WO2014006700A1 - Procédé de production de film mince organique - Google Patents

Procédé de production de film mince organique Download PDF

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WO2014006700A1
WO2014006700A1 PCT/JP2012/067074 JP2012067074W WO2014006700A1 WO 2014006700 A1 WO2014006700 A1 WO 2014006700A1 JP 2012067074 W JP2012067074 W JP 2012067074W WO 2014006700 A1 WO2014006700 A1 WO 2014006700A1
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organic
thin film
substrate
molecule
molecules
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Japanese (ja)
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哲二 伊藤
青森　繁
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シャープ株式会社
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/008—Dyes containing a substituent, which contains a silicium atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
    • 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 a potential-jump barrier or a surface barrier
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/464—Lateral top-gate IGFETs comprising only a single gate
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/466—Lateral bottom-gate IGFETs comprising only a single gate
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/311—Phthalocyanine
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/623—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing five rings, e.g. pentacene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to an organic thin film and a manufacturing method thereof, and a field effect transistor, an organic light emitting element, a solar cell, a display device array, and a display device using the organic thin film.
  • a general organic thin film transistor has a structure in which an insulator layer is provided on a gate electrode, and a layer made of an organic semiconductor thin film is provided on the insulator layer.
  • an organic thin film transistor is taken as an example, but the organic thin film is widely applied to various devices regardless of whether it is a semiconductor, and is extremely important in industry.
  • an organic single crystal has almost no defects in orientation and is ideal as an organic electronic device, but it is extremely difficult to create a single crystal of a desired size and place it on the device. Only a small portion of organic semiconductor materials can be realized.
  • an organic thin film is produced by a dry process such as a vacuum deposition method, or a wet process such as a spin coating method or a printing method.
  • organic molecules aggregate in various forms. It is not easy to control the molecular orientation so that an organic thin film can be obtained. This is because organic molecules such as those used for thin film formation are mainly van der Waals forces and relatively weak forces, so organic molecules are strongly influenced by the interaction with the substrate. One reason.
  • SAM film As a method for arranging organic molecules, a method using a technique of a self-assembled monomolecular film (hereinafter abbreviated as SAM film) can be exemplified.
  • the SAM film is a monomolecular film in which organic molecules are integrated in a self-aligned and orderly manner.
  • the SAM film and the film (base material) adjacent to the SAM film are connected by a chemical bond.
  • a SAM film made of a long-chain alkyl group is generally used as a surface modifier for improving wettability in a gate insulating film of a transistor and reducing contact resistance in an electrode.
  • a SAM film containing organic semiconductor molecules can be easily produced in a wide area by a normal solution process, and the substrate and the organic semiconductor molecules can be connected by a strong chemical bond, so that application to flexible devices is expected. Is done. For example, so far, a SAM film has been formed on a substrate using oligothiophene having a silane coupling site, and a transistor device including the SAM film exhibits a mobility of 0.04 cm 2 / (Vs). (See Non-Patent Document 1).
  • Non-Patent Document 1 shows a mobility that is an order of magnitude smaller than this.
  • the main cause is that in the SAM film, which is the active layer of the transistor, the organic molecule molecules have an optimal periodicity of molecular arrangement that can fully exhibit their characteristics, and the organic semiconductor molecules are actually connected to the substrate. It is conceivable that the periodicity of the molecular arrangement is inconsistent (mismatching).
  • An organic semiconductor molecule is usually connected to a substrate via a coupling agent. In this case, the periodicity of the molecular arrangement is determined by the coupling site. This mismatching will be described more specifically with reference to FIG.
  • an organic molecule 63 is connected to a substrate 60 via a silane coupling site 63a to form an organic thin film 6 ′ that is a monomolecular film.
  • the organic molecules 63 are indicated by rectangles.
  • the silane coupling site 63a, the distance L a between adjacent silicon atoms (Si), the distance between the organic adjacent molecules 63 is determined and the period of the molecular arrangement becomes L b.
  • substantially L a and L b are approximately equal, the value is known to be about 4.3 ⁇ (angstroms) (see "An Introduction to Ulutrahin Organic Film, 257 , Academic press 1991 ”) .
  • the distance between molecules considered to have the maximum intermolecular interaction between the adjacent organic molecules 63 is theoretically a fan of the ⁇ -electron conjugated molecule. It is about 3.4 which is the sum of the Delwarus radii.
  • the organic molecule 63 is the above-mentioned oligothiophene, it is about 3.6 ⁇ considering that a sulfur atom having a large van der Waals radius is included. Only.
  • the period L b (about 4.3 cm) of the molecular arrangement of the organic molecules 63 is an intermolecular distance (about 3.4 to 3) at which the intermolecular interaction is maximized. .6 ⁇ ), the intermolecular interaction between the adjacent organic molecules 63 becomes insufficient, and it is considered that the organic thin film 6 ′ cannot exhibit a desired function.
  • the organic molecule that exhibits intermolecular interaction other than the ⁇ - ⁇ interaction has the same problem.
  • the present invention has been made in view of the above circumstances, and provides an organic thin film having a sufficient function with controlled orientation of organic molecules, a method for producing the same, and an organic electronic device and a display device using the organic thin film
  • the task is to do.
  • a first aspect of the present invention is a method for producing an organic thin film provided on a base material, wherein the first organic molecules are stood up on the base material by being chemically bonded and scattered.
  • the second organic molecule may be arranged by intermolecular interaction with respect to the first organic molecule.
  • the first and second organic molecules may have a ⁇ -electron conjugated system.
  • the solution in which the first organic molecule is dissolved may be brought into contact with the base material to chemically bond the first organic molecule on the base material.
  • the density of the first organic molecule chemically bonded on the substrate may be adjusted by the concentration of the solution in which the first organic molecule is dissolved. .
  • the density of the first organic molecules chemically bonded on the substrate by the contact time between the solution in which the first organic molecules are dissolved and the substrate. May be adjusted.
  • the second organic molecule may be introduced onto the substrate by applying a solution in which the second organic molecule is dissolved.
  • the second organic molecule may be deposited on the substrate by vapor deposition.
  • the substrate may have a hydrophilic group
  • the first organic molecule may be an organosilicon compound represented by the following general formula (I).
  • R is an organic group having a ⁇ -electron conjugated system
  • X 1 , X 2 and X 3 are each independently a reaction between a silicon atom (Si) to which they are bonded and the hydrophilic group. It is a group to leave with.
  • a second aspect of the present invention is an organic thin film provided on a base material, wherein the first organic molecules are erected and scattered by chemical bonds on the base material, An organic thin film in which organic molecules are arranged with respect to the first organic molecules.
  • the second organic molecule may be arranged by intermolecular interaction with respect to the first organic molecule.
  • the first and second organic molecules may have a ⁇ -electron conjugated system.
  • the first organic molecule may be chemically bonded onto the substrate by contact between the solution containing the first organic molecule and the substrate.
  • the density of the first organic molecule chemically bonded on the substrate may be adjusted by the concentration of the solution containing the first organic molecule.
  • the density of the first organic molecule chemically bonded on the substrate is determined by the contact time between the solution containing the first organic molecule and the substrate. It may be adjusted.
  • the second organic molecule may be introduced and arranged on the substrate by applying a solution containing the second organic molecule.
  • the second organic molecules may be introduced and arranged on the substrate by vapor deposition.
  • the base material may have a hydrophilic group
  • the first organic molecule may be an organosilicon compound represented by the following general formula (I).
  • R is an organic group having a ⁇ -electron conjugated system
  • X 1 , X 2 and X 3 are each independently a reaction between a silicon atom (Si) to which they are bonded and the hydrophilic group. It is a group to leave with.
  • a third aspect of the present invention is a field effect transistor including an organic semiconductor layer, wherein a first organic molecule is erected and dotted by a chemical bond on a substrate, and a second organic A field effect transistor comprising an organic thin film in which molecules are arranged with respect to the first organic molecule, wherein the first and second organic molecules are organic semiconductor molecules, as the organic semiconductor layer. is there.
  • a gate electrode, a gate insulating film, a source electrode, a drain electrode, and an organic semiconductor layer are provided, and the organic semiconductor layer faces the gate electrode through the gate insulating film.
  • the source electrode and the drain electrode may be provided in contact with the organic semiconductor layer.
  • a gate electrode, a gate insulating film, a source electrode, a drain electrode, and an organic semiconductor layer are provided, and the organic semiconductor layer faces the gate electrode through the gate insulating film.
  • the source electrode and the drain electrode may be provided on the gate insulating film.
  • a fourth aspect of the present invention is an organic light emitting device comprising a pair of electrodes on a base material, and having at least a carrier transport layer and a light emitting layer between the pair of electrodes, In the organic thin film in which the first organic molecules are erected and scattered by chemical bonds, and the second organic molecules are arranged with respect to the first organic molecules, the first and second organic molecules
  • the organic light-emitting device includes an organic thin film whose molecule is an organic semiconductor molecule as the carrier transport layer.
  • a fifth aspect of the present invention is a solar cell including a pair of electrodes on a base material, and a p-type semiconductor layer and an n-type semiconductor layer between the pair of electrodes. Further, in the organic thin film in which the first organic molecules are erected and scattered by chemical bonds, and the second organic molecules are arranged with respect to the first organic molecules, the first and second A solar cell comprising an organic thin film whose organic molecules are organic semiconductor molecules as the p-type semiconductor layer and / or the n-type semiconductor layer.
  • the first organic molecule is erected and scattered by chemical bonds on the substrate, and the second organic molecule is arranged with respect to the first organic molecule.
  • an array for a display device comprising a field effect transistor having, as the organic semiconductor layer, an organic thin film in which the first and second organic molecules are organic semiconductor molecules.
  • an image signal output unit that generates and outputs an image signal
  • a drive unit that generates a current or voltage based on the image signal
  • light emission by the generated current or voltage A light emitting unit, wherein the light emitting unit is erected and interspersed by chemical bonds on the substrate, and the second organic molecule is the first organic molecule.
  • An organic light-emitting device comprising an organic thin film in which the first and second organic molecules are organic semiconductor molecules as the carrier transport layer in an organic thin film arranged with respect to one organic molecule.
  • an organic thin film having a sufficient function by controlling the orientation of organic molecules, a manufacturing method thereof, and an organic electronic device and a display device using the organic thin film.
  • FIG. 6 is a first schematic cross-sectional view for explaining the method of manufacturing the field effect transistor shown in FIG. 5.
  • FIG. 6 is a second schematic cross-sectional view for illustrating the method for manufacturing the field effect transistor shown in FIG. 5.
  • FIG. 6 is a third schematic cross-sectional view for illustrating the method for manufacturing the field effect transistor shown in FIG. 5.
  • FIG. 6 is a fourth schematic cross-sectional view for illustrating the method for manufacturing the field effect transistor shown in FIG. 5.
  • FIG. 7 is a first schematic cross-sectional view for explaining the method of manufacturing the field effect transistor shown in FIG. 6.
  • FIG. 7 is a second schematic cross-sectional view for illustrating the method for manufacturing the field effect transistor shown in FIG. 6.
  • FIG. 7 is a third schematic cross-sectional view for illustrating the method for manufacturing the field effect transistor shown in FIG. 6.
  • FIG. 7 is a fourth schematic cross-sectional view for illustrating the method for manufacturing the field effect transistor shown in FIG. 6.
  • FIG. 7 is a fifth schematic cross-sectional view for illustrating the method for manufacturing the field effect transistor shown in FIG. 6.
  • It is a schematic sectional drawing which illustrates the principal part of the solar cell concerning this invention. It is a 1st schematic sectional drawing for demonstrating the manufacturing method of the solar cell shown in FIG.
  • FIG. 12 is a second schematic cross sectional view for illustrating the method for manufacturing the solar cell shown in FIG. 11.
  • FIG. 12 is a third schematic cross-sectional view for illustrating the method for manufacturing the solar cell shown in FIG. 11.
  • FIG. 12 is a fourth schematic cross-sectional view for illustrating the method for manufacturing the solar cell shown in FIG. 11.
  • FIG. 14 is a first schematic cross-sectional view for explaining the method for manufacturing the organic light-emitting element shown in FIG. 13.
  • FIG. 14 is a second schematic cross-sectional view for explaining the method for manufacturing the organic light-emitting element shown in FIG. 13.
  • FIG. 14 is a third schematic cross-sectional view for explaining the method for manufacturing the organic light-emitting element shown in FIG. 13. It is a 4th schematic sectional drawing for demonstrating the manufacturing method of the organic light emitting element shown in FIG. It is a 5th schematic sectional drawing for demonstrating the manufacturing method of the organic light emitting element shown in FIG. FIG.
  • FIG. 14 is a sixth schematic cross-sectional view for explaining the method for manufacturing the organic light-emitting element shown in FIG. 13. It is a 7th schematic sectional drawing for demonstrating the manufacturing method of the organic light emitting element shown in FIG. It is a top view which illustrates the principal part of the array for display apparatuses which concerns on this invention.
  • FIG. 3 is an enlarged plan view illustrating the main part of the array for display devices according to the present invention.
  • FIG. 16B is a diagram illustrating the main part of the array for display devices according to the present invention, which is a cross-sectional view taken along the line CC of FIG. 15B.
  • 16B is a diagram illustrating the main part of the array for display devices according to the present invention, and a cross-sectional view taken along the line DD in FIG. 15B. It is a 1st schematic sectional drawing for demonstrating the manufacturing method of the organic-semiconductor device in the array for display apparatuses which concerns on this invention. It is a 2nd schematic sectional drawing for demonstrating the manufacturing method of the organic-semiconductor device in the array for display apparatuses which concerns on this invention. It is a 3rd schematic sectional drawing for demonstrating the manufacturing method of the organic-semiconductor device in the array for display apparatuses which concerns on this invention.
  • the method for producing an organic thin film according to the present invention is a method for producing an organic thin film provided on a base material, wherein the first organic molecules are chemically bonded to the base material, and are disposed and scattered.
  • spotting step a second organic molecule is introduced onto the base material, and the second organic molecule is arranged with respect to the first organic molecule to form a thin film.
  • film formation step a step of forming
  • FIGS. 2A and 2B are schematic views for explaining a method for producing an organic thin film according to the present invention.
  • the first organic molecules 61 are stood up on the base material 60 by being chemically bonded and interspersed.
  • the first organic molecules 61 do not form a thin film.
  • the first organic molecule 61 is shown as a rectangle, and the binding site between the first organic molecule 61 and the substrate 60 is shown as a triangle for easy understanding.
  • the base material 60 can be arbitrarily selected according to the use of the organic thin film.
  • the base material 60 may be appropriately selected in consideration of the material of the thin film, the configuration and performance of the device, and the specific materials include silicon single crystal, polycrystalline Elemental semiconductors such as silicon, amorphous silicon and germanium (Ge); compound semiconductors such as gallium arsenide (GaAs), indium gallium arsenide (InGaAs) and zinc selenide (ZnSe); glass such as quartz glass; polyimide, polyethylene terephthalate (PET) ), Polyethylene naphthalate (PEN), polyethersulfone (PES), insulating polymer compounds such as polytetrafluoroethylene.
  • a thin film may be used as the base material 60 as long as the first organic molecules 61 can be bonded. That is, the first organic molecule 61 can be bonded to form a thin film having a two-layer structure.
  • the base material 60 may have a metal oxide film such as silicon oxide (SiO 2 ), aluminum oxide (Al 2 O 3 ), indium tin oxide (ITO), zinc oxide (ZnO) formed on the surface thereof.
  • Preferred substrates 60 include a hydroxyl group (—OH), a carboxyl group (—C ( ⁇ O) —OH), an amino group (—NH 2 ), a hydroxylamino group (—NHOH), and an imino group ( ⁇ NH). Examples thereof include those subjected to hydrophilic treatment in which hydrophilic groups having active hydrogen such as thiol groups (—SH) are exposed on the surface.
  • the hydrophilic treatment can be performed, for example, by immersing an untreated substrate in a solution containing hydrogen peroxide and concentrated sulfuric acid. Further, the substrate on which the metal oxide film is formed can be performed by UV ozone treatment, oxidation plasma treatment, or the like.
  • the base material 60 may be either a single layer structure or a multi-layer structure, and in the case of a multi-layer structure, the number of layers is not particularly limited, and all may be the same material, or all may be different materials. Different parts may be used.
  • the substrate 60 is preferably in the form of a film or a plate, and the thickness may be appropriately selected depending on the purpose, but is preferably 0.1 to 3 mm.
  • the first organic molecule 61 is not particularly limited as long as the second organic molecule 62 described later is arranged and chemically bonded to the surface of the substrate 60. Those that exhibit an intermolecular interaction are preferred. Examples of intermolecular interactions include ⁇ - ⁇ interaction, van der Waals force interaction, hydrogen bond interaction, Coulomb force interaction (charge-charge interaction), charge transfer interaction, etc. it can.
  • a semiconductor molecule is also preferable.
  • the first organic molecule 61 preferably has a binding site with the substrate 60 at or near the end of the molecule, and preferably has a single binding site with the substrate 60.
  • the first organic molecule 61 is preferably an organosilicon compound, and more preferably one that forms a siloxane bond (—Si—O—) and bonds with the substrate 60.
  • FIG. 3 is a schematic view illustrating a state in which the first organic molecule 61 is bonded to the base material 60 by forming a siloxane bond (—Si—O—).
  • a substrate 60 having a silicon oxide (SiO 2 ) film formed on the surface is shown, and a hydroxyl group (—OH) is partially exposed to make it hydrophilic.
  • the 1st organic molecule 61 reacts with the hydroxyl group on the base material 60 in the silicon atom in the structure, forms a siloxane bond, and forms the silane coupling site
  • One silicon atom in the silane coupling site 61 a is derived from the first organic molecule 61, and three oxygen atoms in the silane coupling site 61 a are derived from the base material 60.
  • it is considered that the three oxygen atoms in the silane coupling portion 61 a are bonded to the silicon atoms of the base material 60 in a tripod shape on the base material 60.
  • the effect of the first organic molecules 61 extending and bonding the molecular chains in a direction substantially perpendicular to the surface of the substrate 60 is promoted.
  • bonding changes a part of 1st organic molecule by couple
  • the first organic molecule 61 is preferably an organosilicon compound represented by the following general formula (I) (hereinafter abbreviated as organosilicon compound (I)).
  • R is an organic group having a ⁇ -electron conjugated system
  • X 1 , X 2 and X 3 are each independently a reaction between a silicon atom (Si) to which they are bonded and the hydrophilic group. It is a group to leave with.
  • R is an organic group having a ⁇ -electron conjugated system, and a group capable of forming a ⁇ - ⁇ stacking structure with a second organic molecule described later by an intermolecular interaction ( ⁇ - ⁇ interaction). It is.
  • the organic group is not particularly limited as long as it has a ⁇ electron conjugated system, and examples thereof include groups having various aromatic groups.
  • the aromatic group may be monocyclic or polycyclic, and may be either an aromatic hydrocarbon group or an aromatic heterocyclic group.
  • the aromatic hydrocarbon group include benzene (C 6 H 6 ), naphthalene (C 10 H 8 ), anthracene (C 14 H 10 ), tetracene (C 18 H 12 ), pyrene (C 16 H 10 ), pentacene.
  • examples thereof include groups in which one or more hydrogen atoms have been removed from monocyclic or polycyclic aromatic hydrocarbons such as (C 22 H 14 ) and coronene (C 24 H 12 ). The number of hydrogen atoms removed is determined according to the position or number of the aromatic hydrocarbon group in R, and is not particularly limited.
  • the aromatic heterocyclic group is not particularly limited as long as it has a hetero atom as an atom constituting the aromatic ring, and examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom, and a selenium atom. it can. More specifically, examples of the aromatic heterocyclic group include groups in which one or more hydrogen atoms have been removed from a monocyclic or polycyclic aromatic heterocyclic compound. Preferred examples of the aromatic heterocyclic compound include Examples include thiophene and phthalocyanine metal complexes. Here, a transition metal can be illustrated as a metal which comprises a complex. The number of hydrogen atoms removed is determined according to the position or number of the aromatic heterocyclic group in R and is not particularly limited.
  • the organic group may be composed only of an aromatic group, or may have a group other than an aromatic group such as an aliphatic group, an atom, or an ion.
  • preferable atoms and ions include metal atoms and metal ions.
  • the number of aromatic groups that the organic group has is not particularly limited. For example, when the aromatic group is monocyclic, it is preferably a plurality, more preferably 3 or more, and practicality is also considered. Then, it is preferably 3-6. When the organic group has a plurality of aromatic groups, these aromatic groups may be directly bonded to each other or indirectly bonded via a linking group, directly What was combined and what was indirectly combined may be mixed.
  • Preferred structures having a plurality of monocyclic aromatic groups include oligothiophene or polythiophene in which a plurality of thiophenes are directly bonded to each other, oligophenylene or polyphenylene in which a plurality of benzenes are directly bonded to each other, and a plurality of benzenes.
  • a structure in which one or more hydrogen atoms are removed from oligovinylene phenylene or polyvinylene phenylene bonded to each other via a vinylene group (—C ⁇ C—) can be exemplified.
  • X 1 , X 2 and X 3 are each independently a group which is released by a reaction between a silicon atom (Si) to which these are bonded and a hydrophilic group. That is, when the silicon atom in the organosilicon compound (I) reacts with the hydrophilic group of the substrate, it is a leaving group that breaks the bond with the silicon atom, and is a hydrolyzable group. preferable.
  • Preferred examples of X 1 to X 3 include a halogen atom and an alkoxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the alkoxy group is preferably a lower alkoxy group, can be exemplified by an alkoxy group having 1 to 5 carbon atoms, more preferably has 1 to 3 carbon atoms, and can be exemplified by a methoxy group, an ethoxy group, and a propoxy group.
  • organosilicon compound (I) examples include those represented by the following general formula.
  • X 1 , X 2 and X 3 are each independently a group which is released by the reaction of a silicon atom (Si) to which they are bonded and the hydrophilic group; M is a transition metal atom; is there.)
  • X 1, X 2 and X 3 are the same as X 1, X 2 and X 3 in the general formula (I).
  • M is a transition metal atom, and a copper atom is preferable.
  • the organosilicon compound (I) exemplified above usually exhibits properties as a p-type semiconductor, but one or more hydrogen atoms constituting the aromatic ring of these compounds are substituted with fluorine atom, chlorine atom, trifluoromethyl. Substitution with an electron withdrawing group such as a group (—CF 3 ) or a cyano group (—C ⁇ N) can also be used as an n-type organic semiconductor.
  • the first organic molecule 61 may be one kind or two or more kinds. When there are two or more kinds, the combination and the ratio thereof are not particularly limited, but in order to improve the orientation of the organic thin film, it is one kind. Preferably there is.
  • the first organic molecule 61 can be chemically bonded onto the substrate 60 by contacting with the substrate 60, but preferably a liquid containing the first organic molecule 61, more preferably the first organic molecule. A solution in which the molecules 61 are dissolved may be brought into contact with the substrate 60.
  • the first organic molecules 61 bonded to the base material 60 exist on the base material 60 in a state of standing up so as to extend the molecular chain upward. And when the surface of the base material 60 is hydrophilized, it is thought that this state is more easily taken. Most preferably, the first organic molecules 61 extend in a direction substantially perpendicular to the surface of the substrate 60.
  • the first organic molecule 61 When the first organic molecule 61 has a hydrolyzable group such as the organosilicon compound (I), the first organic molecule 61 is hydrolyzed in the presence of water to cause a self-condensation reaction. Sometimes. Therefore, when such a liquid containing the first organic molecule 61 is used, it is preferable to use an anhydrous solvent component or to reduce the concentration of the first organic molecule 61. It is more preferable to satisfy.
  • a hydrolyzable group such as the organosilicon compound (I)
  • the first organic molecules 61 can be interspersed by bringing them into contact with the base material 60 at a predetermined distance so as not to approach each other too much on the base material 60.
  • the density of the first organic molecules 61 on the base material 60 (the degree of the scattering).
  • the density can be easily adjusted by, for example, the concentration of the first organic molecule 61 in the liquid or the contact time between the liquid and the substrate 60. Specifically, the density can be reduced by reducing the concentration, and the density can be reduced by shortening the contact time.
  • ⁇ WF ⁇ d / 2 ⁇ 0 (1) (Where d is the molecular density on the substrate; ⁇ is the dipole moment the molecule has; ⁇ WF is the amount of change in the work function of the substrate surface due to the dipole moment ⁇ ; ⁇ 0 is in vacuum Dielectric constant.)
  • WF 0 the work function of the material itself constituting the substrate surface
  • WF WF 0 + ⁇ WF (2) (Where WF is the work function of the substrate surface to which the molecules are bonded; WF 0 is the work function of the material itself constituting the substrate surface; ⁇ WF is the work function of the substrate surface due to the dipole moment ⁇ )
  • WF 0 is a constant, and ⁇ WF is proportional to the molecular density d on the substrate. Therefore, by evaluating the change in the work function WF, the change in the molecular density d on the substrate is calculated. Can be evaluated.
  • reaction rate equation between the substrate and the first organic molecule can be expressed by the concentration of the first organic molecule in the liquid and the treatment time (reaction time, contact time). Therefore, when the reaction rate equation is incorporated into ⁇ WF of the equation (2), the following equation (3) is obtained.
  • WF WF 0 + WF sat ⁇ 1-exp ( ⁇ k ⁇ t ⁇ Z 1 ) ⁇ (3)
  • WF sat is the saturated work function in the high concentration region or long time treatment
  • t is the treatment time
  • k is the reaction rate constant
  • Z 1 is the concentration of the first organic molecule
  • WF and WF 0 are the same as above.
  • WF 0 is the same as described above, but can be rephrased as a work function when the concentration is zero.
  • K is a reaction rate constant, which is a value determined by the first organic molecule and the type (material) of the substrate.
  • Z 1 is the concentration of the first organic molecule in the liquid.
  • FIG. 4 is a graph illustrating the relationship between the concentration of the first organic molecule and the work function when the processing time is constant (1 minute).
  • the unit “ ⁇ M” indicates “ ⁇ mol / L”. Note that the graph of FIG. 4 is merely an example, and the relationship between the concentration of the first organic molecule and the work function is not limited to this. This graph shows that the work function can be adjusted by adjusting the concentration of the first organic molecule, and thus the molecular density of the substrate surface correlated with the work function can also be adjusted.
  • a concentration region in which the change in work function is small should be selected from the graph of FIG. From this graph, for example, a range of 1 ⁇ 10 ⁇ 4 to 1 ⁇ 10 ⁇ 2 ⁇ mol / L can be selected as a preferred concentration of the first organic molecule.
  • the concentration of the first organic molecule is constant (1 ⁇ 10 ⁇ 4 ⁇ mol / L), and the relationship between the processing time and the work function can be obtained, From the graph at this time, 1 to 100 minutes can be selected as a preferable processing time.
  • the second organic molecule 62 is introduced onto the base material 60 on which the first organic molecule 61 is scattered, and the first organic molecule 61 Then, the second organic molecules 62 are arranged to form the thin film 6. In this step, the second organic molecules 62 are arranged together with the first organic molecules 61, so that a thin film is formed for the first time.
  • the second organic molecule 62 does not need to be chemically bonded to the substrate 60 and is not particularly limited as long as it is arranged with respect to the first organic molecule 61. And / or what expresses the intermolecular interaction between the second organic molecules 62 is preferable. Here, “intermolecular interaction” is the same as in the case of the first organic molecule 61.
  • a semiconductor molecule is also preferable. Specific examples of the second organic molecule 62 include a group in which the group that binds to the substrate 60 in the first organic molecule 61 is substituted with another group that does not bind to the substrate 60. Those in which the group is a hydrogen atom are preferred.
  • a particularly preferred second organic molecule 62 is an organosilicon compound represented by the following general formula (II) (hereinafter abbreviated as organosilicon compound (II)).
  • organosilicon compound (II) organosilicon compound represented by the following general formula (II) (hereinafter abbreviated as organosilicon compound (II)).
  • RH (II) In the formula, R is an organic group having a ⁇ electron conjugated system.)
  • R is the same as R in the general formula (I). That is, the organosilicon compound (II) is obtained by replacing the group represented by the general formula “—SiX 1 X 2 X 3 ” with a hydrogen atom (—H) in the organosilicon compound (I). Therefore, as the second organic molecule 62, a compound exhibiting properties as a p-type semiconductor can be used as in the case of the first organic molecule 61, but one compound constituting the aromatic ring of the compound is used.
  • the above hydrogen atom may be used as an n-type organic semiconductor by substituting an electron withdrawing group such as a fluorine atom, a chlorine atom, a trifluoromethyl group (—CF 3 ) or a cyano group (—C ⁇ N). Good.
  • an electron withdrawing group such as a fluorine atom, a chlorine atom, a trifluoromethyl group (—CF 3 ) or a cyano group (—C ⁇ N).
  • the second organic molecule 62 may be one kind or two or more kinds.
  • the combination and ratio thereof are not particularly limited, but in order to further improve the orientation of the organic thin film, one kind is used. Preferably there is.
  • the second organic molecule 62 forms a stacking structure with the first organic molecule 61 by an intermolecular interaction such as ⁇ - ⁇ interaction, and also between the second organic molecules 62.
  • the orientation is better controlled on the base material 60 to form a thin film.
  • the second organic molecule 62 is a first organic molecule that is combined with a site that exhibits intermolecular interaction, such as a skeleton having a ⁇ -electron conjugated system, because the stacking structure is further strengthened.
  • the same as 61 is preferable.
  • the second organic molecules 62 are continuously introduced into the base material 60 and the second organic molecules 62 are densely arranged. It is often the simplest method to introduce an excess amount of the second organic molecule 62.
  • the method for introducing the second organic molecule 62 is not particularly limited, but preferably a method in which a liquid containing the second organic molecule 62, more preferably a solution in which the second organic molecule 62 is dissolved, is brought into contact with the substrate 60. Can be illustrated.
  • a liquid containing the second organic molecule 62 examples include various printing methods such as an immersion method, a coating method, and an ink jet method, and a casting method and a spin coating method. Etc. are more preferable.
  • a vapor deposition method can be exemplified as a method not using the liquid containing the second organic molecule 62.
  • the introduced second organic molecule 62 is preferably arranged by intermolecular interaction with respect to the scattered first organic molecule 61 so that the molecular chain extends upward on the substrate 60. Exist in a standing state. And when the surface of the base material 60 is hydrophilized, it is thought that this state is more easily taken. Most preferably, the second organic molecules 62 extend in a direction substantially perpendicular to the surface of the substrate 60. Further, the second organic molecule 62 not only forms a layer (first layer) containing the first organic molecule 61 on the base material 60, but is further laminated on the first layer to form a plurality of layers. You may do it.
  • the formed organic thin film may be washed according to a known method as appropriate.
  • An organic thin film in which the first organic molecules 61 are erected and scattered by chemical bonds on the base material 60 and the second organic molecules 62 are arranged with respect to the first organic molecules 61 by the above manufacturing method. 6 is obtained.
  • the thickness of the organic thin film 6 is determined by the size (molecular length) of the first organic molecule 61 and the second organic molecule 62 and is not particularly limited.
  • the organic thin film 6 has a mismatch between the optimal periodicity of the molecular arrangement and the periodicity of the actual molecular arrangement for the first organic molecule 61 and the second organic molecule 62. Since no matching) occurs, disorder of alignment and defects are suppressed, and a dense film having a sufficient function is obtained.
  • the ratio between the thickness and width of the molecule is larger than that of an organic molecule having an alkyl group or the like instead of the ⁇ -electron conjugated system, and the radial radius Is expected to increase.
  • the degree of freedom of the arrangement structure is usually increased, and the thin film has many orientation disturbances and defects.
  • such a problem does not occur in the organic thin film according to the present invention for the above reasons.
  • the organic thin film 6 with controlled orientation is obtained regardless of the size of the first organic molecule 61 and the second organic molecule 62, various organic molecules can be used, and the versatility is high. .
  • the field effect transistor according to the present invention is a field effect transistor provided with an organic semiconductor layer, wherein the organic thin film in which the first and second organic molecules are organic semiconductor molecules is provided as the organic semiconductor layer. It is characterized by. And it can be set as the structure similar to the conventional field effect transistor except having provided this organic-semiconductor layer.
  • the field effect transistor according to the present invention can be operated at high speed by including the organic thin film.
  • the organic thin film is mainly used as a p-type semiconductor layer.
  • an organic molecule into which a group has been introduced is used, or depending on the selection of the electrode material, it can function as an n-type semiconductor layer.
  • FIG. 5 is a schematic cross-sectional view illustrating the main part of the field effect transistor according to the first embodiment.
  • the field effect transistor 1 ⁇ / b> A shown here is schematically configured by laminating a gate electrode 12, a gate insulating film 13, an organic semiconductor layer 16, a source electrode 14 and a drain electrode 15 on a substrate 11. More specifically, a gate electrode 12 is provided on a part of the substrate 11, a gate insulating film 13 is provided on the substrate 11 so as to cover the gate electrode 12, and an organic semiconductor layer is formed on the gate insulating film 13. 16 is provided. A source electrode 14 and a drain electrode 15 are provided on the organic semiconductor layer 16 so as to be in contact with each other. The organic semiconductor layer 16 is provided so as to face the gate electrode 12 with the gate insulating film 13 interposed therebetween.
  • the field effect transistor 1A has a bottom gate / top contact type transistor structure.
  • the material of the substrate 11 can be appropriately selected according to the configuration and performance of the device.
  • the substrate 11 may have a single layer structure made of one kind of material, or may have a multiple layer structure in which two or more kinds of materials are laminated.
  • the material of the gate electrode 12 is not particularly limited, and may be one normally used in the field. Specifically, low resistance metals such as gold, platinum, silver, copper, aluminum, tantalum, and doped silicon; 3,4-polyethylenedioxythiophene (hereinafter abbreviated as PEDOT) / polystyrene sulfonate (hereinafter, referred to as “PETOT”) Examples thereof include organic conductors such as PSS).
  • PEDOT 3,4-polyethylenedioxythiophene
  • PET polystyrene sulfonate
  • the material of the source electrode 14 and the drain electrode 15 is the highest occupied molecular orbital (HOMO) level of the organic semiconductor molecule for the p-type organic semiconductor, and the organic semiconductor for the n-type organic semiconductor.
  • HOMO occupied molecular orbital
  • Examples include those having a work function at the lowest unoccupied molecular orbital (LUMO) level of the molecule.
  • Materials close to the HOMO level include metals with relatively high work functions such as gold, platinum, silver, or alloys containing one or more of these; transparent oxides such as indium tin oxide (ITO) and zinc oxide (ZnO)
  • Physical conductors Organic conductors such as PEDOT / PSS can be exemplified.
  • Examples of the material close to the LUMO level include metals having a relatively low work function such as aluminum, titanium, alkali metals, or alloys containing one or more of these.
  • Examples of the alkali metal include lithium, sodium, and potassium.
  • the surface of the source electrode 14 and the drain electrode 15 may be provided with a surface modification layer made of organic molecules or the like.
  • the surface modification layer can be formed, for example, by allowing a surface modifier to act on the surfaces of the source electrode 14 and the drain electrode 15.
  • the thicknesses of the gate electrode 12, the source electrode 14, and the drain electrode 15 are not particularly limited as long as they are normal transistor thicknesses, and are preferably adjusted as appropriate according to the purpose.
  • the material is a metal, it is preferably 30 to 200 nm.
  • These electrodes can be formed, for example, by vapor deposition, sputtering, coating, or the like depending on the material.
  • the material of the gate insulating film 13 is preferably a material having a high dielectric constant and hardly causing defects such as pinholes when forming a thin film. Since the dielectric constant is high, the threshold value of the field effect transistor can be further reduced. In addition, by reducing defects such as pinholes when forming a thin film, a function effect of the gate insulating film 13 is suppressed and a field effect transistor with better characteristics can be obtained.
  • the gate insulating film 13 is formed of, for example, a group such as alkoxysilane or halogenosilane constituting the silane coupling agent (for example, in the organosilicon compound (I), so that the first organic molecule can be chemically bonded.
  • At least the surface has a reactive group such as a hydroxyl group having excellent reactivity with the group represented by the general formula “—SiX 1 X 2 X 3 ”).
  • a reactive group such as a hydroxyl group having excellent reactivity with the group represented by the general formula “—SiX 1 X 2 X 3 ”.
  • examples of such a film include inorganic insulating films such as silicon oxide films, tantalum pentoxide films, and aluminum oxide films; organic insulating films such as polyvinylphenol films.
  • the film thickness of the gate insulating film 13 is preferably set so that the capacitance per unit area is increased, and the threshold voltage of the field effect transistor can be further reduced by reducing the film thickness.
  • the film thickness of the gate insulating film 13 is preferably adjusted as appropriate according to the relative dielectric constant, insulation, etc. of the material, and is preferably 50 to 300 nm, for example.
  • the gate insulating film 13 can be formed by, for example, vapor deposition, sputtering, coating, or the like depending on the material.
  • the organic semiconductor layer 16 is the organic thin film according to the present invention.
  • the film thickness of the organic semiconductor layer 16 is preferably 1 to 100 nm.
  • the organic semiconductor layer 16 has a sufficient function because the orientation of the first and second organic molecules constituting the thin film is controlled.
  • FIG. 6 is a schematic cross-sectional view illustrating the main part of the field effect transistor according to the second embodiment.
  • the field effect transistor 1 ⁇ / b> B shown here has a gate electrode 12, a gate insulating film 13, a source electrode 14, a drain electrode 15, and an organic semiconductor layer 16 stacked on a substrate 11 and is schematically configured. More specifically, the gate electrode 12 is provided on a part of the substrate 11, and the gate insulating film 13 is provided on the substrate 11 so as to cover the gate electrode 12.
  • a source electrode 14 and a drain electrode 15 are provided apart from each other on the gate insulating film 13, and an organic semiconductor layer 16 is provided on the gate insulating film 13 between the source electrode 14 and the drain electrode 15. .
  • the organic semiconductor layer 16 is provided so as to face the gate electrode 12 with the gate insulating film 13 interposed therebetween.
  • the field effect transistor 1B has a bottom-gate / bottom-contact transistor structure.
  • the gate insulating film 13 preferably has at least a reactive group such as a hydroxyl group on the surface. Furthermore, since the organic semiconductor layer 16 is provided on the source electrode 14 and the drain electrode 15, it is preferable that a hydrophilic film as a surface modification layer is provided on the surface of these electrodes. Further, the source electrode 14 and the drain electrode 15 may be formed on the gate insulating film 13 through an adhesion layer (not shown). Examples of the material for the adhesion layer include chromium.
  • the field effect transistor according to the present invention is not limited to those shown in FIGS. 5 to 6, and some of these configurations may be changed. For example, the following are mentioned.
  • the organic semiconductor layer 16 is provided on the substrate 11, and the source electrode 14 and the drain electrode 15 are provided on the organic semiconductor layer 16 so as to be separated from each other, and the source electrode 14 and the drain electrode are provided.
  • a field effect transistor 1C in which a gate insulating film 13 and a gate electrode 12 are provided in this order on an organic semiconductor layer 16 between 15 (third embodiment).
  • the source electrode 14 and the drain electrode 15 are provided separately on the substrate 11, and the organic semiconductor layer 16 is formed on the substrate 11 so as to cover the source electrode 14 and the drain electrode 15.
  • a field effect transistor 1D (fourth embodiment) in which a gate insulating film 13 is provided on the organic semiconductor layer 16, and a gate electrode 12 is provided on a part of the gate insulating film 13.
  • the material of the substrate 11 is preferably the same as that of the base material 60 (FIGS. 1 to 3). Furthermore, in the field effect transistor 1D, since the organic semiconductor layer 16 is provided on the source electrode 14 and the drain electrode 15, it is preferable that a hydrophilic film is provided as a surface modification layer on the surface of these electrodes. In the case where the organic semiconductor layer 16 is not provided on the gate insulating film 13 in contact with the gate insulating film 13 like the field effect transistors 1C and 1D, the surface of the gate insulating film 13 is not necessarily a hydroxyl group or the like. It is not necessary to have a reactive group.
  • the material of the gate insulating film 13 includes, in addition to the above, an inorganic insulating film such as a silicon nitride film; an organic insulating film such as a polyimide film and a parylene film. It can be illustrated.
  • the field effect transistor according to the present invention can be manufactured, for example, by the following method. First, a method for manufacturing the field effect transistor 1A shown in FIG. 5 will be described. 9A to 9D are schematic cross-sectional views for explaining a method of manufacturing the field effect transistor 1A.
  • a film made of the material constituting the gate electrode 12 is formed on the substrate 11, and the film is formed into a desired pattern by photolithography and etching. As shown in FIG. A gate electrode 12 is formed.
  • An example of the film formation method is a sputtering method.
  • a gate insulating film 13 is formed on the substrate 11 so as to cover the gate electrode 12.
  • An example of a method for forming the gate insulating film 13 is a sputtering method.
  • an organic semiconductor layer 16 is formed on the gate insulating film 13.
  • the method for forming the organic semiconductor layer 16 is as described in the method for manufacturing the organic thin film.
  • the source electrode 14 and the drain electrode 15 are formed on the organic semiconductor layer 16 by a vacuum deposition method or the like through a metal mask (not shown) having a predetermined opening.
  • a field effect transistor 1A shown in FIG. 5 is obtained.
  • 10A to 10E are schematic cross-sectional views for explaining a method for manufacturing the field effect transistor 1A.
  • a gate electrode 12 and a gate insulating film 13 are formed on the substrate 11 by a method similar to the method described with reference to FIGS. 9A and 9B, as shown in FIGS. 10A and 10B.
  • the photoresist film 90 is for forming the source electrode 14 and the drain electrode 15 and has openings corresponding to these shapes.
  • a metal film made of the material of the source electrode 14 and the drain electrode 15 is formed on the gate insulating film 13 so as to cover the photoresist film 90, and the photoresist film 90 is removed, as shown in FIG. 10D.
  • the source electrode 14 and the drain electrode 15 are formed at predetermined positions on the gate insulating film 13.
  • an adhesion layer (not shown) is formed on the gate insulating film 13 so as to cover the photoresist film 90, and the metal film is formed on the adhesion layer. May be.
  • the material for the adhesion layer include metals such as chromium.
  • An example of a method for forming the metal film and the adhesion layer is a vacuum deposition method.
  • the adhesion layer is also removed together with the photoresist film 90.
  • An example of a method for removing the photoresist film 90 is a lift-off method in which the substrate 11 is immersed in an organic solvent such as acetone.
  • the organic semiconductor layer 16 is formed on the gate insulating film 13 between the source electrode 14 and the drain electrode 15.
  • the method for forming the organic semiconductor layer 16 is as described in the method for manufacturing the organic thin film. By performing the above steps, a field effect transistor 1B shown in FIG. 6 is obtained.
  • the organic semiconductor layer 16 may be formed as shown in FIG. 10E.
  • the solar cell according to the present invention is a solar cell comprising a pair of electrodes on a base material, a p-type semiconductor layer and an n-type semiconductor layer between the pair of electrodes, wherein the first and second types
  • the organic thin film in which an organic molecule is an organic semiconductor molecule is provided as the p-type semiconductor layer and / or the n-type semiconductor layer. And it can be set as the structure similar to the conventional solar cell except having provided this p-type semiconductor layer and / or n-type semiconductor layer. Since the solar cell according to the present invention includes the organic thin film, the photoelectric conversion efficiency is improved.
  • the organic thin film is mainly used as a p-type semiconductor layer.
  • an organic molecule into which a group has been introduced is used, or depending on the selection of the electrode material, it can function as an n-type semiconductor layer.
  • FIG. 11 is a schematic cross-sectional view illustrating the main part of the solar cell according to the present invention.
  • an anode electrode 22, a p-type semiconductor layer 24, an n-type semiconductor layer 25, and a cathode electrode 23 are laminated in this order on a glass substrate 21, and is schematically configured. That is, a pair of electrodes including an anode electrode 22 and a cathode electrode 23 and a pn junction p-type semiconductor layer 24 and an n-type semiconductor layer 25 sandwiched between the pair of electrodes are provided on the glass substrate 21. It is what was done.
  • the p-type semiconductor layer 24 may be formed of a known material or an organic thin film according to the present invention.
  • the p-type semiconductor layer 24 only needs to have a site to which a first organic molecule such as a hydrophilic group can be bonded.
  • the film thickness of the p-type semiconductor layer 24 is preferably 5 to 500 nm.
  • the n-type semiconductor layer 25 may be the organic thin film according to the present invention.
  • a preferable material is a fullerene; a fullerene derivative such as [6,6] -phenyl C61 butyric acid methyl ester (PCBM); one or more constituting a phthalimide ring
  • the fluorinated phthalocyanine in which the hydrogen atom is substituted with a fluorine atom. In the fluorinated phthalocyanine, all hydrogen atoms constituting the phthalimide ring may be substituted with fluorine atoms.
  • the film thickness of the n-type semiconductor layer 25 is preferably 5 to 500 nm.
  • Either one of the p-type semiconductor layer 24 and the n-type semiconductor layer 25 may be a known one.
  • the p-type semiconductor layer 24 and / or the n-type semiconductor layer 25, which are the organic thin films, have a sufficient function because the orientation of the first and second organic molecules constituting the thin film is controlled.
  • the anode electrode 22 is formed of, for example, an alkoxysilane, a halogenosilane, or the like constituting a silane coupling agent so that the first organic molecule can be chemically bonded. It is preferable that at least the surface has a reactive group such as a hydroxyl group excellent in reactivity with a group (for example, a group represented by the general formula “—SiX 1 X 2 X 3 ” in the organosilicon compound (I)). . Examples of such a material include ITO which is a transparent electrode.
  • the thickness of the anode electrode 22 is preferably 10 to 500 nm.
  • Examples of the material of the cathode electrode 23 include silver and aluminum.
  • the film thickness of the cathode electrode 23 is preferably 10 to 500 nm.
  • the solar cell according to the present invention can be manufactured, for example, by the following method.
  • 12A to 12D are schematic cross-sectional views for explaining the manufacturing method of the solar cell 2A.
  • the anode electrode 22 is formed on the glass substrate 21. Examples of the method for forming the anode electrode 22 include a sputtering method.
  • a p-type semiconductor layer 24 is formed on the anode electrode 22.
  • the method for producing the organic thin film can be exemplified.
  • a vacuum deposition method is exemplified. it can.
  • an n-type semiconductor layer 25 is formed on the p-type semiconductor layer 24.
  • the method for producing the organic thin film can be exemplified, and when it is not the organic thin film, a vacuum deposition method is exemplified. it can.
  • the cathode electrode 23 is formed on the n-type semiconductor layer 25.
  • An example of a method for forming the cathode electrode 23 is a vacuum vapor deposition method. By performing the above steps, a solar cell 2A shown in FIG. 11 is obtained.
  • the organic light-emitting device is an organic light-emitting device comprising a pair of electrodes on a substrate, and having at least a carrier transport layer and a light-emitting layer between the pair of electrodes.
  • the organic thin film whose organic molecule is an organic semiconductor molecule is provided as the carrier transport layer. And it can be set as the structure similar to the conventional organic light emitting element except having provided this carrier transport layer. Since the organic light emitting device according to the present invention includes the organic thin film, carrier transport characteristics are improved, and good light emission characteristics are obtained.
  • the organic thin film is mainly used as a p-type semiconductor layer.
  • an organic molecule into which a group is introduced is used or depending on the selection of the electrode material, it can function as an n-type semiconductor layer (electron transport layer).
  • FIG. 13 is a schematic cross-sectional view illustrating the main part of the organic light-emitting device according to the present invention.
  • the organic light emitting element 3A shown here is schematically configured by laminating an anode electrode 32, an organic electroluminescence (hereinafter abbreviated as organic EL) portion 34, and a cathode electrode 33 in this order on a glass substrate 31. That is, a pair of electrodes including an anode electrode 32 and a cathode electrode 33 and an organic EL portion 34 sandwiched between the pair of electrodes are provided on a glass substrate 31.
  • organic EL organic electroluminescence
  • the anode electrode 32 and the cathode electrode 33 are the same as the anode electrode and the cathode electrode in the solar cell, respectively.
  • a carrier (hole) injection layer 34a, a carrier transport layer 34b, a light emitting layer 34c, an electron transport layer 34d, and an electron injection layer 34e are laminated in this order from the anode electrode 32 side to the cathode electrode 33 side. And is roughly structured.
  • the carrier injection layer 34a, the carrier transport layer 34b, the light emitting layer 34c, the electron transport layer 34d, and the electron injection layer 34e may each have a single layer structure or a multilayer structure.
  • the carrier transport layer 34b is the organic thin film according to the present invention.
  • the thickness of the carrier transport layer 34b is preferably 5 to 500 nm.
  • the carrier transport layer 34b has a sufficient function in which the orientation of the first and second organic molecules constituting the thin film is controlled.
  • the carrier injection material may be a known material for organic EL or organic photoconductor.
  • Preferred carrier injection materials include oxides such as vanadium oxide (V 2 O 5 ) and molybdenum oxide (MoO 2 ), and inorganic p-type semiconductor materials; polyaniline (PANI), polyaniline-camphor sulfonic acid (PANI-CSA), 3 , 4-polyethylenedioxythiophene / polystyrene sulfonate (PEDOT / PSS), poly (triphenylamine) derivative (Poly-TPD), polyvinylcarbazole (PVCz), poly (p-phenylene vinylene) (PPV), poly ( Examples thereof include polymer materials such as p-naphthalene vinylene) (PNV).
  • the highest occupied molecular orbital (HOMO) is used as compared with the carrier injection / transport material applied to the carrier transport layer 34b from the viewpoint of more efficiently injecting and transporting carriers from the anode.
  • a material having a low energy level is preferred.
  • the film thickness of the carrier injection layer 34a is preferably 1 to 500 nm.
  • the material of the light emitting layer 34c may be a known material for organic EL, and can be classified into, for example, a low molecular light emitting material and a polymer light emitting material.
  • Preferred examples of the low-molecular light-emitting material include aromatic dimethylidene compounds such as 4,4′-bis (2,2′-diphenylvinyl) -biphenyl (DPVBi); 5-methyl-2- [2- [4- Oxadiazole compounds such as (5-methyl-2-benzoxazolyl) phenyl] vinyl] benzoxazole; 3- (4-biphenylyl) -4-phenyl-5-tert-butylphenyl-1,2,4 -Triazole derivatives such as triazole (TAZ); styrylbenzene compounds such as 1,4-bis (2-methylstyryl) benzene; fluorescent organic materials such as fluorenone derivatives.
  • aromatic dimethylidene compounds such as 4,4′-bis (2,
  • Preferred examples of the polymer light-emitting material include polyphenylene vinylene derivatives such as poly (2-decyloxy-1,4-phenylene) (DO-PPP); polyspiro derivatives such as poly (9,9-dioctylfluorene) (PDAF). Etc. can be exemplified.
  • the thickness of the light emitting layer 34c is preferably 5 to 500 nm.
  • the electron injection / transport material may be a known material for organic EL or organic photoconductor.
  • Preferred electron injecting and transporting materials include inorganic materials that are n-type semiconductors, oxadiazole derivatives, triazole derivatives, thiopyrazine dioxide derivatives, benzoquinone derivatives, naphthoquinone derivatives, anthraquinone derivatives, diphenoquinone derivatives, fluorenone derivatives, benzodifuran derivatives, and the like.
  • Molecular materials Polymer materials such as poly (oxadiazole) (Poly-OXZ) and polystyrene derivatives (PSS) can be exemplified.
  • examples of the electron injection material include fluorides such as lithium fluoride (LiF) and barium fluoride (BaF 2 ); oxides such as lithium oxide (Li 2 O) and the like.
  • the minimum unoccupied molecular orbital (LUMO) than the electron injection / transport material applied to the electron transport layer 34d is used as a material applied to the electron injection layer 34e.
  • a material having a high energy level is preferred.
  • the material applied to the electron transport layer 34d is preferably a material having higher electron mobility than the electron injection transport material applied to the electron injection layer 34e.
  • the film thickness of the electron transport layer 34d is preferably 5 to 500 nm.
  • the film thickness of the electron injection layer 34e is preferably 0.1 to 100 nm.
  • the organic light emitting device is not limited to the one shown in FIG. 13, and a part of its configuration may be changed.
  • the structure of the organic EL unit 34 as follows can be given.
  • An organic EL part in which a carrier injection layer, a carrier transport layer, a light emitting layer, a carrier prevention layer, and an electron transport layer are laminated in this order from the anode electrode 32 side to the cathode electrode 33 side.
  • An organic EL part in which a carrier injection layer, a carrier transport layer, a light emitting layer, a carrier prevention layer, an electron transport layer, and an electron injection layer are laminated in this order from the anode electrode 32 side to the cathode electrode 33 side.
  • V An organic EL in which a carrier injection layer, a carrier transport layer, an electron prevention layer, a light emitting layer, a carrier prevention layer, an electron transport layer, and an electron injection layer are laminated in this order from the anode electrode 32 side to the cathode electrode 33 side. Department.
  • the carrier prevention layer and the electron prevention layer may be known for organic EL, and may have either a single layer structure or a multilayer structure, respectively.
  • the organic light emitting device according to the present invention can be manufactured, for example, by the following method.
  • 14A to 14G are schematic cross-sectional views for explaining a method for manufacturing the organic light emitting device 3A.
  • an anode electrode 32 is formed on a glass substrate 31.
  • An example of a method for forming the anode electrode 32 is a sputtering method.
  • a carrier injection layer 34 a is formed on the anode electrode 32.
  • a spin coating method can be exemplified.
  • a carrier transport layer 34b is formed on the carrier injection layer 34a.
  • the method for forming the carrier transport layer 34b is as described in the method for manufacturing the organic thin film.
  • a light emitting layer 34c is formed on the carrier transport layer 34b.
  • An example of a method for forming the light emitting layer 34c is a vacuum deposition method.
  • an electron transport layer 34d is formed on the light emitting layer 34c.
  • An example of a method for forming the electron transport layer 34d is a vacuum deposition method.
  • an electron injection layer 34e is formed on the electron transport layer 34d.
  • a vacuum deposition method can be exemplified.
  • the cathode electrode 33 is formed on the electron injection layer 34e.
  • a vacuum deposition method can be exemplified. By performing the above steps, an organic light emitting device 3A shown in FIG. 13 is obtained.
  • the array for a display device includes the field effect transistor as a switching element. And it can be set as the structure similar to the array for conventional display apparatuses except having provided this field effect transistor.
  • the display device array according to the present invention includes the field effect transistor, thereby enabling high-speed operation.
  • FIG. 15A to 15D are schematic views illustrating the main part of the array for a display device according to the present invention.
  • FIG. 15A is a plan view
  • FIG. 15B is an enlarged plan view
  • FIG. 15C is a CC line in FIG.
  • FIG. 15D is a sectional view taken along the line DD of FIG. 15B.
  • the display device array 4A shown here is used as a drive array of an image display device by arranging the organic semiconductor devices 42 including the field effect transistors 1B shown in FIG. 6 in a matrix.
  • the display device array 4A is schematically composed of an organic semiconductor device 42 including a gate wiring 40, a source wiring 41, a pixel electrode 43, and a field effect transistor 1B electrically connected to the gate wiring 40 and the source wiring 41 provided on the transparent substrate 11. It is configured.
  • the gate wiring 40 constitutes the gate electrode 12 in FIG. 6 and is also a connection wiring to it.
  • a source electrode 14 and a drain electrode 15 are provided on the gate wiring 40 with a gate insulating film 13 therebetween, and an organic semiconductor layer 16 is formed on the gate insulating film 13 between the source electrode 14 and the drain electrode 15. Is provided. Further, the drain electrode 15 is connected to the pixel electrode 43 and configured as a driving array.
  • the organic semiconductor device 42 can be manufactured by the same method as that for the field-effect transistor 1B except that, for example, the source wiring 41 and the pixel electrode 43 are formed. Specifically, it is as follows. 16A to 16E are schematic cross-sectional views for explaining a method for manufacturing the organic semiconductor device 42. FIG. First, as shown in FIGS. 16A to 16C, a gate wiring 40 (gate electrode 12) and a gate insulating film 13 are sequentially formed on the substrate 11 by a method similar to the method described with reference to FIGS. 10A to 10C. Next, a photoresist film 90 having a predetermined pattern is formed.
  • the gate insulating film 13 is formed so as to cover the surface of the gate wiring 40 and cover the entire surface of the substrate 11, and then etched into a predetermined pattern.
  • the source electrode 14 and the drain electrode 15 are formed by a method similar to the method described with reference to FIG. 10D.
  • the source wiring 41 is formed on the gate insulating film 13 so as to be in contact with the source electrode 14, and the pixel electrode 43 is formed so as to be in contact with the drain electrode 15.
  • the source wiring 41 and the pixel electrode 43 are made of a metal such as silver (Ag), for example, and can be formed by various printing methods.
  • the organic semiconductor layer 16 is formed on the gate insulating film 13 between the source electrode 14 and the drain electrode 15 by a method similar to the method described with reference to FIG. 10E.
  • the method for forming the organic semiconductor layer 16 is as described in the method for manufacturing the organic thin film.
  • the organic semiconductor device 42 is obtained.
  • the obtained organic semiconductor devices 42 are arranged in a matrix, whereby the display device array 4A is obtained.
  • the array for a display device according to the present invention is suitable for driving an image display device such as a liquid crystal display device or an organic EL display device.
  • the display device includes an image signal output unit that generates and outputs an image signal, a drive unit that generates a current or a voltage based on the image signal, and a light emitting unit that emits light based on the generated current or voltage.
  • the light emitting unit is the organic light emitting element.
  • the display device includes the organic light-emitting element, so that good light emission characteristics can be obtained.
  • FIG. 17A to 17C are schematic views illustrating the main part of the display device according to the present invention.
  • FIG. 17A is a plan view
  • FIG. 17B is an equivalent circuit diagram of one pixel
  • FIG. 17C is a plan view of one pixel.
  • the display device 5 ⁇ / b> A shown here is an organic EL display device using the organic light emitting element 3 according to the present invention as an element of the organic EL display device.
  • a matrix is formed in which a plurality of scanning lines (gate lines) 50 and a plurality of signal lines (source lines) 51 are arranged vertically and horizontally, and one pixel is provided at each intersection.
  • a pixel array is formed.
  • a scanning line driving circuit (gate driver) 55 connected to the scanning line 50 and a signal line driving circuit (source driver) 56 connected to the signal line 51 are arranged.
  • the scanning line driving circuit 55 and the signal line driving circuit 56 are connected to a controller 57 for supplying an image signal such as a timing signal for displaying an image or an RGB luminance signal.
  • a power supply circuit 59 for supplying a signal voltage to be applied to the line 51 is connected.
  • the controller 57 is connected to an external processing device 58 for supplying a horizontal / vertical synchronizing signal and an image signal from the outside to the display device 5A. As shown in FIG.
  • one pixel of the pixel array constituting the display device 5A includes a switching transistor 52 connected to the scanning line 50 and the signal line 51, a driving transistor 53 for driving the pixel, and a storage capacitor. 54, and a pixel portion made of the organic light emitting element 3 (organic EL element) is connected to the driving transistor 53.
  • the organic light emitting element 3 emits light by a driving current or voltage.
  • the switching transistor 52 and the driving transistor 53 can be configured by, for example, a transistor using general polycrystalline silicon as a semiconductor.
  • the display device 5A is configured as described above. As the organic light emitting element 3, any organic light emitting element 3A shown in FIG. 13 can be used as long as it is an element according to the present invention.
  • the Si substrate hydrophilized is immersed in an anhydrous toluene solution (concentration: 1 ⁇ 10 ⁇ 3 ⁇ mol / L) of 2 and X 3 is a chlorine atom, and slowly lifted up and washed with a solvent. Then, quarterthiophene was bonded onto the Si substrate.
  • the field effect transistor 1A shown in FIG. 5 was manufactured by the manufacturing method described with reference to FIGS. 9A to 9D. More specifically, it is as follows.
  • the material of the gate electrode 12 was an AlSi alloy in which 10% silicon (Si) was added to aluminum (Al). Then, a 40 nm thick metal film made of an AlSi alloy was formed on the substrate 11 by sputtering using a metal target made of this AlSi alloy. The patterning of the metal film was performed by photolithography and etching.
  • the material of the gate insulating film 13 was silicon oxide (SiO 2 ), and a silicon oxide film having a thickness of 300 nm was formed by a sputtering method.
  • the organic semiconductor layer 16 was formed by the same material and method as in Example 1.
  • the film thickness of the organic semiconductor layer 16 was 2 nm.
  • the source electrode 14 and the drain electrode 15 were made of gold (Au), and an Au film having a film thickness of 40 nm was formed by a vacuum deposition method through a metal mask. At this time, the distance (channel length) between the source electrode 14 and the drain electrode 15 was 50 ⁇ m, and the length of the opposing electrode (channel width) was 1000 ⁇ m.
  • the field effect mobility of the obtained field effect transistor 1A was measured and found to be 8 ⁇ 10 ⁇ 2 cm 2 / Vs.
  • the organic semiconductor thin film produced by the same method as in Example 1 as the organic semiconductor layer, a field effect transistor with high characteristics was obtained.
  • the field effect transistor 1B shown in FIG. 6 was manufactured by the manufacturing method described with reference to FIGS. 10A to 10E. More specifically, it is as follows.
  • the substrate 11 a glass substrate (Corning, Eagle 2000, thickness: 0.5 mm) was used.
  • the material of the gate electrode 12 was an AlSi alloy in which 10% silicon (Si) was added to aluminum (Al).
  • a 40 nm thick metal film made of an AlSi alloy was formed on the substrate 11 by sputtering using a metal target made of this AlSi alloy.
  • the patterning of the metal film was performed by photolithography and etching.
  • the material of the gate insulating film 13 was silicon oxide (SiO 2 ), and a silicon oxide film having a thickness of 300 nm was formed by a sputtering method.
  • the photoresist film 90 was formed by spin coating using a negative photoresist (ZPN 1150, manufactured by Nippon Zeon Co., Ltd.) for lift-off process, and then by photolithography.
  • ZPN 1150 negative photoresist
  • a lift-off method in which an adhesion layer made of chromium (Cr) with a thickness of 2 nm and a metal film made of gold (Au) with a thickness of 40 nm are sequentially formed by vacuum deposition, and the substrate 11 is immersed in an organic solvent such as acetone.
  • the photoresist film 90 and the unnecessary Au film / Cr film formed thereon were removed by the method to form the source electrode 14 and the drain electrode 15.
  • the distance (channel length) between the source electrode 14 and the drain electrode 15 was 20 ⁇ m
  • the length of the opposing electrode (channel width) was 1000 ⁇ m.
  • the organic semiconductor layer 16 uses 2-trichlorosilylpentacene instead of quarterthiophene trichlorosilane as the first organic molecule, pentacene instead of quarterthiophene as the second organic molecule, and pentacene is replaced by the spin coating method. It was formed by the same method as in Example 1 except that it was introduced by vapor deposition.
  • the film thickness of the organic semiconductor layer 16 was 3 nm.
  • the field effect mobility was measured in the same manner as in Example 2. As a result, it was 6 ⁇ 10 ⁇ 2 cm 2 / Vs.
  • the organic semiconductor thin film produced by the same method as in Example 1 as the organic semiconductor layer, a field effect transistor with high characteristics was obtained.
  • the solar cell 2A shown in FIG. 11 was manufactured by the manufacturing method described with reference to FIGS. 12A to 12D. More specifically, it is as follows.
  • the p-type semiconductor layer 24 is a quinquethiophene trichlorosilane (in the organosilicon compound represented by the general formula (I) -103, X 1 , X 2 and X This was formed in the same manner as in Example 1 except that 3 was a chlorine atom.
  • the film thickness of the p-type semiconductor layer 24 was 10 nm.
  • a film made of perfluorophthalocyanine having a thickness of 20 nm was formed by a vacuum deposition method.
  • As the cathode electrode 23 an Al film having a thickness of 100 nm was formed by a vacuum deposition method.
  • the obtained solar cell 2A was irradiated with artificial sunlight of AM1.5, the voltage-current characteristics between the positive electrode and the negative electrode were evaluated, and the conversion efficiency was calculated. Was confirmed.
  • the organic light emitting device 3A shown in FIG. 13 was manufactured by the manufacturing method described with reference to FIGS. 14A to 14G. More specifically, it is as follows.
  • As the glass substrate 31 “Corning Corp., Eagle 2000, thickness: 0.5 mm” was used.
  • As the anode electrode 32 an ITO film having a thickness of 150 nm was formed on the glass substrate 31 by a sputtering method.
  • the carrier injection layer 34a was formed by placing PEDOT / PSS (Bytron-P, manufactured by Bayer) on the anode electrode 32 by spin coating (rotation speed: 1500 rpm), and had a thickness of about 50 nm.
  • the carrier transport layer 34b has terthiophene trichlorosilane (in the organosilicon compound represented by the general formula (I) -101 as a first organic molecule, X 1 , X 2 and X 3 are substituted for quarter thiophene trichlorosilane). (Which is a chlorine atom) was formed in the same manner as in Example 1 except that terthiophene was used instead of quarterthiophene as the second organic molecule.
  • the film thickness of the carrier transport layer 34b was 2 nm.
  • the light emitting layer 34c is formed by using 4,4′-N, N′-dicarbazol-biphenyl (CBP) and tris (2-phenylpyridine) iridium (Ir (PPY) 3 ) on the carrier transport layer 34b. It was formed by a vacuum vapor deposition method in which vapor deposition was performed from The concentration of Ir (PPY) 3 in the formed light emitting layer 34c was 6.5% by mass. The film thickness was 30 nm.
  • the electron transport layer 34d was formed by vacuum-depositing tris (8-hydroxyquinoline aluminum) (A1q 3 ) on the light emitting layer 34c, and the film thickness was 40 nm.
  • the electron injection layer 34e was formed by vacuum-depositing lithium oxide (Li 2 O) on the electron transport layer 34d, and the film thickness was 0.5 nm.
  • the cathode electrode 33 was formed by vacuum-depositing aluminum (Al) on the electron injection layer 34e, and the film thickness was 150 nm.
  • voltage was applied between the anode and the cathode, and the emission spectrum was evaluated. As a result, light emission from Ir (PPY) 3 was observed.
  • the display device array 4A shown in FIGS. 15A to 15D was manufactured by the manufacturing method described with reference to FIGS. 16A to 16E. More specifically, it is as follows.
  • the material of the gate wiring 40 was an AlSi alloy in which 10% silicon (Si) was added to aluminum (Al).
  • a 40 nm thick metal film made of an AlSi alloy was formed on the substrate 11 by sputtering using a metal target made of this AlSi alloy.
  • the patterning of the metal film was performed by photolithography and etching.
  • the material of the gate insulating film 13 was silicon oxide (SiO 2 ), and a silicon oxide film having a thickness of 300 nm was formed by a sputtering method.
  • the photoresist film 90 was formed by spin coating using a negative photoresist (ZPN 1150, manufactured by Nippon Zeon Co., Ltd.) for lift-off process, and then by photolithography.
  • ZPN 1150 negative photoresist
  • a lift-off method in which an adhesion layer made of chromium (Cr) with a thickness of 2 nm and a metal film made of gold (Au) with a thickness of 40 nm are sequentially formed by vacuum deposition, and the substrate 11 is immersed in an organic solvent such as acetone.
  • the photoresist film 90 and the unnecessary Au film / Cr film formed thereon were removed by the method to form the source electrode 14 and the drain electrode 15. At this time, the distance (channel length) between the source electrode 14 and the drain electrode 15 was 20 ⁇ m, and the length of the opposing electrode (channel width) was 1000 ⁇ m.
  • the source wiring 41 and the pixel electrode 43 were formed in a desired pattern with a thickness of 50 nm by performing reverse printing of Ag ink and baking at 180 ° C.
  • the organic semiconductor layer 16 is composed of 2-trichlorosilylpentacene (in the organosilicon compound represented by the general formula (I) -303, X 1 , X 2, and X 3 instead of quarterthiophene trichlorosilane) as the first organic molecule. Except that pentacene is used instead of quarterthiophene as the second organic molecule, and pentacene is introduced by vapor deposition instead of spin coating. Formed with. The film thickness of the organic semiconductor layer 16 was 3 nm. Then, the obtained organic semiconductor devices 42 were arranged in a matrix to form a display device array 4A.
  • Example 7 Using the organic light emitting element 3A shown in FIG. 13 as an element of an organic EL display device, a display device 5A shown in FIGS. 17A to 17C was manufactured. The organic light emitting device 3A was manufactured in the same manner as in Example 5.
  • the present invention can be used for semiconductor devices such as field effect transistors, solar cells, and organic light emitting elements.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Thin Film Transistor (AREA)

Abstract

La présente invention a pour objectif de mettre à disposition : un film mince organique dans lequel l'orientation des molécules organiques a été commandée, et qui a une fonction suffisante ; un procédé permettant de produire le film mince organique ; ainsi qu'un dispositif électronique organique et un dispositif d'affichage qui sont obtenus en utilisant le film mince organique. Ce procédé sert à produire un film mince organique sur un substrat, et comprend les étapes suivantes : une étape consistant à disposer verticalement et de manière diffuse des premières molécules organiques sur le substrat à l'aide de liaisons chimiques ; et une étape consistant à introduire sur le substrat des secondes molécules organiques et à les agencer par rapport aux premières molécules organiques afin de former un film mince.
PCT/JP2012/067074 2012-07-04 2012-07-04 Procédé de production de film mince organique WO2014006700A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018137892A1 (fr) * 2017-01-30 2018-08-02 Saralon Gmbh Procédé de production d'électrodes à base de pedot : pss

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JP2009158691A (ja) * 2007-12-26 2009-07-16 Sharp Corp 有機デバイスおよびその製造方法
JP2009218244A (ja) * 2008-03-07 2009-09-24 Hitachi Ltd 有機薄膜トランジスタおよびその製造方法
JP2010272634A (ja) * 2009-05-20 2010-12-02 Sharp Corp 有機トランジスタの製造方法
WO2011135901A1 (fr) * 2010-04-30 2011-11-03 シャープ株式会社 Procédé de fabrication d'élément d'électrode, calculateur et dispositif de fabrication d'élément d'électrode
WO2012077573A1 (fr) * 2010-12-08 2012-06-14 シャープ株式会社 Structure d'électrode, transistor en couche mince organique comportant ladite structure d'électrode, procédé de fabrication de celui-ci, élément d'affichage électroluminescent organique comportant ledit transistor en couche mince organique, élément électroluminescent organique, dispositif comprenant ledit élément électroluminescent organique, et cellule solaire organique

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JP2008192724A (ja) * 2007-02-02 2008-08-21 Konica Minolta Holdings Inc 有機薄膜トランジスタ及び有機薄膜トランジスタの製造方法
JP2009158691A (ja) * 2007-12-26 2009-07-16 Sharp Corp 有機デバイスおよびその製造方法
JP2009218244A (ja) * 2008-03-07 2009-09-24 Hitachi Ltd 有機薄膜トランジスタおよびその製造方法
JP2010272634A (ja) * 2009-05-20 2010-12-02 Sharp Corp 有機トランジスタの製造方法
WO2011135901A1 (fr) * 2010-04-30 2011-11-03 シャープ株式会社 Procédé de fabrication d'élément d'électrode, calculateur et dispositif de fabrication d'élément d'électrode
WO2012077573A1 (fr) * 2010-12-08 2012-06-14 シャープ株式会社 Structure d'électrode, transistor en couche mince organique comportant ladite structure d'électrode, procédé de fabrication de celui-ci, élément d'affichage électroluminescent organique comportant ledit transistor en couche mince organique, élément électroluminescent organique, dispositif comprenant ledit élément électroluminescent organique, et cellule solaire organique

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WO2018137892A1 (fr) * 2017-01-30 2018-08-02 Saralon Gmbh Procédé de production d'électrodes à base de pedot : pss

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