JP2009152623A - Organic electronic device, method for production thereof, and organic semiconductor molecule - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic electronic device which is physically stable and relatively easy to manufacture. <P>SOLUTION: The organic electronic device has a conductive path including fine particles (A) and an organic semiconductor molecule (B) binding the fine particles together and behaving as p-type, wherein the organic semiconductor molecule is represented by structural formula (1) wherein: R<SB>1</SB>and R<SB>2</SB>denote alkyl groups; M denotes 2H, Z<SP>n+2</SP>, Mg<SP>+2</SP>, Fe<SP>+2</SP>, Co<SP>+2</SP>, Ni<SP>+2</SP>, or Cu<SP>+2</SP>; and n is an integer of 1 to 5. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an organic electronic device, a manufacturing method thereof, and a novel organic semiconductor molecule.

Field effect transistors (FETs) including thin film transistors (TFTs) currently used in many electronic devices are, for example, channel formation regions formed in a silicon semiconductor substrate or silicon semiconductor layer. And a source / drain region, a gate insulating layer made of SiO ₂ formed on the surface of the silicon semiconductor substrate or the silicon semiconductor layer, and a gate electrode provided facing the channel forming region through the gate insulating layer. ing. Alternatively, it includes a gate electrode formed on the support, a gate insulating layer formed on the support including the gate electrode, and a channel formation region and a source / drain region formed on the gate insulating layer. ing. For manufacturing field effect transistors (FETs) having these structures, very expensive semiconductor manufacturing apparatuses are used, and reduction of manufacturing costs is strongly demanded.

  Therefore, in recent years, attention has been focused on the research and development of various organic electronic devices including FETs using organic semiconductor materials that can be manufactured based on methods that do not use vacuum technology exemplified by spin coating, printing, and spraying. Gathered. By the way, there are many research reports on the development of organic electronic devices using p-type organic semiconductor materials, but there are few research reports on the development of organic electronic devices using n-type organic semiconductor materials. In order to widely apply organic semiconductor materials to various transistors including pn junctions, photoelectric conversion elements, bipolar transistors and complementary transistors, development of n-type organic semiconductor materials, development of p-type organic semiconductor materials, It is necessary to proceed in parallel (for example, Reference 1: Shinji, A., et. Al. J. Am, Chem. Soc. 2005, 127, 14996, Reference 2: Facchetti. A., et. Al. Angew. Chem. Int. Ed. 2003, 42, 3900, Reference 3: Locklin, AJ, et. Al. Chem. Mater. 2003, 15, 1404, Reference 4: Chesterfield, RJ, et. Al. Adv. Mater. 2003, 15, 1278). Until now, pentacene substituted with a fluoroalkyl group as an applicable n-type organic semiconductor material (refer to Reference 5: Sakamoto, Y., et. Al. J. Am, Chem. Soc. 2004, 126, 8138), Oligothiophene, thiazole oligomers (Ref. 6: see Yoon, MH, et. Al. J. Am, Chem. Soc. 2005, 127, 1348) have been reported. It is also important to develop p-type organic semiconductor materials with even better characteristics.

Shinji, A., et. Al. J. Am, Chem. Soc. 2005, 127, 14996 Facchetti. A., et. Al. Angew. Chem. Int. Ed. 2003, 42, 3900 Locklin, A. J., et. Al. Chem. Mater. 2003, 15, 1404 Chesterfield, R. J., et. Al. Adv. Mater. 2003, 15, 1278 Sakamoto, Y., et. Al. J. Am, Chem. Soc. 2004, 126, 8138 Yoon, M. H., et. Al. J. Am, Chem. Soc. 2005, 127, 1348 X. Xiao et. Al. J. Am. Chem. Soc. 2005, 127, 9235-9240 K. Tashiro et. Al. J. Am. Chem. Soc. 1999, 121, 9477-9478 M. Shiragawa et. Al. J. Am. Chem. Soc. 2003, 125, 9902-9903 H. Imahori et. Al. Chem. Eur. J. 2005, 11, 7265-7275 B. C. Sih et. Al. Chem. Commun. 2005, 3375-3384

  By the way, the n-type organic semiconductor material disclosed in the above-described literature is synthesized by a complicated process of several stages and applied to various devices. However, for the practical application of various organic electronic devices, it is one of very important issues to reduce the manufacturing cost of various organic electronic devices by developing simpler processes. In general, n-type organic semiconductor materials are easily oxidized in the air. Therefore, the degree of freedom of selection of n-type organic semiconductor materials is low, and the manufacturing process of organic electronic devices composed of n-type organic semiconductor materials is complicated. Has the problem of becoming. There is also a high demand for p-type organic semiconductor materials with even better characteristics.

  Accordingly, a first object of the present invention is to provide an organic electronic device that is stable in physical properties and relatively easy to manufacture, and a method for manufacturing the same. A second object of the present invention is to provide an organic semiconductor molecule having further excellent characteristics, an organic electronic device using the organic semiconductor molecule, and a method for producing the same.

The organic electronic device according to the first aspect of the present invention for achieving the first object is as follows.
(A) fine particles,
(B) a first organic semiconductor molecule having a first conductivity type, in which fine particles are combined, and
(C) a second organic semiconductor molecule having a second conductivity type and trapped in a non-covalent bonding state in a molecular recognition field existing between the fine particles;
It comprises the conductive path which consists of.

The method for manufacturing an organic electronic device according to the first aspect of the present invention for achieving the first object is as follows.
On the substrate,
(A) fine particles, and
(B) a first organic semiconductor molecule having a first conductivity type, in which fine particles and fine particles are combined;
After forming the fine particle / first organic semiconductor molecule / bonding layer,
Contacting the fine particle / first organic semiconductor molecule / bonding layer with a second organic semiconductor molecule having the second conductivity type;
(A) fine particles,
(B) a first organic semiconductor molecule having a first conductivity type, in which fine particles are combined, and
(C) a second organic semiconductor molecule having a second conductivity type and trapped in a non-covalent bonding state in a molecular recognition field existing between the fine particles;
It is characterized by obtaining a conductive path consisting of

  Here, molecular recognition generally means that a molecule forms an aggregate, an addition compound, a cluster compound, a mixed crystal, etc. with a limited molecule rather than an arbitrary partner molecule, and exhibits selectivity. Means. The molecular recognition field in the first aspect of the present invention is a field where the second organic semiconductor molecule can form a supramolecular aggregate selectively utilizing intermolecular force with the first organic semiconductor molecule. means. In addition, “captured in a non-covalent bond state” specifically means that the second organic semiconductor molecule is in the following state. That is, the fine particles are linked by the first organic semiconductor molecules to form a network-like network structure, and there are many nanospaces. In the nanospace, the second organic semiconductor molecules are the first organic semiconductor molecules. It means that it is confined by π-π interaction with an organic semiconductor molecule. It can be verified by the method described below that the second organic semiconductor molecule is captured in a molecular recognition field existing between the fine particles in a non-covalent bond state. That is, after sufficiently washing, the UV-Vis absorption spectrum is measured. Then, an absorption peak derived from the second organic semiconductor molecule appears. Further, in the absorption peak derived from the surrounding first organic semiconductor molecule, a shift to the long wavelength of the absorption peak is observed due to intermolecular interaction with the second organic semiconductor molecule. On the other hand, if an aggregate is formed by the first organic semiconductor molecule and the second organic semiconductor molecule, energy transfer or electron transfer between the molecules is promoted, and this is observed by a technique such as fluorescence decay or excessive absorption. be able to.

The organic electronic device according to the second aspect of the present invention for achieving the second object described above,
(A) fine particles, and
(B) an organic semiconductor molecule in which fine particles are combined,
Comprising a conductive path that behaves as a p-type,
The organic semiconductor molecule is represented by the following structural formula (1).

  In addition, the organic electronic device manufacturing method according to the second aspect of the present invention for achieving the second object described above is represented by the following structural formula (1) after forming a fine particle layer on a substrate. By immersing in a solution containing organic semiconductor molecules, a conductive path composed of fine particles and organic semiconductor molecules obtained by combining fine particles and fine particles and exhibiting a p-type behavior is formed.

In Structural Formula (1), R ₁ and R ₂ represent alkyl groups, and M represents 2H, Zn ⁺² , Mg ⁺² , Fe ⁺² , Co ⁺² , Ni ⁺² , and Cu ⁺² . , N is an integer from 1 to 5. Here, the conductive path is composed of fine particles / organic semiconductor molecules / bonding layers.

Furthermore, the organic semiconductor molecule of the present invention for achieving the second object is represented by the following structural formula (2). In Structural Formula (2), R ₁ and R ₂ represent alkyl groups, and M represents 2H, Zn ⁺² , Mg ⁺² , Fe ⁺² , Co ⁺² , Ni ⁺² , and Cu ⁺² . , N is an integer from 1 to 5. In addition, this organic-semiconductor molecule shows a p-type conductivity type.

Structural formula (1) broadly means thiophene porphyrin having a thiol group. Structural formula (2) broadly means thiophene porphyrin having a thioacetyl group. And this porphyrin organic-semiconductor molecule represented by Structural Formula (1) or Structural Formula (2) is comprised from three units of the anchor site | part chemically couple | bonded with the surface of microparticles | fine-particles, (pi) conjugated spacer, and a porphyrin skeleton. . Here, in the structural formula (1) or the structural formula (2), in the alkyl group C _m H _{2m + 1} represented by R ₁ and R ₂ , m is preferably an integer of 3 to 18. R ₁ and R ₂ may be the same or different. In some cases, X ₁ and X ₂ (where X ₁ and X ₂ are aromatic substituents containing an aryl group) can be used instead of R ₁ and R ₂ .

In the organic electronic device or the manufacturing method thereof according to the first aspect of the present invention (hereinafter, these may be collectively referred to simply as the first aspect of the present invention), the first conductivity type is p-type. The second conductivity type can be an n-type, and in this case, the conductive path is in the form of an n-type behavior that is the second conductivity type. In this case, the second organic semiconductor molecule may be a fullerene having stable physical properties (for example, a spherical shell-like carbon molecule such as C ₆₀ or C ₇₀ ), or TNT (2,4,6-trinitrotoluene), It can be composed of quantum dots and conjugated oligomers. However, the first conductivity type and the second conductivity type are not limited to this, and the first conductivity type may be n-type and the second conductivity type may be p-type. The conductive path is in a form showing the behavior as the p-type which is the second conductivity type.

In the first aspect of the present invention including the preferred form and configuration described above, the functional group that the first organic semiconductor molecule has at the end is preferably chemically bonded to the fine particles, It is preferable that a network-like conductive path is constructed by chemically (alternatively) bonding the first organic semiconductor molecules and the fine particles by the functional groups of the first organic semiconductor molecules at both ends. The conductive path may be constituted by a single layer of a combination of fine particles and first organic semiconductor molecules, or a three-dimensional network-like structure may be formed by a laminated structure of the combination of fine particles and first organic semiconductor molecules. A conductive path may be configured. By constructing a network-like conductive path in this way, charge transfer in the conductive path occurs predominantly in the axial direction of the molecule along the main chain of the first organic semiconductor molecule, and the conductive path is intermolecular. This structure does not include the electron transfer. As a result, the mobility is not limited by the electron transfer between molecules, which is the cause of the low mobility in the semiconductor device using the conventional organic semiconductor material, and the mobility in the axial direction of the molecule, for example, delocalization Since the high mobility due to the converted π electrons can be utilized to the maximum extent, it is possible to realize an unprecedented high mobility comparable to that of a monolayer transistor. In this case, the first organic semiconductor molecule is a conjugated organic semiconductor molecule having a functional group capable of chemically bonding or coordinating with atoms constituting the fine particles at both ends of the molecule, More specifically, thiol group (—SH), amino group (—NH ₂ ), isocyano group (—NC), thioacetyl group (—SCOCH ₃ ), trichlorosilane (—Si (Cl) ₃ ), ammonium group ( -NH ₃ ^+), phosphoric acid group, and may be in the form having at least one functional group selected from the group consisting of carboxyl group (-COOH).

  On the other hand, in the organic electronic device or the manufacturing method thereof according to the second aspect of the present invention (hereinafter, these may be collectively referred to simply as the second aspect of the present invention), the organic semiconductor molecule is terminated. It is preferable that the functional group (thiol group) of the organic semiconductor molecule is chemically bonded to the fine particle, and further, the organic semiconductor molecule and the fine particle are chemically bonded to each other by the functional group (thiol group) of the organic semiconductor molecule at both ends. It is preferable that a network-like conductive path is constructed by coupling (alternately). A conductive path may be constituted by a single layer of a conjugate of fine particles and organic semiconductor molecules, or a three-dimensional network-like conductive path is constituted by a laminated structure of a conjugate of fine particles and organic semiconductor molecules. May be. By constructing a network-like conductive path in this way, charge transfer in the conductive path occurs predominantly in the axial direction of the molecule along the main chain of the organic semiconductor molecule, and electron transfer between molecules in the conductive path The structure is not included. As a result, the mobility is not limited by the electron transfer between molecules, which is the cause of the low mobility in the semiconductor device using the conventional organic semiconductor material, and the mobility in the axial direction of the molecule, for example, delocalization Since the high mobility due to the converted π electrons can be utilized to the maximum extent, it is possible to realize an unprecedented high mobility comparable to that of a monolayer transistor.

Furthermore, in the first aspect or the second aspect of the present invention including the preferred modes and configurations described above, the fine particles can be made of a conductor, or can be made of a semiconductor. Alternatively, the structure may be made of an insulator. The fine particles as a conductor refer to fine particles made of a material having a volume resistivity of the order of 10 ⁻⁴ Ω · m (10 ⁻² Ω · cm) or less. The fine particles as a semiconductor refer to fine particles made of a material having a volume resistivity on the order of 10 ⁻⁴ Ω · m (10 ⁻² Ω · cm) to 10 ¹² Ω · m (10 ¹⁴ Ω · cm). . Furthermore, the fine particles as an insulator refer to fine particles made of a material whose volume resistivity exceeds the order of 10 ¹² Ω · m (10 ¹⁴ Ω · cm). More specifically, the material constituting the fine particles as a conductor is gold (Au), silver (Ag), platinum (Pt), copper (Cu), aluminum (Al), palladium (Pd), chromium (Cr). , Nickel (Ni), iron (Fe), or alloys made of these metals. More specifically, as a material constituting the fine particles as a semiconductor, titanium oxide (TiO ₂ ), tin oxide (SnO ₂ ), cadmium sulfide (CdS), cadmium selenide (CdSe), cadmium telluride (CdTe) ), Gallium arsenide (GaAs), or silicon (Si). More specifically, silicon oxide (SiO _x ) can be given as a material constituting the fine particles as the insulator. In these cases, the range of the average particle diameter R _AVE of the fine particles is not limited, but is 5.0 × 10 ⁻¹⁰ m ≦ R _AVE ≦ 1.0 × 10 ⁻⁶ m, preferably R _AVE ≦ It is desirable that 1 × 10 ⁻⁸ m, more preferably 5.0 × 10 ⁻¹⁰ m ≦ R _AVE ≦ 1.0 × 10 ⁻⁸ m. Examples of the shape of the fine particles include, but are not limited to, a spherical shape, a triangular shape, a tetrahedron, a cube, a rectangular parallelepiped, a cone, a cylindrical shape (rod), a triangular prism, a fiber shape, a hairball shape fiber, and the like. Can be mentioned. The average particle size R _AVE of the fine particles when the shape of the fine particles is other than a spherical shape is assumed to be a sphere having the same volume as the measured volume of the fine particles other than the spherical shape, and the average value of the diameters of the spheres is calculated as The particle size R _AVE may be used. The average particle size R _AVE of the fine particles can be obtained, for example, by measuring the particle size of the fine particles observed with a transmission electron microscope (TEM).

  In the first or second aspect of the present invention including the form and configuration described above, the fine particles on the substrate are regularly and two-dimensionally filled in a plane substantially parallel to the surface of the substrate. The fine particles may be arranged in a state to form a fine particle layer, and the fine particles are preferably arranged in a close packed state. Here, “fine particles are arranged in a packed state” means more specifically the first organic semiconductor molecule (the first aspect of the present invention) or the organic semiconductor molecule (the present invention) bonded to the fine particles. The second embodiment) (hereinafter, these may be collectively referred to as “first organic semiconductor molecules, etc.”), for example, at least to the extent that the conductive path is formed between the source / drain electrodes, A state in which fine particles are arranged. Needless to say, there may be some depletion, lattice defects, and the like. In addition, “fine particles are arranged in a close-packed state” means that when the fine particles are regarded as a rigid body, they are regularly arranged at the maximum density that can physically occupy a two-dimensional plane or three-dimensional space. The state of arrangement. However, here, since the first organic semiconductor molecules and the like always exist between the fine particles, the fine particles are not in contact with each other. The distance between the surfaces of adjacent fine particles is equal to or less than the length in the major axis direction of the first organic semiconductor molecule or the like used. In addition, when the fine particles are regularly arranged two-dimensionally in a plane substantially parallel to the surface of the substrate on the substrate, more specifically, such a two-dimensionally regularly arranged layer has a single layer. Even if it is a layer, it may exist in multiple layers in a three-dimensional close-packed state. “Two-dimensionally regularly arranged” means that fine particles having a uniform particle diameter are arranged in a packed space, preferably in a close packed state, in a space of at least approximately one layer of fine particles. Means that Note that “in a plane substantially parallel to the surface of the substrate” means that when there are minute irregularities on the surface of the substrate by the manufacturing method of the substrate, the surface is substantially parallel to the minute irregularities.

  Fine particle / first organic semiconductor molecule / bonding layer (first embodiment of the present invention) or fine particle / organic semiconductor molecule / bonding layer (second embodiment of the present invention) (hereinafter collectively referred to simply as “ In some cases, a fine particle layer is first formed on a substrate. In this case, for example, a thin film made of a solution containing fine particles is applied to a substrate by a coating method such as a dipping method, a cast method, a spin coating method, an electrodeposition method, or an advection accumulation method (AS Dimitrov et al., Langmuir, 10, 432 (1994)), the fine particle layer can be obtained by evaporating the solvent contained in the thin film, whereby the fine particles can be arranged in close packing in the fine particle layer. In this case, when evaporating the solvent contained in the thin film, it is desirable to evaporate the solvent contained in the thin film while controlling the evaporation rate. Alternatively, the fine particle layer can be obtained, for example, by forming a thin film from a solution containing fine particles based on a method similar to the LB (Langmuir-Blodgett) method and then transferring the thin film onto a substrate. . Specifically, a fine particle layer-structured fine particle having a hydrophobic surface is floated on a hydrophilic solvent (for example, water) so as to have a two-dimensional regular array as a single layer, or conversely, on a hydrophobic solvent. A method of floating fine particle layer-structured fine particles having a hydrophilic surface so as to have a two-dimensional regular arrangement in a single layer, and transferring it like the LB method (see V. Santhanam, et al., Langmuir, 2003, 19, 7881) ). This also allows the fine particles to be arranged in a close packed manner in the fine particle layer. More specifically, a fine particle layer can be obtained by depositing a thin film on a water surface based on a solution containing fine particles, and then transferring the fine particle film formed by evaporating the solvent contained in the thin film onto a substrate. In this case as well, it is more preferable to evaporate the solvent contained in the thin film while controlling the evaporation rate in the step of evaporating the solvent contained in the thin film.

  In the formation of the bonding layer, after the formation of the fine particle layer, the step of bringing the first organic semiconductor molecule or the like into contact with the fine particle layer is performed at least once to bond the fine particle and the first organic semiconductor molecule or the like. it can. A single layer of the conjugate can be formed by performing the formation of the fine particle layer and the contact with the first organic semiconductor molecule once, and the formation of the fine particle layer and the first organic semiconductor molecule etc. By repeating the contact twice or more, a laminated structure of the combined body can be formed. In order to bring the first organic semiconductor molecule or the like into contact with the fine particle layer, for example, the fine particle layer may be immersed in a solution containing the first organic semiconductor molecule or the like, or the first organic semiconductor molecule or the like may be used. May be applied or printed on the fine particle layer based on a coating method or a printing method described later. And after that, a bonding layer can be obtained by drying.

  Alternatively, the fine particle / first organic semiconductor molecule / bonding layer combines (reacts) with the fine particle and the first organic semiconductor molecule by mixing the solution containing the fine particle and the first organic semiconductor molecule. It can also be obtained by obtaining a cluster comprising, and forming a thin film containing these clusters on a substrate and drying. The method of mixing the solution containing fine particles and the first organic semiconductor molecules may be appropriately determined based on the solution containing the fine particles to be used and the first organic semiconductor molecules to be used. Depending on the solution containing the fine particles to be used and the first organic semiconductor molecules, the fine particles and the first organic semiconductor molecules can be obtained simply by adding the powdered first organic semiconductor molecules to the solution containing the fine particles and mixing them lightly. In some cases, it is possible to obtain clusters formed by bonding. Examples of a method for forming a thin film including clusters include a coating method such as a dipping method and a casting method, and a method similar to the LB method. The cluster arrangement state includes a state where the clusters are arranged one-dimensionally (a state where they are arranged linearly), a state where the clusters are arranged two-dimensionally (a state where they are arranged in a plane), and a state where the clusters are 3 It may be in any of a dimensionally arranged state (a three-dimensionally arranged state), for example, depending on the application state of a solution containing clusters.

  Here, the cluster formed by combining the fine particles and the first organic semiconductor molecules is more specifically a combination of the fine particles and the fine particles, for example, three-dimensionally via the first organic semiconductor molecules. There are, for example, about several thousand to several million fine particles collected through the first organic semiconductor molecules, and the size is on the order of 0.1 μm to 1 μm. When the clusters are arranged between the source / drain electrodes, on the gate insulating layer, or on the substrate, the first between the clusters and between the clusters or between the clusters and the source / drain electrodes exists on the surface of the cluster. In some cases, or in addition thereto, the first organic semiconductor molecule solution in which the first organic semiconductor molecule is dissolved is applied to the cluster and dried to be bonded to each other. A large amount of “fine particles—first organic semiconductor molecule” conduction paths exist in the cluster. If a cubic cluster of 100 nm square is assumed and fine particles with a particle size of 5 nm are stacked in a cubic lattice, 8,000 fine particles are present in the cubic cluster. A large number of first organic semiconductor molecules are bonded and crosslinked between these fine particles. Therefore, the number of conduction paths is significantly increased, resulting in an increase in the amount of current.

  Examples of the solvent contained in the thin film include nonpolar or low polarity organic solvents such as toluene, chloroform, hexane, and ethanol.

The surface of the fine particles before being bonded to the first organic semiconductor molecules or the like is preferably covered with a protective film made of chain-like insulating organic molecules from the viewpoint of preventing aggregation of the fine particles. The molecules constituting the protective film are bonded to the fine particles, but the binding strength of the molecules covered by the protective film (actually, the aggregate of the fine particles covered by the protective film) This greatly affects the final particle size distribution of the aggregate during production. It is preferable that one end of the insulating organic molecule constituting the protective film has a functional group that chemically reacts (bonds) with the fine particles. For example, mention may be made of a thiol group (-SH) as a functional group, alkanethiol [e.g., dodecanethiol (C ₁₂ H ₂₅ SH)] as one of the molecules with the thiol group at the end can be exemplified. It is thought that when the thiol group of dodecanethiol is bonded to fine particles such as gold, the hydrogen atom is released to become C ₁₂ H ₂₅ S—Au. Alternatively, as an insulating organic molecule constituting the protective film, an alkylamine molecule [for example, dodecylamine (C ₁₂ H ₂₅ NH ₂ )] can be exemplified. When the fine particles are brought into contact with the first organic semiconductor molecules, etc., the first organic semiconductor molecules are replaced with the organic molecules constituting the protective film. As a result, the chemistry of the fine particles with the first organic semiconductor molecules, etc. A natural conjugate is formed.

  The first organic semiconductor molecule or the like that plays a role of crosslinking between the fine particles has functional groups capable of binding to the fine particles at both ends. By the way, when the distance between the fine particles is longer than the total length of the first organic semiconductor molecules and the fine particles are fixed on the substrate and cannot move, the conductive path is cut there. As a result, the number of conductive paths constituted by the first organic semiconductor molecules and the like and the fine particles is reduced, leading to deterioration of the characteristics of the organic electronic device. When trying to obtain an organic electronic device having excellent characteristics, when the organic electronic device is composed of, for example, a field effect transistor (FET), from one source / drain electrode to the other source / drain electrode, The conductive paths need to be connected without breaks. In addition, the number of conductive paths greatly affects the improvement of FET characteristics. In order to increase the number of conductive paths, the fine particles are adjacent to each other at a distance closer to the length of the first organic semiconductor molecule or the like, and furthermore, the fine particles are two-dimensionally arranged in a hexagonal close packed manner. It is desirable. More specifically, the surface of the fine particle before being bonded to the first organic semiconductor molecule or the like is covered with a protective film made of, for example, a chain-like insulating organic molecule. Therefore, the distance between the fine particles is about twice as long as the length of the molecules constituting the protective film (actually, the distance between the particles is slightly shorter because the molecules slightly overlap at the tip). It is preferable that the length of the first organic semiconductor molecule or the like that crosslinks these fine particles is not longer than the distance between the fine particles thus determined.

In the first aspect of the present invention, the first organic semiconductor molecule is an organic semiconductor molecule having a conjugated bond as described above, and has a thiol group (—SH), an amino group (—NH ₂ ) at both ends of the molecule. ), Isocyano group (—NC), cyano group (—CN), thioacetyl group (—SCOCH ₃ ), trichlorosilane (—Si (Cl) ₃ ), ammonium group (—NH ₃ ⁺ ), phosphate group, or It preferably has a carboxy group (—COOH). The thiol group, amino group, isocyano group, cyano group, thioacetyl group, trichlorosilane, ammonium group, and phosphate group are functional groups that bind to fine particles as conductors such as Au, and include carboxy group, trichlorosilane, and ammonium group. The group and the phosphate group are functional groups that bond to fine particles as a semiconductor. Further, the functional groups located at both ends of the molecule may be different, and it is more preferable that the functional groups at both ends are close to the fine particles. Note that the first organic semiconductor molecule is a π-conjugated molecule, and most preferably has a functional group that is chemically bonded to the fine particles in at least two places.

  Specifically, in the first aspect of the present invention, examples of the first organic semiconductor molecule exhibiting p-type conductivity include porphyrin (details will be described later), 4,4′-biphenyl of the structural formula (11) Dithiol (BPDT), 4,4′-diisocyanobiphenyl of structural formula (12), 4,4′-diisocyano-p-terphenyl of structural formula (13), and 2,5- of structural formula (14) Bis (5′-thioacetyl-2′-thiophenyl) thiophene, 4,4′-diisocyanophenyl of structural formula (15), benzidine (biphenyl-4,4′-diamine) of structural formula (16), structural formula TCNQ (tetracyanoquinodimethane) of (17), biphenyl-4,4′-dicarboxylic acid of structural formula (18), 1,4-di (4-thiophenylacetylinyl)-of structural formula (19) 2-ethylbe Zen, 1,4-di (4-isocyanoacetate phenylacetate dust yl) of formula (20) -2-ethylbenzene can be exemplified.

Structural formula (11): 4,4′-biphenyldithiol

Structural formula (12): 4,4′-diisocyanobiphenyl

Structural formula (13): 4,4′-diisocyano-p-terphenyl

Structural formula (14): 2,5-bis (5′-thioacetyl-2′-thiophenyl) thiophene

Structural formula (15): 4,4′-diisocyanophenyl

Structural formula (16): benzidine (biphenyl-4,4′-diamine)

Structural formula (17): TCNQ (tetracyanoquinodimethane)

Structural formula (18): Biphenyl-4,4′-dicarboxylic acid

Structural formula (19): 1,4-di (4-thiophenylacetylinyl) -2-ethylbenzene

Structural formula (20): 1,4-di (4-isocyanophenylacetylinyl) -2-ethylbenzene

  In the first embodiment of the present invention, a dendrimer represented by the structural formula (21) can also be used as the first organic semiconductor molecule.

Structural formula (21): Dendrimer

Alternatively, in the first aspect of the present invention, an organic molecule represented by the structural formula (22) can also be used as the organic semiconductor molecule. “X” in the structural formula (22) is represented by any one of the formula (23-1), the formula (23-2), the formula (23-3), and the formula (23-4). “Y ₁ ” and “Y ₂ ” in (22) are represented by any one of formulas (24-1) to (24-9), and “Z ₁ ”, “Z ₂ ”, “Z ₃ ”. , “Z ₄ ” is represented by any one of formulas (25-1) to (25-11). Here, the value of “n” is 0 or a positive integer. X is a unit in which a unit represented by any one of formula (23-1), formula (23-2), formula (23-3), and formula (23-4) is repeatedly bonded one or more times. Yes, including repetition by different units. Further, the side chains Z ₁ , Z ₂ , Z ₃ , Z ₄ may change to different ones during the repetition.

  As the form in which the fine particle / first organic semiconductor molecule / bonding layer is brought into contact with the second organic semiconductor molecule having the second conductivity type, any form (solid phase, liquid phase, gas phase) of the second organic semiconductor molecule can be used. Phase), a method of immersing the fine particles / first organic semiconductor molecules / bonding layer in a solution containing the second organic semiconductor molecules, and a gas (vapor) containing the second organic semiconductor molecules. And a method of exposing the fine particles / first organic semiconductor molecules / bonding layer.

  Furthermore, in the first aspect of the present invention including the preferred embodiments and configurations described above, the organic electronic device is formed of a field effect transistor (FET), and forms a channel that exhibits a behavior as a second conductivity type by a conductive path. The area may be configured. In addition, in the second aspect of the present invention including the preferred embodiment and configuration described above, the organic electronic device is composed of a field effect transistor (FET), and a channel forming region that exhibits p-type behavior is formed by a conductive path. It can be set as a form. Examples of the field effect transistor include a bottom gate / bottom contact type, a bottom gate / top contact type, a top gate / bottom contact type, and a top gate / top contact type.

Specifically, bottom-gate / bottom-contact field effect transistors are:
(A) a gate electrode formed on a support;
(B) a gate insulating layer (corresponding to a substrate) formed on the gate electrode and the support,
(C) source / drain electrodes formed on the gate insulating layer, and
(D) a channel formation region formed between the source / drain electrodes and on the gate insulating layer and configured by a conductive path;
It has.

Bottom-gate / top-contact field effect transistors are
(A) a gate electrode formed on a support;
(B) a gate insulating layer (corresponding to a substrate) formed on the gate electrode and the support,
(C) a channel formation region forming layer including a channel formation region formed on the gate insulating layer and configured by a conductive path; and
(D) Source / drain electrodes formed on the channel forming region constituting layer,
It has.

Top gate / bottom contact field effect transistors
(A) Source / drain electrodes formed on the substrate,
(B) a channel forming region formed on the substrate between the source / drain electrodes and constituted by a conductive path;
(C) a gate insulating layer formed on the source / drain electrode and the channel formation region, and
(D) a gate electrode formed on the gate insulating layer;
It has.

The top-gate / top-contact field effect transistor is
(A) a channel forming region constituting layer including a channel forming region formed on a substrate and configured by a conductive path;
(B) a source / drain electrode formed on the channel forming region constituting layer;
(C) a gate insulating layer formed on the source / drain electrode and the channel formation region, and
(D) a gate electrode formed on the gate insulating layer;
It has.

The substrate can be composed of a silicon oxide-based material (for example, SiO _x or spin-on glass (SOG)); silicon nitride (SiN _Y ); aluminum oxide (Al ₂ O ₃ ); metal oxide high dielectric insulating film. When the base is composed of these materials, the base may be formed on a support appropriately selected from the following materials (or above the support). That is, as a support or as a substrate other than the above-described substrates, polymethyl methacrylate (polymethyl methacrylate, PMMA), polyvinyl alcohol (PVA), polyvinyl phenol (PVP), polyethersulfone (PES), polyimide, Organic polymers exemplified by polycarbonate (PC) and polyethylene terephthalate (PET) (having the form of a polymer material such as a flexible plastic film, plastic sheet or plastic substrate made of a polymer material) Or mica can be mentioned. If a substrate made of such a flexible polymer material is used, for example, an organic electronic device can be incorporated or integrated into a display device or electronic device having a curved shape. Alternatively, as a substrate (or support), various glass substrates, various glass substrates having an insulating layer formed on the surface, a quartz substrate, a quartz substrate having an insulating layer formed on the surface, and an insulating layer formed on the surface A silicon substrate can be mentioned. As the electrically insulating support, an appropriate material may be selected from the materials described above. Other examples of the support include a conductive substrate (a substrate made of metal such as gold or aluminum, a substrate made of highly oriented graphite). Further, depending on the configuration and structure of the organic electronic device, the organic electronic device is provided on the support, but this support can also be formed from the above-described materials.

  When the organic electronic device is a field effect transistor, platinum (Pt), gold (Au), palladium (Pd), chromium (Cr), nickel are used as materials constituting the gate electrode, source / drain electrode, and various wirings. (Ni), aluminum (Al), silver (Ag), tantalum (Ta), tungsten (W), copper (Cu), titanium (Ti), indium (In), tin (Sn), iron (Fe), cobalt Metals such as (Co) and molybdenum (Mo), or alloys containing these metal elements, conductive particles made of these metals, conductive particles of alloys containing these metals, polysilicon containing impurities, etc. An electroconductive substance can be mentioned and it can also be set as the laminated structure of the layer containing these elements. Furthermore, an organic material (conductive polymer) such as poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid [PEDOT / PSS] is used as a material constituting the gate electrode, the source / drain electrode, and various wirings. It can also be mentioned.

  Various chemical vapor deposition methods (CVD methods) including physical vapor deposition (PVD method) and MOCVD methods, depending on the materials constituting the gate electrodes, source / drain electrodes, and wiring. ); Various printing methods such as screen printing method, inkjet printing method, offset printing method, gravure printing method; spin coating method, dipping method, stamp method, air doctor coater method, blade coater method, rod coater method, knife coater method, squeeze method Various coating methods (coating methods) such as coater method, reverse roll coater method, transfer roll coater method, gravure coater method, kiss coater method, cast coater method, spray coater method, slit orifice coater method, calendar coater method; lift-off method; Sol-gel method; electrodeposition method; shadow Disk method; plating method such as electrolytic plating or electroless plating method, or a combination thereof; and can include any of a spraying method, a combination of a patterning technique as necessary. In addition, as the PVD method, (a) various vacuum deposition methods such as electron beam heating method, resistance heating method, flash deposition, (b) plasma deposition method, (c) bipolar sputtering method, direct current sputtering method, direct current magnetron sputtering method Various sputtering methods such as high-frequency sputtering method, magnetron sputtering method, ion beam sputtering method, bias sputtering method, (d) DC (direct current) method, RF method, multi-cathode method, activation reaction method, electric field evaporation method, high-frequency method Various ion plating methods such as an ion plating method and a reactive ion plating method can be given.

Further, when the organic electronic device is a field effect transistor, as a material constituting the gate insulating layer (which may correspond to the base), a silicon oxide-based material; silicon nitride (SiN _Y ); aluminum oxide (Al ₂ In addition to inorganic insulating materials exemplified by metal oxide high dielectric insulating films such as O ₃ ), polymethyl methacrylate (PMMA); polyvinyl phenol (PVP); polyvinyl alcohol (PVA); polyimide; polycarbonate (PC) Polyethylene terephthalate (PET); polystyrene; silanol derivatives (silanes) such as N-2 (aminoethyl) 3-aminopropyltrimethoxysilane (AEAPTMS), 3-mercaptopropyltrimethoxysilane (MPTMS), octadecyltrichlorosilane (OTS) Coupling agent An organic insulating material (organic polymer) exemplified by linear hydrocarbons having a functional group capable of binding to a gate electrode or the like at one end, such as octadecanethiol and dodecyl isocyanate, and combinations thereof Can also be used. Silicon oxide-based materials include silicon oxide (SiO _x ), BPSG, PSG, BSG, AsSG, PbSG, silicon oxynitride (SiON), SOG (spin-on-glass), low dielectric constant SiO ₂ -based material (for example, polyaryl) And ether, cycloperfluorocarbon polymer and benzocyclobutene, cyclic fluororesin, polytetrafluoroethylene, fluorinated aryl ether, fluorinated polyimide, amorphous carbon, and organic SOG).

In addition, as a method for forming a gate insulating layer, various PVD methods described above; various CVD methods; various printing methods described above; various coating methods including spin coating method and immersion method; casting methods; sol-gel method; One of a method; a shadow mask method; and a spray method can be mentioned. Alternatively, the gate insulating layer can be formed by oxidizing or nitriding the surface of the gate electrode, or can be obtained by forming an oxide film or a nitride film on the surface of the gate electrode. As a method for oxidizing the surface of the gate electrode, although depending on the material constituting the gate electrode, an oxidation method using O ₂ plasma and an anodic oxidation method can be exemplified. Further, as a method of nitriding the surface of the gate electrode, although it depends on the material constituting the gate electrode, a nitriding method using N ₂ plasma can be exemplified. Alternatively, for example, for an Au electrode, it is immersed by an insulating molecule having a functional group that can form a chemical bond with the gate electrode, such as a linear hydrocarbon modified at one end with a mercapto group. A gate insulating layer can also be formed on the surface of the gate electrode by covering the surface of the gate electrode in a self-organized manner by a method such as a method. Alternatively, the gate insulating layer can be formed by modifying the surface of the gate electrode with a silanol derivative (silane coupling agent).

  When an organic electronic device is applied to and used in a display device or various electronic devices, it may be a monolithic integrated circuit in which a large number of organic electronic devices are integrated on a support, or each organic electronic device is cut and individualized for discrete use. It may be used as a part. Moreover, you may seal an organic electronic device with resin.

  As an organic electronic device, in addition to the above-described field-effect transistor, a transistor having molecular recognition ability can be provided, so that it can be applied to a molecular sensor. By selecting the second organic semiconductor molecule such as the organic semiconductor molecule, application to a photoelectric conversion element, a light emitting element, a switching device, or the like becomes possible.

  In the first aspect of the present invention, the first organic semiconductor molecule is used as a linker molecule, and the second recognition layer is formed in a molecular recognition field composed of nanospace formed by networking, for example, a single layer film of fine particles. By selectively capturing the organic semiconductor molecule as a guest molecule, for example, a conductive path that exhibits the behavior as the first conductivity type by the combination of the first organic semiconductor molecule and the fine particles is changed into the behavior as the second conductivity type. Can be easily converted into a conductive path. Specifically, for example, a p-channel transistor can be converted into an n-channel transistor by a simple manufacturing process. That is, it is not necessary to synthesize the n-type organic semiconductor material by a complicated process of several steps, and it becomes possible to reduce the manufacturing cost of various organic electronic devices by developing a simpler process or the like. In addition, since the degree of freedom in selecting an n-type organic semiconductor material that can be used is increased, it is possible to use an n-type organic semiconductor material that is difficult to be oxidized in air and has stable physical properties. It is possible to avoid the occurrence of problems such as complexity.

  Further, in the second aspect of the present invention, by forming a conductive path from a novel organic semiconductor molecule, for example, when a channel formation region is formed by the conductive path, an organic electron having excellent characteristics You can get a device.

  Furthermore, in the organic electronic device according to the first aspect or the second aspect of the present invention, as a result of combining the fine particles with the first organic semiconductor molecules, etc., the charge transfer in the conductive path is the first. It is a structure that occurs predominantly in the axial direction of the molecule along the main chain of organic semiconductor molecules, etc., and maximizes the mobility in the axial direction of the molecule, for example, high mobility due to delocalized π electrons Therefore, high mobility can be realized. In addition, a high-temperature process or a vacuum process is not necessary for forming the conductive path, and a conductive path having a desired thickness can be easily formed, and an organic electronic device can be manufactured at low cost.

FIG. 1 is a conceptual diagram of a conductive path constituting the organic electronic device according to the first aspect of the present invention. 2A and 2B are conceptual diagrams at each stage for explaining the formation of a conductive path constituting the organic electronic device according to the first aspect of the present invention. FIG. 3 is a graph showing the results of measuring the molecular weight of the porphyrin molecule (Example 1) represented by the formula (104), which is the first organic semiconductor molecule, by MALDI-TOF-MS. FIG. 4 is a graph showing the results of measuring the molecular weight of the porphyrin molecule (Reference Example 1) represented by the formula (105) by MALDI-TOF-MS. FIG. 5 is a graph showing the measurement results of the absorption spectrum of plasmon in the porphyrin network membrane. FIG. 6 is a graph showing the results of monitoring the shift in plasmon absorption after immersion in a toluene solution of fullerene (C ₆₀ ) for a certain period of time. 7A and 7B are graphs showing the results of measuring the drain currents of Sample-A and Sample-B obtained in Example 1, respectively. 8A and 8B are schematic partial end views of a substrate and the like for explaining the outline of the manufacturing method of the organic electronic device (field-effect transistor) of Example 3. FIG. FIGS. 9A and 9B are schematic views of a substrate and the like for explaining the outline of the manufacturing method of the organic electronic device (field effect transistor) of Example 3 following FIG. 8B. It is a partial end view. FIG. 10 is a conceptual diagram of a part of the organic electronic device (field effect transistor) of Example 3. FIGS. 11A and 11B are schematic partial end views of a substrate and the like for explaining the outline of the manufacturing method of the organic electronic device (field effect transistor) of Example 4. FIG. 12 (A) and 12 (B) are schematic views of a substrate and the like for explaining the outline of the manufacturing method of the organic electronic device (field effect transistor) of Example 4 following FIG. 11 (B). It is a partial end view. FIGS. 13A and 13B are schematic partial end views of a substrate and the like for explaining the outline of the manufacturing method of the organic electronic device (field effect transistor) of Example 5. FIG. 14A and 14B are schematic views of a substrate and the like for explaining the outline of the manufacturing method of the organic electronic device (field effect transistor) of Example 5 following FIG. 13B. It is a partial end view. 15A and 15B are schematic partial end views of a substrate and the like for explaining the outline of the method for manufacturing the organic electronic device (field effect transistor) of Example 5. FIG. 16 (A) and 16 (B) are schematic views of a substrate and the like for explaining the outline of the manufacturing method of the organic electronic device (field effect transistor) of Example 5 following FIG. 15 (B). It is a partial end view. FIG. 17 is a diagram showing a synthesis scheme of the organic semiconductor molecule of the present invention represented by the formula (104) and the organic semiconductor molecule of the reference example represented by the formula (105). The lower part and the upper part of FIG. 18 are MALDI-TOF-MS of Compound 5 (an organic semiconductor molecule of the example, n = 2) and Compound 6 (an organic semiconductor molecule of the reference example, n = 2) of FIG. It is a graph which shows the result of having measured a spectrum. The lower part and the upper part of FIG. 19 are MALDI-TOF-MS of Compound 5 (organic semiconductor molecule of the example, n = 3) and Compound 6 (organic semiconductor molecule of the reference example, n = 3) of FIG. It is a graph which shows the result of having measured a spectrum.

  Hereinafter, the present invention will be described based on examples with reference to the drawings.

Example 1 relates to the organic electronic device and the manufacturing method thereof according to the first and second aspects of the present invention, and the organic semiconductor molecule of the present invention. The organic electronic device according to the first aspect of the present invention includes a conductive path, and the conductive path is, as shown in a conceptual diagram in FIG.
(A) fine particles,
(B) a first organic semiconductor molecule (also referred to as a linker molecule, corresponding to a host molecule) having a first conductivity type (p-type in Example 1) and binding fine particles to each other; and
(C) Second organic semiconductor molecule (guest molecule) having a second conductivity type (n-type in Example 1) and trapped in a non-covalent bond state in a molecular recognition field existing between the fine particles. Equivalent to
Consists of.

More specifically, in Example 1, the fine particles are composed of gold (Au) particles having an average particle diameter R _AVE = 5 nm whose surface is covered with a protective film (not shown), and the first organic semiconductor molecule is It consists of porphyrin having p-type conductivity, the second organic semiconductor molecule is made of fullerene (C ₆₀ ) having n-type conductivity, and the second organic semiconductor molecule is intermolecular interaction with the first organic semiconductor molecule. Is possible. The conductive path as a whole behaves as an n-type. The functional group at the terminal of the first organic semiconductor molecule is chemically bonded to the fine particles. More specifically, the first organic semiconductor molecule is an organic semiconductor molecule having a conjugated bond, and has thiol groups (—SH) at both ends of the molecule. The structural formula of the first organic semiconductor molecule (provided before the functional group at the terminal is replaced by a thiol group) is shown in the following structural formula (101). For reference, a first organic semiconductor molecule having a thiol group (—SH) only at one end of the molecule was also synthesized. The structural formula of the first organic semiconductor molecule of Reference Example 1 (however, the structural formula before the functional group at the terminal is replaced by a thiol group) is shown in the following structural formula (102).

On the other hand, the organic electronic device according to the second aspect of the present invention includes a conductive path, and the conductive path is, as shown in a conceptual diagram in FIG.
(A) fine particles, and
(B) an organic semiconductor molecule in which fine particles are combined,
And shows the behavior as a p-type. And the organic-semiconductor molecule | numerator which is a thiophene porphyrin which has this thiol group is represented by following Structural formula (1). Moreover, it is a kind of precursor for obtaining the organic semiconductor molecule of the structural formula (1), and the novel organic semiconductor molecule of the present invention before the functional group at the terminal is substituted with a thiol group has the following structural formula It is represented by (2). However, in Structural Formula (1) and Structural Formula (2), R ₁ and R ₂ are alkyl groups, specifically, C ₅ H ₁₁ in Example 1, and M is in Example 1. In that case, Zn ⁺² and n = 3. The fine particles are as described above. And the functional group (specifically thiol group (-SH)) which the organic semiconductor molecule has at the terminal is chemically bonded to the fine particles. Note that the value of m in R ₁ and R ₂ affects the solubility of the organic semiconductor molecule, and if the value of m becomes too large, the solubility of the organic semiconductor molecule becomes poor.

  Hereinafter, the manufacturing method of the organic electronic device of Example 1 is demonstrated.

[Step-100]
Porphyrin molecules of the formula (104) and the formula (105) were synthesized from the starting material represented by the following formula (103). In Example 1, the value of “n” in the porphyrin molecule represented by Formula (104) and Formula (105) is “3”. The porphyrin molecule represented by formula (104) (referred to as a porphyrin molecule / precursor in Example 1 for convenience) has a thioacetyl group (—SCOCH ₃ ) at both ends. On the other hand, the porphyrin molecule represented by formula (105) (referred to as a porphyrin molecule / precursor in Reference Example 1 for convenience) has a thioacetyl group only at one end. Here, the structural formula (104) is a structure in which R ₁ and R ₂ are alkyl groups (C ₅ H ₁₁ ), M is Zn ^+2, and n is 3 in the above-described structural formula (1). . Details of the synthesis of the porphyrin molecule represented by formula (104) and formula (105) will be described later.

  The molecular weight of the porphyrin molecule / precursor of Example 1 and Reference Example 1 represented by the formula (104) and formula (105) was measured by MALDI-TOF-MS, and the result (see FIGS. 3 and 4). Were 1151.881 and 902.158, respectively, which coincided with the respective calculated values (1152.083 and 902.216).

  When a conductive path is formed based on the porphyrin molecule / precursor of Example 1 and Reference Example 1 shown in Formula (104) and Formula (105), the thioacetyl group at the end of the molecule is replaced with a thiol group (- SH) must be substituted. Since the porphyrin molecule whose end is substituted with a thiol group is easily oxidized in the atmosphere, it is desirable to keep the end in the form of a thioacetyl group until just before use. Substitution with this thiol group was performed based on the method described in X. Xiao et. Al. J. Am. Chem. Soc. 2005, 127, 9235-9240. That is, since both ends of these molecules are acetyl groups, a hydrolysis reaction was performed immediately before chemical bonding between the fine particles and the organic semiconductor molecules, and both ends of these molecules were made thiol groups. Specifically, after adding the porphyrin molecule to ethanol (at this time, the porphyrin molecule does not dissolve in ethanol), 50 mL of 0.2N NaOH aqueous solution is added and stirred for 30 minutes, resulting in a clear green solution. . The concentration of the porphyrin molecule solution is 1 millimol and is in an argon saturated state.

  Using the porphyrin molecular solution prepared in Example 1 and Reference Example 1 thus prepared, an organic electronic device prototype was produced based on the method described below.

[Step-110]
As a support, a silicon semiconductor substrate doped with a high concentration of impurities is used. This silicon semiconductor substrate itself is used as a gate electrode, and a gate insulating layer (corresponding to a base) is heated on the surface of the silicon semiconductor substrate. It was composed of SiO ₂ formed by oxidation. Then, a titanium (Ti) layer with a thickness of about 0.5 nm as an adhesion layer and a gold (Au) layer with a thickness of about 25 nm as a source / drain electrode are sequentially deposited on the gate insulating layer by a vacuum deposition method. Formed on the basis. When these layers were formed, the source / drain electrodes could be formed without a photolithography process by covering a part of the gate insulating layer with a hard mask.

[Step-120]
Next, based on a method similar to the LB method, after forming a thin film on the water surface based on a toluene solution containing Au fine particles, the fine particle film formed by evaporating the solvent contained in the thin film is formed on the substrate (more specifically, First, a single layer film of a fine particle layer was obtained by transferring onto a source / drain electrode and a gate insulating layer. This state is shown in the conceptual diagram of FIG. In FIG. 2A, the fine particles are illustrated as being discretely arranged, but in reality, the substrate is in contact with a protective film (not shown) formed on the surface of the fine particles. Are arranged two-dimensionally and regularly in a filled state (more specifically, in a close-packed state) in a plane substantially parallel to the surface of

[Step-130]
Then, the whole was immersed in the porphyrin molecular solution mentioned above. As a result of the porphyrin molecule which is the first organic semiconductor molecule or the organic semiconductor molecule (first organic semiconductor molecule, etc.) being replaced with the organic molecule constituting the protective film, the chemical reaction between the fine particles and the first organic semiconductor molecule, etc. A simple combined body is formed (see the conceptual diagram of FIG. 2B). Thus, on the substrate,
(A) fine particles, and
(B) a first organic semiconductor molecule having a first conductivity type, in which fine particles and fine particles are combined;
It was possible to form a fine particle / first organic semiconductor molecule / bonding layer (porphyrin network monolayer film) comprising: Alternatively,
(A) fine particles, and
(B) an organic semiconductor molecule in which fine particles are combined,
It was possible to obtain a conductive path consisting of

  Through the above steps, the method for manufacturing the organic electronic device according to the second aspect of the present invention is completed, and the organic electronic device according to the second aspect of the present invention can be obtained. And in order to obtain the organic electronic device which concerns on the 1st aspect of this invention, the manufacturing method of the organic electronic device which concerns on the 1st aspect of this invention demonstrated below is further performed.

[Step-140]
That is, the fine particle / first organic semiconductor molecule / bonding layer was then brought into contact with the second organic semiconductor molecule having the second conductivity type. Specifically, the whole was immersed in a toluene solution of fullerene (C ₆₀ ). As a result, fullerene (C ₆₀ ) was taken into the molecular recognition field (network space), and a conductive path could be obtained (see FIG. 1A).

Regarding the formation of a porphyrin-fullerene molecular complex by π-π interaction, C ₆₀ capture by porphyrin cycle dimer (K. Tashiro et. Al. J. Am. Chem. Soc. 1999, 121, 9477- 9478), C ₆₀ capture by porphyrin gel (see M. Shiragawa et. Al. J. Am. Chem. Soc. 2003, 125, 9902-9903), porphyrin / C ₆₀ complex on the surface of gold nanoparticles (see H. Imahori et. Al. Chem. Eur. J. 2005, 11, 7265-7275).

  Here, the test which confirms that the porphyrin molecule which is the 1st organic-semiconductor molecule etc. is substituted with the organic molecule which comprises a protective film by immersing the whole in a porphyrin molecule solution. Specifically, the change in the UV-Vis absorption spectrum on the glass substrate was examined. First, ultrasonic cleaning using ethanol, ultrasonic cleaning using acetone, and ultrasonic cleaning using pure water were sequentially performed on a glass substrate having a size of 1.8 cm × 1.8 cm. Then, as described above, a single layer film of gold nanoparticles was formed on a glass substrate based on a method similar to the LB method. And the porphyrin network film | membrane was formed into a film on the glass substrate only by immersing this glass substrate in a porphyrin solution. And the absorption spectrum of the plasmon in this porphyrin network membrane was measured. In addition, the shift of the plasmon absorption peak of the gold nanoparticle with the immersion time was monitored. The immersion time was 0 minutes, 10 minutes, 1 hour, 5 hours, and 24 hours. The result is shown in FIG. Here, the graph shown by the black square mark in FIG. 5 is the result when the porphyrin molecular solution of Example 1 is used, and the graph shown by the black triangle mark is when the porphyrin molecular solution of Reference Example 1 is used. It is a result.

In the absorption of gold plasmons,
(1) interaction between gold nanoparticles and first organic semiconductor molecules, and
(2) It is known that a long wavelength shift occurs due to the interaction between gold nanoparticles (for example, see BC Sih et. Al. Chem. Commun. 2005, 3375-3384). When the porphyrin molecular solution of Example 1 was used, the plasmon shift was almost saturated after 1 hour of immersion, and a large plasmon absorption shift of 25 nm was observed. In addition, plasmon absorption shift saturation was observed in the first hour or so, strongly suggesting the formation of Au—S bonds. When the porphyrin molecular solution of Reference Example 1 in which the particles cannot be linked is used, the total plasmon shift amount is 15 nm, which is smaller than when the porphyrin molecular solution of Example 1 is used. From this result, it was found that the strong interaction between the gold nanoparticle and the first organic semiconductor molecule or the like is generated by linking, and the shift of plasmon absorption becomes large.

Further, the sample thus obtained was immersed in a toluene solution of fullerene (C ₆₀ ) for a certain time, and the shift in plasmon absorption was monitored. The immersion time was 0 minutes, 10 minutes, 1 hour, 5 hours, and 24 hours. The results are shown in FIG. 6. The graph indicated by black circles in FIG. 6 is the results when the porphyrin molecule solution of Example 1 was used, and the graph indicated by black triangles is the porphyrin molecule solution of Reference Example 1. It is a result when using. The porphyrin molecule solution obtained when the result of FIG. 5 is obtained is different from the porphyrin molecule solution obtained when the result of FIG. 6 is obtained. By capturing fullerene (C ₆₀ ) in a molecular recognition field (network space), a long wavelength shift of plasmons is observed. Even in this case, shift saturation was observed within a few hours. Here, when the porphyrin molecule solution of Example 1 was used, a large shift of about 10 nm occurred compared to when the porphyrin molecule solution of Reference Example 1 was used. It was found that C ₆₀ ) capture occurs. From the above results, the linker reaction by the porphyrin molecule and the fullerene (C ₆₀ ) capturing action by the network structure were clarified.

The above-described conductive path characteristics were evaluated. Specifically, Sample-A obtained by completing [Step-130] (corresponding to the organic electronic device according to the second aspect of the present invention) and immersion in a fullerene (C ₆₀ ) toluene solution for 1 hour. The drain current was measured for Sample-B (corresponding to the organic electronic device according to the first aspect of the present invention) obtained by completing [Step-140]. The measurement result of Sample-A is shown in FIG. 7A, and the measurement result of Sample-B is shown in FIG. As shown in FIG. 7A, in Sample-A, the drain-side current increased by swinging the gate voltage _Vg to the minus side, and the operation of the p-channel transistor was clearly confirmed. . On the other hand, as shown in FIG. 7B, in Sample-B, by swinging the gate voltage _Vg to the plus side, the absolute value of the drain-side current increases, and the operation of the n-channel transistor is improved. It could be confirmed. From this result, it can be seen that in Example 1, host-guest interaction is possible, and a p-channel transistor can be converted to an n-channel transistor by simply incorporating a second organic semiconductor molecule that is a guest molecule. It was.

  The second embodiment is a modification of the first embodiment. In Example 2, an organic electronic device prototype was produced based on the method described below using a porphyrin molecule solution based on an organic semiconductor molecule or the like where n = 2 in formula (104). In addition, an organic electronic device prototype was produced as Reference Example 2 based on the method described below using a porphyrin molecule solution based on an organic semiconductor molecule or the like where n = 2 in formula (105). Since both ends of these molecules are acetyl groups, a hydrolysis reaction was performed immediately before chemical bonding between the fine particles and the organic semiconductor molecules, and both ends of these molecules were made thiol groups. Specifically, after adding the porphyrin molecule to ethanol (at this time, the porphyrin molecule does not dissolve in ethanol), 50 mL of 0.2N NaOH aqueous solution is added and stirred for 30 minutes, resulting in a clear green solution. . The concentration of the porphyrin molecule solution was two types of 0.1 millimol and 0.5 millimol. In addition, it is an argon saturation state.

[Step-210]
As in Example 1, a silicon semiconductor substrate doped with a high concentration of impurities is used as a support, the silicon semiconductor substrate itself is used as a gate electrode, and a gate insulating layer (corresponding to a substrate) is used. The surface of the silicon semiconductor substrate was composed of SiO ₂ (thickness 150 nm) formed by thermal oxidation. Then, a chromium (Cr) layer as an adhesion layer and a gold (Au) layer having a thickness of about 25 nm as a source / drain electrode were sequentially formed on the gate insulating layer based on a vacuum deposition method. When these layers were formed, the source / drain electrodes could be formed without a photolithography process by covering a part of the gate insulating layer with a hard mask. The channel length was 50 μm and the width was 8.8 mm.

[Step-220]
Next, based on a method similar to the LB method, a thin film is formed on the water surface based on a toluene solution containing Au fine particles (average particle size R _AVE = 4.7 ± 1.1 nm), and then the solvent contained in the thin film is evaporated. The fine particle film thus formed was transferred onto the substrate (more specifically, on the source / drain electrodes and the gate insulating layer) to obtain a single layer film of the fine particle layer. This state is the same as that shown in the conceptual diagram of FIG.

[Step-230]
Thereafter, the whole was immersed in the porphyrin molecule solution (temperature: 50 ° C.) for 3 hours. As a result of the replacement of the porphyrin molecule, which is an organic semiconductor molecule, with the organic molecule constituting the protective film, a chemical bond between the fine particles and the organic semiconductor molecule is formed (see the conceptual diagram in FIG. 1B). ). Thus, on the substrate,
(A) fine particles, and
(B) an organic semiconductor molecule in which fine particles are combined,
It was possible to obtain a conductive path consisting of

  Through the above steps, the method for manufacturing the organic electronic device according to the second aspect of the present invention was completed, and the organic electronic device according to the second aspect of the present invention was obtained.

[Step-240]
Thereafter, the bonding layer was brought into contact with a second organic semiconductor molecule having the second conductivity type. Specifically, the whole was immersed in a toluene solution of fullerene (C ₆₀ ). As a result, fullerene (C ₆₀ ) was taken into the molecular recognition field (network space), and a conductive path could be obtained (see FIG. 1A).

The electrical characteristics of the organic electronic device (samples of Example 2 and Reference Example 2) according to the second aspect of the present invention obtained in [Step-230] were measured. Current-voltage characteristics were measured using a plurality of samples of 2 to 4. The measurement results (average values) of conductivity (σ) and mutual conductance (g _m ) of Example 2 and Reference Example 2 are shown below.

Conductivity σ Mutual conductance g _m / W _g
(S / cm) (S / cm)
Example 2
0.1 millimol 7.71 × 10 ^-2 1.83 × 10 ^-5
0.5 millimoles 5.70 × 10 ⁻² 8.54 × 10 ⁻⁶
Reference example 2
0.1 millimol 5.82 × 10 ⁻⁴ 8.43 × 10 ⁻⁸
0.5 millimoles 1.23 × 10 ⁻⁴ 8.89 × 10 ⁻⁹

In Example 2, which is an organic electronic device according to the second aspect of the present invention, the conductivity σ is about 10 ² times or more and the mutual conductance g _m is 10 ³ times or more larger than that of Reference Example 2. The result was obtained. In Reference Example 2, since no link between gold particles occurs, hopping between molecules becomes a conduction path. On the other hand, in Example 2 in which a link between particles occurs, it is considered that the value of the flowing current is large due to the contribution of intramolecular conduction. Furthermore, in Example 2, since a relatively high transconductance g _m was obtained, it has been found that it is effective to network gold nanoparticles in order to obtain a larger gate effect. In addition, it became clear that organic electronic devices using dithiol linker molecules show better properties (large conductivity and gate effect) than organic electronic devices using monothiol porphyrin linker molecules. .

The third embodiment is a modification of the first embodiment. In Example 3, the organic electronic device was composed of a field effect transistor (FET), more specifically, a thin film transistor (TFT). In the field effect transistor (specifically, thin film transistor) of the third embodiment, a channel forming region that exhibits the behavior as the second conductivity type is configured by the conductive path. Furthermore, the field-effect transistor (more specifically, n-channel TFT) of Example 3 is a bottom gate / bottom contact type, and FIG. 9B shows a schematic partial cross-sectional view. like,
(A) a gate electrode 14B formed on the support 10;
(B) a gate insulating layer 15 (corresponding to the base 13) formed on the gate electrode 14B and the support 10;
(C) a source / drain electrode 16B formed on the gate insulating layer 15, and
(D) a channel forming region 17B formed between the source / drain electrodes 16B and on the gate insulating layer 15 and configured by the conductive path 21B;
It has. The field effect transistor (more specifically, p-channel TFT) of Example 3 is a bottom gate / bottom contact type, and a schematic partial cross-sectional view is shown in FIG. 9B. In addition,
(A) a gate electrode 14A formed on the support 10;
(B) a gate insulating layer 15 (corresponding to the base 13) formed on the gate electrode 14A and the support 10;
(C) a source / drain electrode 16A formed on the gate insulating layer 15, and
(D) a channel forming region 17A formed between the source / drain electrodes 16A and on the gate insulating layer 15 and configured by the conductive path 21A;
It has.

  The channel formation regions 17A and 17B in the third embodiment or the fourth to sixth embodiments described later have the same configuration and structure as the conductive path described in the first embodiment. The conductive path can be formed by the same method as that described above.

In Example 3, as in Example 1, gold fine particles (gold nanoparticles) having an average particle size R _AVE = 5 nm are used as the fine particles 23 made of a conductor. The first organic semiconductor molecule or the like is composed of p-type conductivity porphyrin having thiol groups (—SH) at both ends of the molecule, and the second organic semiconductor molecule is an n-type conductivity fullerene (C ₆₀ ). Consists of. The support 10 is composed of a glass substrate 11 and an insulating layer 12 made of SiO ₂ formed on the surface thereof, and the base 13 is made of a gate insulating layer 15 (specifically, SiO ₂ ).

  Hereinafter, referring to FIGS. 8A and 8B and FIGS. 9A and 9B, which are schematic partial end views of the substrate and the like, and FIG. An outline of a method for manufacturing an electronic device (field effect transistor) will be described.

[Step-300]
First, gate electrodes 14 </ b> A and 14 </ b> B are formed on the support 10. Specifically, a resist layer (not shown) from which the portions where the gate electrodes 14A and 14B are to be formed is removed on the insulating layer 12 made of SiO ₂ formed on the surface of the glass substrate 11 is applied to the lithography technique. Form based on. Thereafter, a titanium (Ti) layer (not shown) as an adhesion layer and a gold (Au) layer as the gate electrodes 14A and 14B are sequentially formed on the entire surface by a vacuum evaporation method, and then a resist layer. Remove. Thus, the gate electrodes 14A and 14B can be obtained based on the so-called lift-off method.

[Step-310]
Next, the gate insulating layer 15 corresponding to the base 13 is formed on the support 10 (more specifically, the insulating layer 12 formed on the surface of the glass substrate 11) including the gate electrodes 14A and 14B. Specifically, the gate insulating layer 15 made of SiO ₂ is formed on the gate electrodes 14A and 14B and the insulating layer 12 based on the sputtering method. When the gate insulating layer 15 is formed, a part of the gate electrodes 14A and 14B is covered with a hard mask, so that extraction portions (not shown) of the gate electrodes 14A and 14B are formed without a photolithography process. Can do.

[Step-320]
Thereafter, source / drain electrodes 16A and 16B made of a gold (Au) layer are formed on the gate insulating layer 15 (see FIG. 8A). Specifically, a titanium (Ti) layer (not shown) having a thickness of about 0.5 nm as an adhesion layer and a gold (Au) layer having a thickness of about 25 nm as the source / drain electrodes 16A and 16B are sequentially formed. And formed based on a vacuum deposition method. When these layers are formed, the source / drain electrodes 16A and 16B can be formed without a photolithography process by covering a part of the gate insulating layer 15 with a hard mask.

[Step-330]
Next, a fine particle layer 20 composed of the fine particles 23 is formed on the base 13 (see FIG. 8B). Specifically, in the same manner as in [Step-120] in Example 1, the fine particle layer 20 composed of the fine particles 23 is formed on the gate insulating layer 15 and the source / drain electrodes 16A and 16B.

[Step-340]
Thereafter, the whole is immersed in the porphyrin molecule solution of Example 1 in the same manner as in [Step-130] of Example 1. As a result of substitution of the porphyrin molecules, such as the first organic semiconductor molecules, with the organic molecules constituting the protective film, a chemical conjugate of the fine particles 23 and the first organic semiconductor molecules 24 is formed (FIG. 10). (See the conceptual diagram). Thus, on the base 13 (gate insulating layer 15), as shown in FIG.
(A) the fine particles 23 and
(B) a first organic semiconductor molecule having the first conductivity type, in which the fine particles 23 and the fine particles 23 are bonded;
A coupling layer (porphyrin network single layer film) 22 for forming an n-channel TFT can be formed. Also,
(A) a gate electrode 14A formed on the support 10;
(B) a gate insulating layer 15 (corresponding to the base 13) formed on the gate electrode 14 and the support 10;
(C) a source / drain electrode 16A formed on the gate insulating layer 15, and
(D) a channel forming region 17A formed between the source / drain electrodes 16A and on the gate insulating layer 15 and configured by the first conductive type (p-type) conductive path 21A;
Thus, a p-channel TFT (corresponding to the organic electronic device according to the second aspect of the present invention) configured from the above can be obtained.

[Step-350]
Next, a p-channel TFT other than the p-channel TFT to be converted into an n-channel TFT is covered with a mask layer 30 made of a hydrophobic polymer such as polyvinyl chloride (PVC), polyethylene (PE), or polypropylene (PE). . Then, in the same manner as in [Step-140] of Example 1, the bonding layer 22 is brought into contact with the second organic semiconductor molecule having the second conductivity type. Specifically, the whole is immersed in a toluene solution of fullerene (C ₆₀ ). Thereby, fullerene (C ₆₀ ) is taken into the molecular recognition field (network space), and the conductive path 21B can be obtained. Thus, a channel forming region 17B formed between the source / drain electrodes 16B and on the gate insulating layer 15 and constituted by the conductive path 21B can be formed, and an n-channel TFT (the first channel of the present invention) can be formed. (Corresponding to the organic electronic device according to the embodiment) can be obtained (see FIG. 9B).

[Step-360]
Finally, by forming a passivation film (not shown) on the entire surface, a bottom gate / bottom contact type FET (specifically, a TFT) can be obtained.

  Here, in [Step-330], the self-organization phenomenon by the microparticles 23 themselves is actively used to achieve the two-dimensional regular arrangement. Specifically, the fine particle layer 20 is based on a solution (for example, a fine particle colloid solution) containing the fine particles 23, and for example, a gold nanoparticle having a hydrophobic surface on a hydrophilic solvent (eg, water) is two-dimensionally formed as a single layer. Floating to have a regular arrangement, or conversely, floating gold nanoparticles having a hydrophilic surface on a hydrophobic solvent to have a two-dimensional regular arrangement in a single layer, which is similar to the LB method Transfer onto the substrate 13 based on the method. However, the method for forming the fine particle layer 20 is not limited to such a method, and for example, the fine particle layer 20 can be formed based on a casting method.

  Then, in [Step-340], the functional group possessed by the terminal of the first organic semiconductor molecule 24 is chemically bonded to the fine particles 23. More specifically, the functional group that the first organic semiconductor molecule 24 has at both ends (in Example 3, the first organic semiconductor molecule having a conjugated bond, which is a porphyrin molecule represented by the formula (104) The first organic semiconductor molecules 24 whose both ends are substituted with thiol groups [—SH]) and the fine particles 23 are chemically (alternatively) bonded to form the network-like conductive paths 21A and 21B. The Here, the conductive paths 21A and 21B are constituted by a single layer of a conjugate of the fine particles 23 and the first organic semiconductor molecules 24, or alternatively, a conjugate of the fine particles 23 and the first organic semiconductor molecules 24, etc. Conductive paths 21A and 21B are configured by the laminated structure. That is, after the fine particles 23 are regularly arranged two-dimensionally in a plane substantially parallel to the surface of the substrate 13 and in a filled state, the first organic semiconductor molecules 24 are brought into contact with each other. By performing the process once, a single layer of a conjugate of the microparticles 23 and the first organic semiconductor molecules 24 can be formed. By performing the process twice or more, the microparticles 23 and the first organic semiconductor molecules 24 can be combined. A layer composed of a bonded body is stacked, and a stacked structure of the bonded body can be obtained. Alternatively, by repeating the formation process of the fine particle layer 20 a plurality of times, the fine particles 23 are regularly arranged three-dimensionally in a filled state, and then the first organic semiconductor molecules 24 are contacted. By performing this step at least once, it is possible to obtain a laminated structure in which a layer made of a conjugate of the fine particles 23 and the first organic semiconductor molecules 24 is laminated. Thus, since the channel formation regions 17A and 17B can be formed by forming the fine particle layer 20 one by one, the channel formation regions 17A and 17B having a desired thickness can be formed by repeating this process. Can be formed. The channel formation regions 17A and 17B finally obtained in this way are composed of a combined body in which the fine particles 23 and the first organic semiconductor molecules 24 are connected in a network shape, and are applied to the gate electrodes 14A and 14B. Carrier movement is controlled by the gate voltage.

  In the channel formation regions 17A and 17B, the fine particles 23 are two-dimensionally or three-dimensionally connected by the first organic semiconductor molecules 24 to form network-like conductive paths 21A and 21B. The conductive paths 21A and 21B do not include the intermolecular electron movement that is the cause of the low mobility in the channel forming region made of the conventional organic semiconductor, and the electron movement within the molecule follows the molecular skeleton. Therefore, high mobility is expected. Electron conduction in the channel formation regions 17A and 17B is performed through the network-like conductive paths 21A and 21B, and the conductivity of the channel formation regions 17A and 17B is controlled by a gate voltage applied to the gate electrodes 14A and 14B. .

  Alternatively, in a step similar to [Step-330] and [Step-340], a toluene solution stock solution containing 30% by weight of gold fine particles (gold nanoparticles) is diluted to 200 ml with toluene, and powdered into 10 ml of toluene solution. By adding 200 milligrams of BPDT and mixing, gold fine particles and BPDT react in a short time, and the fine particles 23 and the first organic semiconductor molecules are combined to form a three-dimensional network. The formed cluster is formed and deposited as a precipitate at the bottom of the solution. That is, a functional group at the terminal of the first organic semiconductor molecule (a thiol group [—SH] which is a first organic semiconductor molecule having a conjugated bond, and is present at both ends of 4,4′-biphenyldithiol (BPDT)) Are chemically bonded to the fine particles 23. More specifically, the first organic semiconductor molecules and the fine particles 23 are chemically (alternately) by functional groups (thiol groups) possessed by the first organic semiconductor molecules at both ends. ) By bonding, the fine particles 23 and the first organic semiconductor molecules are bonded in a three-dimensional network form, and a cluster is formed. And the cluster obtained in this way is apply | coated to the whole surface, and is naturally dried. Also by this, the fine particle / first organic semiconductor molecule / bonding layer 22 and the conductive path 21A can be obtained.

The fourth embodiment is also a modification of the first embodiment. In Example 4, the organic electronic device was a bottom gate / top contact type FET (specifically, a TFT). The field-effect transistor of Example 4 (more specifically, an n-channel TFT) has a schematic partial cross-sectional view shown in FIG.
(A) a gate electrode 14B formed on the support 10;
(B) a gate insulating layer 15 (corresponding to the base 13) formed on the gate electrode 14B and the support 10;
(C) a channel formation region constituting layer 18B including the channel formation region 17B formed on the gate insulating layer 15 and constituted by the conductive path 21B; and
(D) source / drain electrodes 16B formed on the channel formation region constituting layer 18B,
It has. Alternatively, the field effect transistor of the fourth embodiment (more specifically, a p-channel TFT) has a schematic partial cross-sectional view shown in FIG.
(A) a gate electrode 14A formed on the support 10;
(B) a gate insulating layer 15 (corresponding to the base 13) formed on the gate electrode 14A and the support 10;
(C) a channel formation region constituting layer 18A including the channel formation region 17A formed on the gate insulating layer 15 and constituted by the conductive path 21A; and
(D) source / drain electrodes 16A formed on the channel formation region constituting layer 18A,
It has.

  Hereinafter, with reference to FIGS. 11A and 11B and FIGS. 12A and 12B which are schematic partial end views of the substrate and the like, the organic electronic device of Example 4 (field effect) The outline of the manufacturing method of the type transistor) will be described.

[Step-400]
First, after forming the gate electrodes 14A and 14B on the support 10 in the same manner as [Step-300] in the third embodiment, the gate electrodes 14A and 14B are formed in the same manner as in [Step-310] in the third embodiment. A gate insulating layer 15 corresponding to the base 13 is formed on a support (more specifically, the insulating layer 12) including

[Step-410]
Next, in the same manner as in [Step-330] of Example 3, the fine particle layer 20 composed of the fine particles 23 is formed on the substrate 13 (see FIG. 11A). Furthermore, a channel formation region constituting layer 18A including the channel formation region 17A can be formed by executing the same step as [Step-340] in the third embodiment. At the same time, a coupling layer 22 for forming an n-channel TFT can be obtained (see FIG. 11B). The coupling layer 22 also corresponds to the channel formation region constituting layer 18B.

[Step-420]
Thereafter, the source / drain electrode 16A is formed on the channel forming region constituting layer 18A for the p-channel TFT so as to sandwich the channel forming region 17A, and at the same time, the channel forming region constituting layer 18B for the n-channel TFT is formed. A source / drain electrode 16B for an n-channel TFT is formed on the region of this portion so as to sandwich this portion (see FIG. 12A). Specifically, in the same manner as in [Step-320] of Example 3, a titanium (Ti) layer (not shown) as an adhesion layer and a gold (Au) layer as source / drain electrodes 16A and 16B. Are sequentially formed on the basis of a vacuum deposition method. When these layers are formed, the source / drain electrodes 16A and 16B can be formed without a photolithography process by covering part of the channel formation region constituting layers 18A and 18B with a hard mask. In this way, a p-channel TFT can be obtained.

[Step-430]
Next, in the same manner as in [Step-350] in Example 3, the p-channel TFT other than the p-channel TFT to be converted into the n-channel TFT is covered with the mask layer 30. Then, in the same manner as in [Step-140] in Example 1, the bonding layer (porphyrin network monolayer film) 22 constituting the exposed channel forming region constituting layer 18B is formed into the second organic material having the second conductivity type. Contact with semiconductor molecules. Specifically, the whole is immersed in a toluene solution of fullerene (C ₆₀ ). Thereby, fullerene (C ₆₀ ) is taken into the molecular recognition field (network space), and the conductive path 21B can be obtained. Thus, a channel formation region 17B formed between the source / drain electrodes 16B and on the gate insulating layer 15 and constituted by the conductive path 21B can be formed, and an n-channel TFT can be obtained (FIG. 12 (B)).

[Step-440]
Finally, by forming a passivation film (not shown) on the entire surface, the semiconductor device of Example 4 can be completed.

The fifth embodiment is also a modification of the first embodiment. In Example 5, the organic electronic device was a top gate / bottom contact type FET (specifically, a TFT). The field effect transistor (more specifically, the n-channel TFT) of Example 5 has a schematic partial cross-sectional view shown in FIG.
(A) a source / drain electrode 16B formed on the insulating layer 12 corresponding to the base 13;
(B) a channel forming region 17B formed on the base 13 between the source / drain electrodes 16B and configured by the conductive path 21B;
(C) a gate insulating layer 15B formed on the source / drain electrode 16B and the channel formation region 17B, and
(D) a gate electrode 14B formed on the gate insulating layer 15B;
It has. Alternatively, the field effect transistor of the fifth embodiment (more specifically, a p-channel TFT) has a schematic partial cross-sectional view as shown in FIG.
(A) a source / drain electrode 16A formed on the insulating layer 12 corresponding to the substrate 13;
(B) a channel forming region 17A formed on the base 13 between the source / drain electrodes 16A and configured by the conductive path 21A;
(C) a gate insulating layer 15A formed on the source / drain electrode 16A and the channel formation region 17A, and
(D) a gate electrode 14A formed on the gate insulating layer 15A;
It has.

  Hereinafter, referring to FIGS. 13A and 13B and FIGS. 14A and 14B, which are schematic partial end views of the substrate and the like, the organic electronic device of Example 5 (field effect) The outline of the manufacturing method of the type transistor) will be described.

[Step-500]
First, after the source / drain electrodes 16A and 16B are formed on the insulating layer 12 corresponding to the substrate 13 by the same method as [Step-320] of Example 3, the same as [Step-120] of Example 1 is performed. Then, the fine particle layer 20 composed of the fine particles 23 is formed on the substrate 13 (more specifically, the insulating layer 12) including the source / drain electrodes 16A and 16B (see FIG. 13A).

[Step-510]
Thereafter, the whole is immersed in the porphyrin molecule solution of Example 1 in the same manner as in [Step-130] of Example 1. As a result of replacement of the porphyrin molecules, such as the first organic semiconductor molecules, with the organic molecules constituting the protective film, a chemical conjugate of the fine particles 23 and the first organic semiconductor molecules 24 is formed, and the conductive path 21A. (Channel forming region 17A) and a coupling layer (porphyrin network single layer film) 22 can be formed (see FIG. 13B).

[Step-520]
Next, a gate insulating layer 15A for the p-channel TFT is formed by the same method as in [Step-310] of the third embodiment. Thereafter, a gate electrode 14A is formed in the same manner as in [Step-300] of Example 3 on the portion of the gate insulating layer 15A above the channel formation region 17A to obtain a p-channel TFT (FIG. 14). (See (A)), the p-channel TFT is covered with the mask layer 30 in the same manner as in [Step-350] of Example 3.

[Step-530]
Thereafter, in the same manner as in [Step-140] in Example 1, the exposed bonding layer 22 is brought into contact with the second organic semiconductor molecule having the second conductivity type. Specifically, the whole is immersed in a toluene solution of fullerene (C ₆₀ ). Thereby, fullerene (C ₆₀ ) is taken into the molecular recognition field (network space), and the conductive path 21B can be obtained.

[Step-540]
Next, after forming the gate insulating layer 15B for the n-channel TFT by the same method as [Step-310] in Example 3, the gate insulating layer 15B above the channel formation region 17B is formed. A gate electrode 14B is formed in the same manner as in [Step-300] in Example 3 (see FIG. 14B). Thus, an n-channel TFT can be obtained.

[Step-550]
Finally, by forming a passivation film (not shown) on the entire surface, the semiconductor device of Example 5 can be completed.

The sixth embodiment is also a modification of the first embodiment. In Example 6, the organic electronic device was a top gate / top contact type FET (specifically, TFT). In the field effect transistor of Example 6 (more specifically, an n-channel TFT), as shown in a schematic partial cross-sectional view in FIG.
(A) a channel formation region constituting layer 18B including a channel formation region 17B formed on the insulating layer 12 corresponding to the base 13 and constituted by the conductive path 21B;
(B) a source / drain electrode 16B formed on the channel formation region constituting layer 18B,
(C) a gate insulating layer 15B formed on the source / drain electrode 16B and the channel formation region 17B, and
(D) a gate electrode 14B formed on the gate insulating layer 15B;
It has. Alternatively, the field-effect transistor of Example 6 (more specifically, a p-channel TFT) has a schematic partial cross-sectional view as shown in FIG.
(A) A channel forming region constituting layer 18A including a channel forming region 17A formed on the insulating layer 12 corresponding to the base 13 and constituted by the conductive path 21A;
(B) a source / drain electrode 16A formed on the channel formation region constituting layer 18A,
(C) a gate insulating layer 15A formed on the source / drain electrode 16A and the channel formation region 17A, and
(D) a gate electrode 14A formed on the gate insulating layer 15A;
It has.

  Hereinafter, with reference to FIGS. 15A and 15B and FIGS. 16A and 16B which are schematic partial end views of the substrate and the like, the organic electronic device of Example 6 (field effect) The outline of the manufacturing method of the type transistor) will be described.

[Step-600]
First, in the same manner as in [Step-120] of Example 1, the fine particle layer 20 composed of the fine particles 23 is formed on the substrate 13 (more specifically, the insulating layer 12).

[Step-610]
Thereafter, the whole is immersed in the porphyrin molecule solution of Example 1 in the same manner as in [Step-130] of Example 1. As a result of replacement of the porphyrin molecules, such as the first organic semiconductor molecules, with the organic molecules constituting the protective film, a chemical conjugate of the fine particles 23 and the first organic semiconductor molecules 24 is formed, and the conductive path 21A. (Channel forming region 17A) and coupling layer (porphyrin network monolayer film) 22 can be formed (see FIG. 15A). The conductive path 21A and the coupling layer 22 correspond to the channel formation region constituting layers 18A and 18B.

[Step-620]
Next, source / drain electrodes 16A and 16B are formed on the channel formation region constituting layers 18A and 18B in the same manner as in [Step-320] in Example 3 (see FIG. 15B).

[Step-630]
Thereafter, a gate insulating layer 15A for the p-channel TFT is formed in the same manner as in [Step-310] in Example 3. Next, after forming a gate electrode 14A in the same manner as in [Step-300] of Example 3 on the portion of the gate insulating layer 15A above the channel formation region 17A to obtain a p-channel TFT (FIG. 16). (See (A)), the p-channel TFT is covered with the mask layer 30 in the same manner as in [Step-350] of Example 3.

[Step-640]
Next, in the same manner as in [Step-140] in Example 1, the exposed bonding layer 22 is brought into contact with the second organic semiconductor molecule having the second conductivity type. Specifically, the whole is immersed in a toluene solution of fullerene (C ₆₀ ). Thereby, fullerene (C ₆₀ ) is taken into the molecular recognition field (network space), and the conductive path 21B can be obtained.

[Step-650]
Thereafter, a gate insulating layer 15B for an n-channel TFT is formed by the same method as in [Step-310] of Example 3, and then the part of the gate insulating layer 15B above the channel forming region 17B is formed in the example. The gate electrode 14B is formed by the same method as in [Step-300] in FIG. 3 (see FIG. 16B). Thus, an n-channel TFT can be obtained.

[Step-660]
Finally, by forming a passivation film (not shown) on the entire surface, the semiconductor device of Example 6 can be completed.

  Porphyrin is a cyclic conjugated molecule having 18 electrons formed by combining four pyrroles. And in the center part, a stable complex is formed with many metals, such as zinc, ruthenium, cobalt, gold | metal | money, magnesium, and iron. In natural photosynthesis, it is known that photoelectric conversion occurs by using an assembly of porphyrin molecules. For example, when a porphyrin molecule absorbs light, electrons are excited from the ground state to form stable excitons. This excitation energy passes electrons to the reaction center while repeating the movement between molecules with very high efficiency, and causes photosynthesis.

  As shown in FIG. 17, the organic semiconductor molecule of the present invention represented by the formula (104) has a thiol-modified oligothiophene derivative (compound 3 in FIG. 17) and an alkyl group-modified dipyrromethene (see FIG. 17). 17 is a porphyrin derivative (compound 5 in FIG. 17) synthesized by a condensation reaction of 17 compound 4). That is, the porphyrin molecule, which is the organic semiconductor molecule of the present invention, is obtained by, for example, binding a thioacetyl group to one end of oligothiophene (n = 1 to 5, compound 1 in FIG. 17) (compound 2 in FIG. 17). Then, an aldehyde group is generated at the other end (compound 3 in FIG. 17). Next, a porphyrin derivative (the organic semiconductor molecule of the present invention, compound 5 in FIG. 17) is synthesized by a condensation reaction with dipyrromethene (compound 4 in FIG. 17) and an oxidation reaction. In addition, the 1st organic-semiconductor molecule | numerator (refer Formula (105)) of the reference example 1 is synthesize | combined by a condensation reaction with a pyrrole, and an oxidation reaction.

  Hereinafter, a method for synthesizing the organic semiconductor molecule of the present invention represented by the formula (104) will be described.

[Synthesis of Compound 2 in FIG. 17 where n = 2]
In a 100 milliliter THF solution containing 10 grams (60 millimoles) of Compound 1 (n = 2), 37 milliliters (60 millimoles) 1.6 M at −78 ° C. in an argon stream. The n-butyllithium solution is slowly added dropwise. After 30 minutes, 1.9 grams (60 millimoles) of sulfur (S) is added and stirred at 0 ° C. for 1 hour. Next, after cooling the atmosphere to −78 ° C., 5 milliliters (72 millimoles) of acetyl chloride is added and stirred for 1 hour. Then, the reaction solution is allowed to return to room temperature and stirred overnight. Thereafter, water is added to stop the reaction, and then dichloromethane is added. Next, it is washed successively with water and saturated saline and dried. When purified by silica gel column chromatography (hexane: ether = 2: 1), 10.5 g (yield 73%) of a yellow solid was obtained. The analysis results were as follows.
¹ HNMR (CDCl ₃ ): δ 7.25 (s, 1H), 7.20 (d, 1H), 7.15 (d, 1H), 7.07 (d, 1H), 7.03 (d, 1H) ), 2.41 (s, 3H)

[Synthesis of Compound 3 in FIG. 17 where n = 2]
To a 10 milliliter dichloroethane solution containing 2 grams (8.3 millimoles) of Compound 2 (n = 2) and 1.3 milliliters of DMF was added 0.9 milliliter (9 Slowly add 1 millimol) of phosphorus oxychloride. Then, after refluxing overnight, the reaction solution is slowly added dropwise to 50 milliliters of a saturated aqueous solution of sodium acetate to stop the reaction. Thereafter, dichloromethane is added, and the mixture is washed successively with water and saturated brine and dried. Purification by silica gel column chromatography (hexane: dichloromethane = 1: 3) gave 1.1 grams (yield 50%) of a yellow solid. The analysis results were as follows.
¹ HNMR (CDCl ₃ ): δ 9.85 (s, 1H), 7.91 (d, 1H), 7.80 (d, 1H), 7.51 (d, 1H), 7.12 (d, 1H) ), 7.04 (d, 1H), 2.40 (s, 3H)
MALDI-TOF-MS: m / z = 268.37 [M ⁺ ]
C ₁₁ H ₈ O ₂ S ₃ calculated value: m / z = 268.69 [M ⁺ ]

[Synthesis of Compound 4 in FIG. 17]
After replacing 150 milliliters (1.5 moles) of pyrrole containing 6 milliliters (50 millimoles) of n-hexanal with argon (20 minutes), 0.9 milliliters of TFA (trifluoroacid) was added. In addition, after stirring at room temperature for 30 minutes, 1 milliliter of TEA is added to stop the reaction. Excess pyrrole was removed by distillation under reduced pressure and purified by silica gel column chromatography (hexane: ethyl acetate: TEA = 8: 2: 0.1) to give 3.36 grams (yield 30%) of brown oil. was gotten. The analysis results were as follows.
¹ HNMR (CDCl ₃ ): δ 7.77 (s, 1H), 6.65 (s, 2H), 6.17 (t, 2H), 6.09 (s, 2H), 3.99 (t, 1H) ), 1.96 (m, 2H), 1.32 (m, 6H), 0.89 (t, 3H)

[Synthesis of Compound 5 in FIG. 17 where n = 2]
A 300 milliliter chloromethane solution containing 0.8 grams (3.0 millimoles) of compound 3 (n = 2) and 0.68 grams (3.0 millimoles) of compound 4 was purged with argon ( 20 minutes), add 0.36 milliliters TFA and stir at room temperature for 3 hours. An additional 0.72 grams of p-chloroanil is added and stirred for 1 hour, then 0.64 milliliters of TEA is added to stop the reaction. Thereafter, a 50 milliliter methanol solution containing 0.77 grams of Zn (OAc) ₂ is added and stirred at room temperature for 2 hours. Next, after filtration through a silica shot column, the mixture is washed successively with water and saturated brine and dried. Purification by silica gel column chromatography (hexane: dichloromethane = 1: 2) gave 0.22 grams (15% yield) of a red solid. The analysis results were as follows.
MALDI-TOF-MS: m / z = 990.10 [M ⁺ ]
Calculated value of C ₅₀ H ₄₄ N ₄ O ₂ S ₈ Zn: m / z = 990.69 [M ⁺ ]

[Synthesis of Compound 6 in FIG. 17 where n = 2]
350 milligrams (1.0 millimoles) of compound 3 (n = 2), 120 milligrams (1.0 millimoles) of n-hexanal and 460 milligrams (2.0 millimoles) After 200 milliliters of the chloromethane solution containing Compound 4 was replaced with argon (20 minutes), 0.24 milliliter of TFA was added and stirred at room temperature for 3 hours. Further, 460 milligrams of p-chloroanil is added and stirred for 1 hour, followed by the addition of 20 milliliters of methanol solution containing 0.28 grams of Zn (OAc) ₂ . Next, after filtration through a silica shot column, the mixture is washed successively with water and saturated brine and dried. Purification by silica gel column chromatography (hexane: dichloromethane = 1: 2) gave 0.09 grams (11% yield) of a red solid. The analysis results were as follows.
MALDI-TOF-MS: m / z = 820.19 [M ⁺ ]
Calculated value of C ₄₅ H ₄₈ N ₄ OS ₃ Zn: m / z = 820.22 [M ⁺ ]

  In addition, the result of having measured the MALDI-TOF-MS spectrum of the compound 5 (the organic semiconductor molecule of an Example, n = 2) of FIG. 17 and the compound 6 (the organic semiconductor molecule of a reference example, n = 2) of FIG. FIG. 18 shows the lower and upper stages.

[Synthesis of Compound 2 in FIG. 17 where n = 3]
A 15 milliliter THF solution containing 1.0 gram (4.0 millimoles) of Compound 1 (n = 3) was charged with 3.0 milliliters (4.8 at −78 ° C. in an argon stream). A 1.6M n-butyllithium solution in millimoles is slowly added dropwise. After 30 minutes, 0.15 grams (4.8 millimoles) of sulfur (S) is added and stirred at 0 ° C. for 1 hour. Next, after cooling the atmosphere to −78 ° C., 0.33 milliliter (4.8 millimol) of acetyl chloride is added and stirred for 1 hour. Then, the reaction solution is allowed to return to room temperature and stirred overnight. Thereafter, water is added to stop the reaction, and then dichloromethane is added. Next, it is washed successively with water and saturated saline and dried. Purification by silica gel column chromatography (hexane: ether = 2: 1) gave 0.8 gram (yield 63%) of a yellow solid. The analysis results were as follows.
¹ HNMR (CDCl ₃ ): δ 7.26-7.05 (m, 7H), 2.45 (s, 3H)
MALDI-TOF-MS: m / z = 321.77 [M ⁺ ]
C ₁₄ H ₁₀ OS ₄ calculated value: m / z = 321.96 [M ⁺ ]

[Synthesis of Compound 3 in FIG. 17 where n = 3]
0.18 milliliters in a 10 milliliter dichloroethane solution containing 0.54 grams (1.7 millimoles) of Compound 2 (n = 3) and 0.14 milliliter DMF in a stream of argon. Slowly add (2.0 millimoles) of phosphorus oxychloride. Then, after refluxing overnight, the reaction solution is slowly added dropwise to 50 milliliters of a saturated aqueous solution of sodium acetate to stop the reaction. Thereafter, dichloromethane is added, and the mixture is washed successively with water and saturated brine and dried. Purification by silica gel column chromatography (hexane: dichloromethane = 1: 3) gave 1.9 grams (34% yield) of a yellow solid. The analysis results were as follows.
¹ HNMR (CDCl ₃ ): δ 9.88 (s, 1H), 7.29-7.08 (m, 6H), 2.46 (s, 3H)
MALDI-TOF-MS: m / z = 350.37 [M ⁺ ]
C ₁₅ H ₁₀ O ₂ S ₄ calculated value: m / z = 349.95 [M ⁺ ]

[Synthesis of Compound 5 in FIG. 17 where n = 3]
A 300 milliliter chloromethane solution containing 1 gram (2.85 millimoles) of compound 3 (n = 3) and 0.66 grams (2.85 millimoles) of compound 4 was purged with argon (20 minutes). ), Add 0.34 milliliters of TFA, and stir at room temperature for 3 hours. An additional 0.67 grams of p-chloroanil is added and stirred for 1 hour, then 0.67 milliliters of TEA is added to stop the reaction. Thereafter, a 50 milliliter methanol solution containing 0.77 grams of Zn (OAc) ₂ is added and stirred at room temperature for 2 hours. Next, after filtration through a silica shot column, the mixture is washed successively with water and saturated brine and dried. Purification by silica gel column chromatography (hexane: dichloromethane = 1: 2) gave 0.16 grams (10% yield) of a red solid. The analysis results were as follows.
MALDI-TOF-MS: m / z = 1153.87 [M + H] ⁺
C ₅₈ H ₄₉ N ₄ O ₂ S ₈ Zn Calculated value: m / z = 1153.08 [M + H] ⁺

[Synthesis of Compound 6 in FIG. 17 where n = 3]
174 milligrams (0.5 millimoles) of compound 3 (n = 3), 60 milligrams (0.5 millimoles) of n-hexanal and 230 milligrams (1.0 millimoles) After replacing 100 mL of the chloromethane solution containing Compound 4 with argon (20 minutes), add 0.12 mL of TFA, and stir at room temperature for 3 hours. Further, 230 milligrams of p-chloroanil is added and stirred for 1 hour, followed by the addition of 10 milliliters of methanol solution containing 0.14 grams of Zn (OAc) ₂ . Next, after filtration through a silica shot column, the mixture is washed successively with water and saturated brine and dried. Purification by silica gel column chromatography (hexane: dichloromethane = 1: 2) gave 45 milligrams (10% yield) of a red solid. The analysis results were as follows.
MALDI-TOF-MS: m / z = 903.97 [M + H] ⁺
C ₄₉ H ₅₁ N ₄ OS ₄ Zn calculated value: m / z = 903.21 [M + H] ⁺

  In addition, the result of having measured the MALDI-TOF-MS spectrum of the compound 5 (the organic semiconductor molecule of an Example, n = 3) of FIG. 17 and the compound 6 (an organic semiconductor molecule of a reference example, n = 3) of FIG. FIG. 19 shows the lower and upper stages.

As mentioned above, although this invention was demonstrated based on the preferable Example, this invention is not limited to these Examples. The structure, configuration, formation conditions, and manufacturing conditions of the organic electronic device and the conductive path are examples, and can be changed as appropriate. When a field effect transistor (FET), which is an organic electronic device obtained by the present invention, is applied to and used in a display device or various electronic devices, it is a monolithic integrated circuit in which a large number of FETs are integrated on a support or a support member. Alternatively, each FET may be cut and individualized and used as a discrete component. The fine particles are not limited to gold (Au), but are not limited to other metals (for example, silver and platinum), cadmium sulfide, cadmium selenide, silicon and the like as semiconductors, but also poly (3,4- It can also be composed of a conductive organic material such as ethylenedioxythiophene) / polystyrene sulfonic acid [PEDOT / PSS], polythiophene, polyaniline. Further, the first organic semiconductor molecule and the second organic semiconductor molecule are not limited to porphyrin, 4,4′-biphenyldithiol (BPDT), and fullerene (C ₆₀ ). An element isolation region may be formed between the p-channel transistor and the n-channel transistor, or may not be formed in some cases.

DESCRIPTION OF SYMBOLS 10 ... Support body, 11 ... Glass substrate, 12 ... Insulating layer, 13 ... Base | substrate, 14A, 14B ... Gate electrode, 15, 15A, 15B ... Gate insulating layer, 16A, 16B ... source / drain electrodes, 17A, 17B ... channel forming region, 18A, 18B ... channel forming region constituting layer, 20 ... fine particle layer, 21A, 21B ... conductive path, 22. Fine particles / first organic semiconductor molecules / bonding layer (bonding layer), 23... Fine particles, 24... First organic semiconductor molecule, etc. 30.

Claims (6)

(A) fine particles, and
(B) an organic semiconductor molecule in which fine particles are combined,
Comprising a conductive path that behaves as a p-type,
The organic semiconductor device is represented by the following structural formula (1).
In Structural Formula (1), R ₁ and R ₂ represent alkyl groups, and M represents 2H, Zn ⁺² , Mg ⁺² , Fe ⁺² , Co ⁺² , Ni ⁺² , and Cu ⁺² . , N is an integer from 1 to 5. The organic electronic device according to claim 1 , wherein a thiol group at a terminal of the organic semiconductor molecule is chemically bonded to the fine particles. 2. The organic electronic device according to claim 1 , wherein an average particle diameter of the fine particles is 1 × 10 ⁻⁸ m or less. Organic electronic devices consist of field-effect transistors,
The organic electronic device according to claim 1 , wherein a channel forming region is constituted by the conductive path. After the fine particle layer is formed on the substrate, it is immersed in a solution containing an organic semiconductor molecule represented by the following structural formula (1) to form fine particles and organic semiconductor molecules in which the fine particles and the fine particles are combined. A method for producing an organic electronic device, comprising forming a conductive path exhibiting a p-type behavior.
In Structural Formula (1), R ₁ and R ₂ represent alkyl groups, and M represents 2H, Zn ⁺² , Mg ⁺² , Fe ⁺² , Co ⁺² , Ni ⁺² , and Cu ⁺² . , N is an integer from 1 to 5. An organic semiconductor molecule represented by the following structural formula (2).
In Structural Formula (2), R ₁ and R ₂ represent alkyl groups, and M represents 2H, Zn ⁺² , Mg ⁺² , Fe ⁺² , Co ⁺² , Ni ⁺² , and Cu ⁺² . , N is an integer from 1 to 5.