JP2012144456A - Organic thin film, method for manufacturing organic thin film, field-effect transistor, organic light-emitting element, solar cell, array for display device, and display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic thin film controlled in the orientation of an organic molecule and having enough functions, a manufacturing method thereof, and an organic electron device using the organic thin film, and a display device.SOLUTION: The organic thin film 6 is formed by chemically bonding a first organic molecule 61 on a base 60 to stand, sprinkling it, introducing a second organic molecule 62, and arranging the second organic molecule 62 with respect to the first organic molecule 61. This organic thin film with the first organic molecule 61 and the second organic molecule 62 being organic semiconductor molecules is provided as an organic semiconductor layer to provide a field-effect transistor.

Description

  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.

  With the ubiquitous information society, flexible, lightweight and inexpensive devices are required as information terminals. Furthermore, when such an application as an information terminal is assumed, a process capable of quickly responding to not only mass production but also various user requests is required. Such devices and processes cannot sufficiently meet the demand by extending the conventional silicon-based device technology. In recent years, research on electronic device technology using organic materials for semiconductors has been actively conducted as a technology that can meet such demands. Among them, organic electronic devices such as organic transistors (OFETs), organic light emitting diodes (OLEDs), and organic solar cells using organic semiconductor materials have attracted attention, and some of them have already been put into practical use.

  In order for such an organic electronic device to exhibit its function, it is necessary to provide an organic thin film as a basic structure. For example, 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. Here, 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.

  In organic electronic devices, the orientation of the constituent molecules is an extremely important factor in the device function expression. 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. On the other hand, 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. However, depending on the production conditions, 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. It is a cause.

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. The For example, 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. In addition, 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).

Nature, 455, 956 (2008)

However, in a transistor using an oligothiophene single crystal that is an organic molecule having a similar π-electron conjugated system and has no orientation defect (see “Appl. Phys. Lett., Vol. 73, (1998)”), A mobility of 0.5 cm ² / (Vs) is shown, and the transistor device described in 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.

In FIG. 1, 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. Here, for easy understanding, the organic molecules 63 are indicated by rectangles. Then, 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. Then, substantially _{L a} and L _b are approximately equal, the value is known to be about 4.3 Å (angstroms) (see "An Introduction to Ulutrahin Organic Film, 257 , Academic press 1991 ") .
On the other hand, when the organic molecule 63 has a π-electron conjugated system, the distance between molecules considered to have the maximum intermolecular interaction between the adjacent organic molecules 63 is theoretically a fan of the π-electron conjugated molecule. It is about 3.4 which is the sum of the Delwarus radii. For example, when the organic molecule 63 is the above-mentioned oligothiophene, it is about 3.6Å considering that a sulfur atom having a large van der Waals radius is included. Only. Thus, in the conventional organic thin film 6 ′, the period L _b (about 4.3 cm) of the molecular arrangement of the organic molecules 63 is the distance between molecules (about 3.4-3) that maximizes the intermolecular interaction. .6Å), 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. In addition, although the case where an organic molecule has a π-electron conjugated system has been described here, an organic molecule that exhibits an intermolecular interaction other than the π-π interaction has a similar 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.

The present invention is a method for producing an organic thin film provided on a base material, wherein the first organic molecule is chemically bonded on the base material, and the organic thin film is erected and scattered. Providing a method for producing an organic thin film, comprising: introducing a second organic molecule; and arranging the second organic molecule with respect to the first organic molecule to form a thin film. To do.
The present invention also provides a method for producing an organic thin film, characterized in that in the method for producing an organic thin film, the second organic molecule is arranged by intermolecular interaction with respect to the first organic molecule. .
The present invention also provides a method for producing an organic thin film, wherein the first and second organic molecules have a π electron conjugated system.
In the method for producing an organic thin film according to the present invention, the solution in which the first organic molecule is dissolved is brought into contact with the substrate to chemically bond the first organic molecule onto the substrate. The manufacturing method of the organic thin film characterized by this is provided.
According to the present invention, in the method for producing an organic thin film, the density of the first organic molecule chemically bonded on the substrate is adjusted by the concentration of the solution in which the first organic molecule is dissolved. The manufacturing method of the organic thin film characterized by this is provided.
Further, the present invention provides the method for producing an organic thin film, wherein the first organic molecule chemically bonded on the base material according to a contact time between the base material and the solution in which the first organic molecule is dissolved. The method of manufacturing an organic thin film is characterized by adjusting the density of the organic thin film.
Further, the present invention is characterized in that in the method for producing an organic thin film, the second organic molecule is introduced onto the substrate by applying a solution in which the second organic molecule is dissolved. A method for producing an organic thin film is provided.
Moreover, this invention provides the manufacturing method of the organic thin film characterized by introduce | transducing on the said base material by vapor-depositing said 2nd organic molecule in the manufacturing method of this organic thin film.
In the method for producing an organic thin film according to the present invention, the base material has a hydrophilic group, and the first organic molecule is an organosilicon compound represented by the following general formula (I). Provided is a method for producing an organic thin film.

（式中、Ｒはπ電子共役系を有する有機基であり；Ｘ^１、Ｘ^２及びＸ^３はそれぞれ独立して、これらが結合しているケイ素原子（Ｓｉ）と前記親水性基との反応で離脱する基である。）

(Wherein R is an organic group having a π-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.)

The present invention is also an organic thin film provided on a substrate, wherein the first organic molecules are erected and scattered by chemical bonds on the substrate, and the second organic molecules are the first organic molecules. Provided is an organic thin film characterized by being arranged with respect to one organic molecule.
The present invention also provides an organic thin film characterized in that in the organic thin film, the second organic molecule is arranged by intermolecular interaction with respect to the first organic molecule.
The present invention also provides an organic thin film characterized in that in the organic thin film, the first and second organic molecules have a π-electron conjugated system.
Further, the present invention is characterized in that, in such an organic thin film, the first organic molecule is chemically bonded onto the substrate by contact between the solution containing the first organic molecule and the substrate. An organic thin film is provided.
Further, the present invention is characterized in that in the organic thin film, the density of the first organic molecule chemically bonded on the substrate is adjusted by the concentration of the solution containing the first organic molecule. An organic thin film is provided.
According to the present invention, in the organic thin film, the density of the first organic molecule chemically bonded on the substrate is adjusted by the contact time between the solution containing the first organic molecule and the substrate. An organic thin film is provided.
Further, the present invention provides an organic thin film characterized in that in the organic thin film, the second organic molecule is introduced and arranged on the substrate by application of a solution containing the second organic molecule. I will provide a.
The present invention also provides an organic thin film characterized in that in the organic thin film, the second organic molecule is introduced and arranged on the substrate by vapor deposition.
In the organic thin film according to the present invention, the base material has a hydrophilic group, and the first organic molecule is an organosilicon compound represented by the following general formula (I). Provide organic thin film.

（式中、Ｒはπ電子共役系を有する有機基であり；Ｘ^１、Ｘ^２及びＸ^３はそれぞれ独立して、これらが結合しているケイ素原子（Ｓｉ）と前記親水性基との反応で離脱する基である。）

(Wherein R is an organic group having a π-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.)

Moreover, this invention is a field effect transistor provided with the organic-semiconductor layer, Comprising: In this organic thin film, the said organic thin film in which said 1st and 2nd organic molecule is an organic-semiconductor molecule was provided as said organic-semiconductor layer. A field effect transistor is provided.
In addition, the present invention provides a field effect transistor including a gate electrode, a gate insulating film, a source electrode, a drain electrode, and an organic semiconductor layer, and the organic semiconductor layer faces the gate electrode through the gate insulating film. A field effect transistor is provided, wherein the source electrode and the drain electrode are provided in contact with the organic semiconductor layer.
In addition, the present invention provides a field effect transistor including a gate electrode, a gate insulating film, a source electrode, a drain electrode, and an organic semiconductor layer, and the organic semiconductor layer faces the gate electrode through the gate insulating film. A field effect transistor is provided in which the source electrode and the drain electrode are provided on the gate insulating film.

The present invention also provides 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. Provided is an organic light emitting device comprising an organic thin film in which two organic molecules are organic semiconductor molecules as the carrier transport layer.
The present invention also provides a solar cell comprising 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. Provided is a solar cell comprising an organic thin film whose second organic molecule is an organic semiconductor molecule as the p-type semiconductor layer and / or the n-type semiconductor layer.
In addition, the present invention provides an array for a display device comprising such a field effect transistor as a switching element.
The present invention also includes an image signal output unit that generates and outputs an image signal, a drive unit that generates current or voltage based on the image signal, and a light emitting unit that emits light based on the generated current or voltage. Provided is a display device, wherein the light emitting unit is such an organic light emitting element.

  ADVANTAGE OF THE INVENTION According to this invention, the organic thin film which has the sufficient function by which the orientation of an organic molecule is controlled, its manufacturing method, the organic electronic device and display apparatus using this organic thin film can be provided.

It is a schematic diagram for demonstrating the mismatching of the periodicity of the molecular arrangement | sequence in an organic thin film. It is a schematic diagram for demonstrating the manufacturing method of the organic thin film which concerns on this invention. It is a schematic diagram which illustrates a mode that the 1st organic molecule forms the siloxane bond and has couple | bonded with the base material. A graph illustrating the relationship between the concentration of the first organic molecule in the liquid and the work function in the case where the first organic molecule is scattered on the substrate using the liquid containing the first organic molecule. is there. It is a schematic sectional drawing which illustrates the principal part of the field effect transistor concerning a first embodiment. It is a schematic sectional drawing which illustrates the principal part of the field effect transistor which concerns on 2nd embodiment. It is a schematic sectional drawing which illustrates the principal part of the field effect transistor which concerns on 3rd embodiment. It is a schematic sectional drawing which illustrates the principal part of the field effect transistor which concerns on 4th embodiment. It is a schematic sectional drawing for demonstrating the manufacturing method of the field effect transistor shown in FIG. It is a schematic sectional drawing for demonstrating the manufacturing method of the field effect transistor shown in FIG. It is a schematic sectional drawing which illustrates the principal part of the solar cell concerning this invention. It is a schematic sectional drawing for demonstrating the manufacturing method of the solar cell shown in FIG. It is a schematic sectional drawing which illustrates the principal part of the organic light emitting element which concerns on this invention. It is a schematic sectional drawing for demonstrating the manufacturing method of the organic light emitting element shown in FIG. It is the schematic which illustrates the principal part of the array for display apparatuses which concerns on this invention, (a) is a top view, (b) is an enlarged plan view, (c) is sectional drawing in CC line of (b), (D) is sectional drawing in the DD line of (b). It is a schematic sectional drawing for demonstrating the manufacturing method of the organic-semiconductor device in the array for display apparatuses which concerns on this invention. 1A and 1B are schematic views illustrating the main part of a display device according to the present invention, in which FIG. 1A is a plan view, FIG. 1B is an equivalent circuit diagram of one pixel, and FIG.

<Organic thin film and manufacturing method thereof>
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. (Hereinafter abbreviated as “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. And a step of forming (hereinafter abbreviated as “film formation step”). This manufacturing method will be described in detail below with reference to FIG.

[Distributed process]
FIG. 2 is a schematic diagram for explaining a method for producing an organic thin film according to the present invention.
In the interspersing step, as shown in FIGS. 2A and 2B, the first organic molecules 61 are stood on the base material 60 by being chemically bonded, and are interspersed. In this step, since the first organic molecules 61 are only scattered on the substrate 60, the first organic molecules 61 do not form a thin film. In FIG. 2, for easy understanding, the first organic molecule 61 is indicated by a rectangle, and the binding site between the first organic molecule 61 and the substrate 60 is indicated by a triangle.

The base material 60 can be arbitrarily selected according to the use of the organic thin film. For example, when an organic semiconductor thin film is manufactured, 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.

Further, 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. .
And, preferred substrates 60, a hydroxyl group (-OH), a carboxyl group (-C (= O) -OH) , an amino group _(-NH 2), hydroxyl amino group (-NHOH), an imino group (= NH) And a hydrophilic group having an active hydrogen such as a thiol group (—SH) exposed on the surface and subjected to a hydrophilic treatment.
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 according to 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. Here, examples of the intermolecular interaction include π-π interaction, interaction by van der Waals force, interaction by hydrogen bond, interaction by Coulomb force (charge-charge interaction), charge transfer interaction, etc. it can. As the first organic molecule 61, a semiconductor molecule is also preferable.
In addition, 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—). Here, the substrate 60 is shown with a silicon oxide (SiO ₂ ) film formed on the surface, and the hydroxyl group (—OH) is partially exposed and rendered hydrophilic. And 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 | part 61a. This is the same if the surface of the substrate 60 is subjected to a hydrophilic treatment. 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.
On the other hand, 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. Thereby, it is considered that 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.
In addition, although the structure of the site | part which participated in this coupling | bonding changes a part of 1st organic molecule by couple | bonding with a base material, in this specification, for the sake of convenience, after binding to a base material, the 1st organic molecule Called.

  The first organic molecule 61 is preferably an organosilicon compound represented by the following general formula (I) (hereinafter abbreviated as organosilicon compound (I)).

（式中、Ｒはπ電子共役系を有する有機基であり；Ｘ^１、Ｘ^２及びＸ^３はそれぞれ独立して、これらが結合しているケイ素原子（Ｓｉ）と前記親水性基との反応で離脱する基である。）

(Wherein R is an organic group having a π-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.)

  In the formula, R is an organic group having a π-electron conjugated system, and a group capable of forming a π-π stacking structure with a second organic molecule described later by an intermolecular interaction (π-π interaction). It is. The organic group is not particularly limited as long as it has a π 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.
Examples of 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. Examples of 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 preferable that it is 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. Examples thereof include 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—).

In the formula, 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.

  Preferred examples of the organosilicon compound (I) include those represented by the following general formula.

（式中、Ｘ^１、Ｘ^２及びＸ^３はそれぞれ独立して、これらが結合しているケイ素原子（Ｓｉ）と前記親水性基との反応で離脱する基であり；Ｍは遷移金属原子である。）

(In the 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.)

^Wherein, X 1, ^{X 2} and ^{X 3} are the same as ^X 1, ^{X 2} and ^{X 3} in the general formula (I).
In the formula, 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. It can also be used as an n-type organic semiconductor by substituting with an electron withdrawing group such as a group (—CF ₃ ) or a cyano group (—C≡N).

  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.

  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.

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.
When the first organic molecules 61 are scattered on the base material 60 using the liquid containing the first organic molecules 61, the density of the first organic molecules 61 on the base material 60 (the degree of the scattering). 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.

Usually, it is difficult to directly measure the density of molecules on the substrate (molecular density). Therefore, a method of indirectly evaluating the molecular density by evaluating the change in the work function of the substrate surface, which is known to have a correlation with the molecular density, is applied.
For example, when the molecule on the substrate is considered to have a dipole moment μ, the molecular density d on the substrate and the work function change ΔWF on the substrate surface due to the dipole moment μ are expressed by the following equation (1). Have the relationship expressed.
ΔWF = μd / 2ε ₀ (1)
(Where d is the molecular density on the substrate; μ is the dipole moment the molecule has; ΔWF is the amount of change in the work function of the substrate surface due to the dipole moment μ; ε ₀ is in vacuum Dielectric constant.)
On the other hand, when the work function of the material itself constituting the substrate surface is WF ₀ , the work function WF of the substrate surface to which molecules are bonded is represented by the following formula (2).
WF = WF ₀ + ΔWF (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; ΔWF is the work function of the substrate surface due to the dipole moment μ) The amount of change
In Equation (2), WF ₀ is a constant, and ΔWF 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.

Here, as described above, when the first organic molecule is scattered on the substrate using the liquid containing the first organic molecule, the reaction of the first organic molecule binding on the substrate is The 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 ΔWF of the equation (2), the following equation (3) is obtained.
WF = WF ₀ + WF _sat {1-exp (−k × t × Z ₁ )} (3)
( _Where 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.

Thus, in certain materials, changing the concentration and processing time of the first organic molecule changes the number of first organic molecules that bind to the substrate, which can be evaluated as a change in work function. . 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 “μM” indicates “μmol / 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. In order to reduce the density of the first organic molecules on the substrate, 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 μmol / L can be selected as a preferred concentration of the first organic molecule. Here, the case where the treatment time is constant has been described, but conversely, when the concentration of the first organic molecule is constant, by adjusting the treatment time, the molecules on the surface of the substrate are similarly treated. The density can also be adjusted. For example, in the reaction conditions when the graph of FIG. 4 is created, the concentration of the first organic molecule is constant (1 × 10 ⁻⁴ μmol / 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.

[Film formation process]
Next, in the film forming step, as shown in FIG. 2C, the second organic molecules 62 are introduced onto the base material 60 on which the first organic molecules 61 are scattered, and the first organic molecules are introduced. The second organic molecules 62 are arranged with respect to 61 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. As the second organic molecule 62, 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)).
RH (II)
(In the formula, R is an organic group having a π electron conjugated system.)

In the formula, 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.

  The second organic molecule 62 may be one kind or two or more kinds. When there are 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.

For example, the second organic molecule 62 forms a stacking structure with the first organic molecule 61 by an intermolecular interaction such as a π-π interaction, and also between the second organic molecules 62. Similarly, when a stacking structure is formed, the orientation is better controlled on the base material 60 to form a thin film. From this point of view, 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 π-electron conjugated system, because the stacking structure is further strengthened. The same as 61 is preferable.
In order to form the thin film as described above, for example, as long as the thin film can be formed, 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. When the second organic molecule 62 is introduced, unlike the case where the first organic molecule 61 is chemically bonded to the substrate 60, precise adjustment of conditions is unnecessary, and a lower cost method can be applied. . When a liquid containing the second organic molecule 62 is used, examples of a preferable method for introducing the second organic molecule 62 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.
Moreover, as a preferable method for introducing the second organic molecule 62, 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.

  After the film forming step, the formed organic thin film may be washed or the like 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.
Unlike the conventional SAM film, 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. When the first and second organic molecules have a π-electron conjugated system, for example, 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 π-electron conjugated system, and the radial radius Is expected to increase. As a result, it is considered that, as a result, the degree of freedom of the arrangement structure is usually increased, and the thin film has many orientation disturbances and defects. However, such a problem does not occur in the organic thin film according to the present invention for the above reasons.
Moreover, since 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. .

<Field effect transistor>
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.
For example, when the first and second organic molecules exemplified above are used as the organic thin film, the organic thin film is mainly used as a p-type semiconductor layer. When 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.
Hereinafter, description will be given with reference to the drawings.

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. For example, glass, quartz, silicon single crystal, polycrystalline silicon, amorphous silicon; high insulation such as polyimide, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polytetrafluoroethylene Examples thereof include molecular compounds.
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, a low-resistance metal such as gold, platinum, silver, copper, aluminum, tantalum, and doped silicon; 3,4-polyethylenedioxythiophene (hereinafter abbreviated as PEDOT) / polystyrene sulfate (hereinafter, Examples thereof include organic conductors such as PSS).

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. 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. For example, when 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.
In addition, 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. It is preferable that 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 ”.
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 thickness of the gate insulating film 13 is preferably adjusted as appropriate according to the relative dielectric constant, insulating properties, etc. of the material, and is preferably 50 to 300 nm, for example. By doing so, the capacitance per unit area can be increased, and the threshold voltage of the field effect transistor can be reduced.
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.
As described above, 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. In FIG. 6, the same components as those shown in FIG. 5 are denoted by the same reference numerals as those in FIG. 5, and detailed description thereof is omitted. The same applies to the following drawings.
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.

As with the field effect transistor 1A, 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.
(I) As illustrated in FIG. 7, 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).
(II) As illustrated in FIG. 8, 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.

In the field effect transistors 1C and 1D, since the organic semiconductor layer 16 is provided on the substrate 11, 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. In this case, 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. FIG. 9 is a schematic cross-sectional view for explaining the method of manufacturing the field effect transistor 1A.
A film made of a 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. 9A, the film on the substrate 11 is formed. A gate electrode 12 is formed at a predetermined location. An example of the film formation method is a sputtering method.

  Next, as shown in FIG. 9B, 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.

  Next, as shown in FIG. 9C, the 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.

Next, as shown in FIG. 9D, 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. To do.
By performing the above steps, a field effect transistor 1A shown in FIG. 5 is obtained.

Next, a method for manufacturing the field effect transistor 1B shown in FIG. 6 will be described. FIG. 10 is a schematic cross-sectional view for explaining the method of manufacturing the field effect transistor 1A.
As shown in FIGS. 10A and 10B, the gate electrode 12 and the gate insulating film 13 are formed on the substrate 11 by the same method as described with reference to FIGS. To do.

  Next, after a resist film is formed on the gate insulating film 13 by a spin coating method or the like, exposure and development are performed by a photolithography method, so that a photoresist having a predetermined pattern is obtained as shown in FIG. A film 90 is formed. The photoresist film 90 is for forming the source electrode 14 and the drain electrode 15 and has openings corresponding to these shapes.

  Next, 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, so that FIG. As shown, a source electrode 14 and a drain electrode 15 are formed at predetermined locations on the gate insulating film 13. At this time, before forming the metal film, 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. Examples of 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. When the metal film formed on the photoresist film 90 and further an adhesion layer are formed by removing the photoresist film 90, 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.

Next, as shown in FIG. 10E, 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.
When providing a surface modification layer on the surface of the source electrode 14 and the drain electrode 15, after forming the source electrode 14 and the drain electrode 15 as shown in FIG.10 (d), a surface modifier is made to act on these surfaces. Then, after forming the surface modification layer, the organic semiconductor layer 16 may be formed as shown in FIG.

<Solar cell>
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.
For example, when the first and second organic molecules exemplified above are used as the organic thin film, the organic thin film is mainly used as a p-type semiconductor layer. When 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.
Hereinafter, description will be given with reference to the drawings.

FIG. 11 is a schematic cross-sectional view illustrating the main part of the solar cell according to the present invention.
In the solar cell 2A shown here, 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. When the n-type semiconductor layer 25 is the organic thin film, 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. When the n-type semiconductor layer 25 is formed of a known material, preferred materials include fullerene; fullerene derivatives such as [6,6] -phenyl C61 butyric acid methyl ester (PCBM); one or more constituting a phthalimide ring Examples of 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.

  Any 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.

In the case where the p-type semiconductor layer 24 is the organic thin film, 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 having excellent 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 film 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.
FIG. 12 is a schematic cross-sectional view for explaining a method for manufacturing solar cell 2A.
First, as shown in FIG. 12A, an anode electrode 22 is formed on a glass substrate 21. Examples of the method for forming the anode electrode 22 include a sputtering method.

  Next, as shown in FIG. 12B, a p-type semiconductor layer 24 is formed on the anode electrode 22. As a method for forming the p-type semiconductor layer 24, when the p-type semiconductor layer 24 is the organic thin film, the method for producing the organic thin film can be exemplified. When the p-type semiconductor layer 24 is not the organic thin film, a vacuum deposition method is exemplified. it can.

  Next, as shown in FIG. 12C, an n-type semiconductor layer 25 is formed on the p-type semiconductor layer 24. As a method for forming the n-type semiconductor layer 25, when the n-type semiconductor layer 25 is the organic thin film, 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.

Next, as shown in FIG. 12D, 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.

<Organic light emitting device>
The organic light-emitting device according to the present invention 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.
For example, when the first and second organic molecules exemplified above are used as the organic thin film, the organic thin film is mainly used as a p-type semiconductor layer. When 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).
Hereinafter, description will be given with reference to the drawings.

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.

  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.

In the organic EL section 34, 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.
As described above, 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.

In the carrier injection layer 34a, 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).
As a material applied to the carrier injection layer 34a, 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 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-t-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.
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.

In the electron transport layer 34d and the electron injection layer 34e, 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. In particular, 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.
Further, as a material applied to the electron injection layer 34e, from the viewpoint of more efficiently injecting and transporting electrons from the cathode, the minimum unoccupied molecular orbital (LUMO) than the electron injection / transport material applied to the electron transport layer 34d is used. 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 according to the present invention is not limited to the one shown in FIG. 13, and a part of its configuration may be changed. For example, the structure of the organic EL unit 34 as follows can be given.
(I) An organic EL part in which a carrier transport layer, a light emitting layer, and an electron transport layer are laminated in this order from the anode electrode 32 side to the cathode electrode 33 side.
(Ii) An organic EL part in which a carrier injection layer, a carrier transport layer, a light emitting layer, and an electron transport layer are laminated in this order from the anode electrode 32 side to the cathode electrode 33 side.
(Iii) 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.
(Iv) 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.
FIG. 14 is a schematic cross-sectional view for explaining the method for manufacturing the organic light emitting device 3A.
First, as shown in FIG. 14A, the anode electrode 32 is formed on the glass substrate 31. An example of a method for forming the anode electrode 32 is a sputtering method.

  Next, as shown in FIG. 14B, a carrier injection layer 34 a is formed on the anode electrode 32. As a method for forming the carrier injection layer 34a, a spin coating method can be exemplified.

  Next, as shown in FIG. 14C, 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.

  Next, as shown in FIG. 14D, the 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.

  Next, as shown in FIG. 14E, 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.

  Next, as shown in FIG. 14F, an electron injection layer 34e is formed on the electron transport layer 34d. As a method for forming the electron injection layer 34e, a vacuum deposition method can be exemplified.

Next, as shown in FIG. 14G, the cathode electrode 33 is formed on the electron injection layer 34e. As a method for forming the cathode electrode 33, a vacuum deposition method can be exemplified.
By performing the above steps, an organic light emitting device 3A shown in FIG. 13 is obtained.

<Arrays for display devices>
The array for a display device according to the present invention 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.
Hereinafter, description will be given with reference to the drawings.

FIG. 15 is a schematic view illustrating the main part of the array for a display device according to the present invention, where (a) is a plan view, (b) is an enlarged plan view, and (c) is a CC line of (b). (D) is sectional drawing in the DD line of (b).
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. FIG. 16 is a schematic cross-sectional view for explaining a method for manufacturing the organic semiconductor device 42.
First, in the same manner as described with reference to FIGS. 10A to 10C, the gate wiring 40 (gate electrode 12) is formed on the substrate 11 as shown in FIGS. Then, the gate insulating film 13 is sequentially formed, and then 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.
Next, as shown in FIG. 16D, the source electrode 14 and the drain electrode 15 are formed by a method similar to the method described with reference to FIG. Further, 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.
Next, 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. Form. 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, the organic semiconductor device 42 is obtained.
Then, the obtained organic semiconductor devices 42 are arranged in a matrix, whereby the display device array 4A is obtained.

Here, an example is shown in which the field effect transistor 1B is used as the field effect transistor, but other field effect transistors can also be used, and the configuration of the organic semiconductor device may be adjusted according to the configuration.
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.

<Display device>
The display device according to the present invention 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. , Wherein the light emitting unit is the organic light emitting element. And it can be set as the structure similar to the conventional display apparatus except having provided this organic light emitting element.
The display device according to the present invention includes the organic light-emitting element, so that good light emission characteristics can be obtained.
Hereinafter, description will be given with reference to the drawings.

17A and 17B are schematic views illustrating the main part of the display device according to the present invention, in which FIG. 17A is a plan view, FIG. 17B is an equivalent circuit diagram of one pixel, and 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.
In the display device 5A, 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. In the peripheral region of the pixel array, 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. 17B, 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, In addition, a storage capacitor 54 is provided, and a pixel portion including 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.

  Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples.

<Manufacture of organic semiconductor thin film>
[Example 1]
In the Si substrate (thickness: 1 mm) having a silicon oxide film (SiO ₂ ) having a thickness of 300 nm on the surface, the surface of the oxide film was hydrophilized by UV ozone treatment. Next, in an inert gas atmosphere, the concentration of quarterthiophenetrichlorosilane having a concentration determined based on the relationship of the above formula (3) (in the organosilicon compound represented by the above general formula (I) -102, X ¹ , X ^The Si substrate hydrophilized is immersed in an anhydrous toluene solution (concentration: 1 × 10 ⁻³ μmol / 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.
Next, a chloroform saturated solution of quarterthiophene (second organic molecule) was applied to the Si substrate to which quarterthiophene was bonded by spin coating (rotation speed: 1500 rpm) to form an organic semiconductor thin film. The film thickness of the obtained organic semiconductor thin film was about 2 nm.
When this thin film was observed with an atomic force microscope (AFM), it was confirmed that the orientation of organic molecules was controlled and the film was uniform without grains.

<Manufacture of field effect transistors>
[Example 2]
The field effect transistor 1A shown in FIG. 5 was manufactured by the manufacturing method described with reference to FIG. More specifically, it is as follows.
As 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). 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 μm, and the length of the opposing electrode (channel width) was 1000 μm.
The field effect mobility of the obtained field effect transistor 1A was measured and found to be 8 × 10 ⁻² cm ² / Vs. By using 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.

[Example 3]
The field effect transistor 1B shown in FIG. 6 was manufactured by the manufacturing method described with reference to FIG. More specifically, it is as follows.
As 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). 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 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.
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 μm, and the length of the opposing electrode (channel width) was 1000 μm.
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 replaces pentacene with 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.
With respect to the obtained field effect transistor 1B, 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. By using 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.

<Manufacture of solar cells>
[Example 4]
The solar cell 2A shown in FIG. 11 was manufactured by the manufacturing method described with reference to FIG. More specifically, it is as follows.
As the glass substrate 21, “Corning Corp., Eagle 2000, thickness: 0.5 mm” was used.
As the anode electrode 22, an ITO film having a thickness of 150 nm was formed on the glass substrate 21 by a sputtering method.
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.
As the n-type semiconductor layer 25, 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.

<Manufacture of organic light emitting devices>
[Example 5]
The organic light emitting device 3A shown in FIG. 13 was manufactured by the manufacturing method described with reference to FIG. 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 the film thickness was about 50 nm.
The carrier transport layer 34b has terthiophenetrichlorosilane as the first organic molecule instead of quarterthiophenetrichlorosilane (in the organosilicon compound represented by the general formula (I) -101, X ¹ , X ^2, and X ³ are (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 composed of 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 co-evaporation was performed. 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.
With respect to the obtained organic light emitting device 3A, a 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.

<Manufacture of arrays for display devices>
[Example 6]
The display device array 4A shown in FIG. 15 was manufactured by the manufacturing method described with reference to FIG. More specifically, it is as follows.
As the substrate 11, a glass substrate (Corning, Eagle 2000, thickness: 0.5 mm) was used.
The material of the gate wiring 40 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 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.
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 μm, and the length of the opposing electrode (channel width) was 1000 μm.
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 replaced with quarter-triophentrichlorosilane as a first organic molecule, 2-trichlorosilylpentacene (in the organosilicon compound represented by the general formula (I) -303, X ¹ , X ² and X ³ 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.

<Manufacture of display devices>
[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 FIG. 17 was manufactured. The organic light emitting device 3A was manufactured by the same method as in Example 5.

  The present invention is applicable to semiconductor devices such as field effect transistors, solar cells, and organic light emitting elements.

  DESCRIPTION OF SYMBOLS 1A, 1B ... Field effect transistor, 11 ... Substrate, 12 ... Gate electrode, 13 ... Gate insulating film, 14 ... Source electrode, 15 ... Drain electrode, 16 ... Organic Semiconductor layer, 2A ... solar cell, 21 ... glass substrate, 22 ... anode electrode, 23 ... cathode electrode, 24 ... p-type semiconductor layer, 25 ... n-type semiconductor layer, 3 , 3A ... organic light emitting device, 31 ... glass substrate, 32 ... anode electrode, 33 ... cathode electrode, 34b ... carrier transport layer, 34c ... light emitting layer, 4A ... display Array for device, 40 ... gate wiring, 5A ... display device, 55 ... scanning line driving circuit (gate driver), 56 ... signal line driving circuit (source driver), 57 ... controller, 6 ... Organic thin film, 60 ... Base , 61 ... first of organic molecules, 62 ... second organic molecules

Claims (25)

A method for producing an organic thin film provided on a substrate,
A step of establishing a chemical bond of the first organic molecules on the base material,
Introducing a second organic molecule on the substrate, arranging the second organic molecule with respect to the first organic molecule, and forming a thin film;
A method for producing an organic thin film characterized by comprising:   2. The method for producing an organic thin film according to claim 1, wherein the second organic molecule is arranged by intermolecular interaction with respect to the first organic molecule.   The method for producing an organic thin film according to claim 1, wherein the first and second organic molecules have a π-electron conjugated system.   The solution in which the first organic molecule is dissolved is brought into contact with the base material to chemically bond the first organic molecule onto the base material. The manufacturing method of the organic thin film of description.   The organic thin film manufacturing method according to claim 4, wherein the density of the first organic molecule chemically bonded on the substrate is adjusted according to the concentration of the solution in which the first organic molecule is dissolved. Method.   The density of the first organic molecule chemically bonded on the substrate is adjusted according to a contact time between the solution in which the first organic molecule is dissolved and the substrate. 5. The method for producing an organic thin film according to 5.   The organic according to any one of claims 1 to 6, wherein the second organic molecule is introduced onto the substrate by applying a solution in which the second organic molecule is dissolved. Thin film manufacturing method.   The method for producing an organic thin film according to any one of claims 1 to 6, wherein the second organic molecule is introduced onto the base material by vapor deposition. 9. The substrate according to claim 1, wherein the substrate has a hydrophilic group, and the first organic molecule is an organosilicon compound represented by the following general formula (I). The manufacturing method of the organic thin film of description.

(Wherein R is an organic group having a π-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.) An organic thin film provided on a substrate,
On the substrate, the first organic molecules are erected and scattered by chemical bonds,
An organic thin film characterized in that second organic molecules are arranged with respect to the first organic molecules.   The organic thin film according to claim 10, wherein the second organic molecule is arranged by intermolecular interaction with respect to the first organic molecule.   The organic thin film according to claim 10 or 11, wherein the first and second organic molecules have a π electron conjugated system.   The said 1st organic molecule was chemically bonded on the said base material by the contact of the solution containing said 1st organic molecule, and the said base material, The any one of Claims 10-12 characterized by the above-mentioned. Organic thin film as described in 2.   14. The organic thin film according to claim 13, wherein the density of the first organic molecules chemically bonded on the substrate is adjusted by the concentration of the solution containing the first organic molecules.   The density of the first organic molecule chemically bonded on the base material is adjusted by the contact time between the solution containing the first organic molecule and the base material. 14. The organic thin film as described in 14.   The said 2nd organic molecule was introduce | transduced and arranged on the said base material by application | coating of the solution containing said 2nd organic molecule | numerator, It is any one of Claims 10-15 characterized by the above-mentioned. Organic thin film.   The organic thin film according to any one of claims 10 to 15, wherein the second organic molecules are introduced and arranged on the base material by vapor deposition. The base material has a hydrophilic group, and the first organic molecule is an organosilicon compound represented by the following general formula (I). The organic thin film as described.

(Wherein R is an organic group having a π-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 field effect transistor comprising an organic semiconductor layer,
The organic thin film according to any one of claims 10 to 18, wherein the organic semiconductor layer includes an organic thin film in which the first and second organic molecules are organic semiconductor molecules. Transistor. A gate electrode, a gate insulating film, a source electrode, a drain electrode and an organic semiconductor layer;
The organic semiconductor layer is provided so as to face the gate electrode through the gate insulating film,
The field effect transistor according to claim 19, wherein the source electrode and the drain electrode are 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;
The organic semiconductor layer is provided so as to face the gate electrode through the gate insulating film,
The field effect transistor according to claim 19, wherein the source electrode and the drain electrode are provided on the gate insulating film. An organic light emitting device comprising a pair of electrodes on a substrate, and comprising at least a carrier transport layer and a light emitting layer between the pair of electrodes,
The organic thin film according to any one of claims 10 to 18, wherein the organic thin film in which the first and second organic molecules are organic semiconductor molecules is provided as the carrier transport layer. element. A solar cell comprising a pair of electrodes on a substrate, and comprising a p-type semiconductor layer and an n-type semiconductor layer between the pair of electrodes,
19. The organic thin film according to claim 10, wherein the first and second organic molecules are organic semiconductor molecules as the p-type semiconductor layer and / or the n-type semiconductor layer. A solar cell characterized by that.   An array for a display device comprising the field effect transistor according to any one of claims 19 to 21 as a switching element. An image signal output unit that generates and outputs an image signal, a drive unit that generates current or voltage based on the image signal, and a light emitting unit that emits light by the generated current or voltage. And
The display device, wherein the light emitting unit is the organic light emitting element according to claim 22.

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