa Short circuit reduction in a ferroelectric memory cell comprising a stack of layers arranged on a flexible substrate
CN103620681B (zh) * 2011-06-27 2016-11-02 薄膜电子有限公司 具有横向尺寸改变吸收缓冲层的电子部件及其生产方法
WO2013000825A1 (fr) * 2011-06-27 2013-01-03 Thin Film Electronics Asa Réduction de court-circuit dans un composant électronique comprenant une pile de couches disposées sur un substrat flexible
US9934836B2 (en) 2011-06-27 2018-04-03 Thin Film Electronics Asa Short circuit reduction in an electronic component comprising a stack of layers arranged on a flexible substrate
US10453853B2 (en) 2011-06-27 2019-10-22 Thin Film Electronics Asa Short circuit reduction in a ferroelectric memory cell comprising a stack of layers arranged on a flexible substrate
WO2013000501A1 (fr) * 2011-06-27 2013-01-03 Thin Film Electronics Asa Réduction de court-circuit dans une cellule de mémoire ferroélectrique comprenant une pile de couches disposées sur un substrat flexible
US9018704B2 (en) 2011-10-20 2015-04-28 Panasonic Corporation Thin-film transistor and method of manufacturing the same

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