JP2006108400A - Semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a semiconductor device having a configuration in which a particulate and an organic semiconductor molecule for constituting a conductive path can join certainly and firmly. <P>SOLUTION: The semiconductor device includes the particulate 21 which is a conductor or a semiconductor and made of an organic material and a conductive path 20 configured by an organic semiconductor molecule 22 is formed on the substrate 13. The functional group provided in the organic molecule for constituting the organic material and the functional group provided in the organic semiconductor molecule are joined. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a semiconductor device.

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

  Thus, in recent years, attention has been focused on the research and development of 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.

  By the way, since it is required to be incorporated into many electronic devices including a display device, the FET is required to operate at high speed. For example, there is a need for an FET that can convert a video signal into necessary data at any time and can perform an on / off switching operation at high speed.

However, the mobility, which is a characteristic index of a TFT having a channel formation region made of an organic semiconductor material (hereinafter sometimes referred to as an organic TFT), is typically 10 ^{−3 to 1} cm ² / Vs. (See, for example, CD Dimitrakopoulos, et al., Adv. Mater. (2002), 14, 99). This value is lower than several cm ² / Vs, which is the mobility of amorphous silicon, and approximately 100 cm ² / Vs, which is the mobility of polysilicon, and is 1 to 3 cm ² / Vs required for TFTs for display devices. Not reached. Therefore, in organic FETs, improvement of mobility is a major issue.

  Mobility in organic FETs is determined by intramolecular charge transfer and intermolecular charge transfer. Intramolecular charge transfer is made possible by overlapping atomic bonds in adjacent multiple bonds across a single bond and delocalizing electrons to form a conjugated system. The movement of charge between molecules is performed by intermolecular bonding, conduction due to overlapping of molecular orbitals by van der Waals forces, or hopping conduction through trap levels between molecules.

In this case, if the intramolecular mobility is μ _intra , the intermolecular mobility is μ _inter , and the intermolecular hopping mobility is μ _hop , the following relationship is established. In an organic semiconductor material, the charge mobility is low because slow intermolecular charge transfer limits the overall mobility.

μ _intra ≫μ _inter > μ _hop

International Publication WO2004 / 006337A1 JP 2004-6827 A C. D. Dimitrakopoulos, et al., Adv. Mater. (2002), 14, 99

  Therefore, various studies have been made to improve the mobility in organic FETs.

  For example, in the semiconductor device disclosed in International Publication WO2004 / 006337A1, a conductive path is formed by fine particles made of a conductor or a semiconductor and organic semiconductor molecules bonded to the fine particles, and the conductivity of the conductive path is controlled by an electric field. Is done. By adopting such a structure, charge movement in the conductive path occurs predominantly in the axial direction of the molecule along the main chain of the organic semiconductor molecule, and the mobility in the axial direction of the molecule, for example, non-locality It is possible to make maximum use of the high intramolecular mobility due to the activated p electrons. As a result, an unprecedented high mobility comparable to that of a monolayer transistor can be realized.

  Japanese Patent Application Laid-Open No. 2004-6827 discloses an organic thin film transistor element. In this organic thin film transistor element, when an electric field is not applied to the organic semiconductor layer connecting the source electrode and the drain electrode, the source electrode or drain A conductive region is provided that is insulative with at least one of the electrodes. And this electroconductive area | region is comprised from electroconductive fine particles, and various electroconductive polymer and metal microparticles | fine-particles are mentioned as electroconductive fine particles.

  By the way, in the semiconductor device disclosed in International Publication WO2004 / 006337A1, since the fine particles are made of an inorganic material, the entire conductive path has a drawback of poor flexibility. In addition, fine particles made of an inorganic material are difficult to artificially change the structure and composition, so the only way to improve the performance of the conductive path is to change the material itself of the fine particles.

  In the organic thin film transistor element disclosed in Japanese Patent Application Laid-Open No. 2004-6827, although various conductive polymers are listed as the conductive fine particles, specific bonding modes and bonding methods between the conductive fine particles and the organic semiconductor material Is not mentioned at all.

  Accordingly, an object of the present invention is to provide a semiconductor device having a configuration capable of reliably and firmly bonding fine particles constituting a conductive path and organic semiconductor molecules.

A semiconductor device for achieving the above object is a semiconductor device in which a conductive path formed of a fine particle made of an organic material, which is a conductor or a semiconductor, and an organic semiconductor molecule is formed on a substrate,
The functional group which the organic molecule which comprises an organic material has, and the functional group which an organic-semiconductor molecule has are couple | bonded.

  In the semiconductor device of the present invention, examples of the bond between the functional group of the organic molecule constituting the organic material and the functional group of the organic semiconductor molecule include a covalent bond, a hydrogen bond, an ionic bond, a coordinate bond, and a van der Waals bond. Among them, a covalent bond is desirable from the viewpoint of achieving a strong bond.

  In the semiconductor device of the present invention, the bond between the functional group of the organic molecule constituting the organic material and the functional group of the organic semiconductor molecule can be based on a diazo coupling reaction. As a combination of (functional group possessed by organic molecule constituting organic group, functional group possessed by organic semiconductor molecule), (diazonium group, phenol group), (diazonium group, phenylamino group), (phenol group, diazonium group), or ( Phenylamino group, diazonium group).

  Alternatively, in the semiconductor device of the present invention, the bond between the functional group of the organic molecule constituting the organic material and the functional group of the organic semiconductor molecule can be based on aldol condensation. As a combination of the functional group of the organic molecule constituting the material and the functional group of the organic semiconductor molecule), (aldehyde group, aldehyde group), (aldehyde group, phosphorus ylide group), (ketone group, phosphorus ylide group), (phosphorus ylide group) , Aldehyde group) or (phosphorus ylide group, ketone group).

  Alternatively, in the semiconductor device of the present invention, the bond between the functional group of the organic molecule constituting the organic material and the functional group of the organic semiconductor molecule can be based on an ester bond. As a combination of the functional group of the organic molecule constituting the material, the functional group of the organic semiconductor molecule), (carboxyl group, hydroxyl group), (halogenated acyl group, hydroxyl group), (anhydrous carboxyl group, hydroxyl group), (Hydroxyl group, carboxyl group), (hydroxyl group, halogenated acyl group), or (hydroxyl group, anhydrous carboxyl group).

  Alternatively, in the semiconductor device of the present invention, the bond between the functional group of the organic molecule constituting the organic material and the functional group of the organic semiconductor molecule can be based on an amide bond. As a combination of the functional group of the organic molecule constituting the material, the functional group of the organic semiconductor molecule), (carboxyl group, amino group), (halogenated acyl group, amino group), (anhydrous carboxyl group, amino group), (Amino group, carboxyl group), (amino group, acyl halide group), or (amino group, anhydrous carboxyl group) can be mentioned.

  Alternatively, in the semiconductor device of the present invention, the bond between the functional group of the organic molecule constituting the organic material and the functional group of the organic semiconductor molecule can be based on a urethane bond. As a combination of the functional group of the organic molecule constituting the material and the functional group of the organic semiconductor molecule), (isocyanate group, hydroxyl group), (hydroxyl group, isocyanate group), (isocyanate group, thiol group), (thiol group) , Isocyanate group), (isothiocyanate group, hydroxyl group), (hydroxyl group, isothiocyanate group), (isothiocyanate group, thiol group), or (thiol group, isothiocyanate group).

  Alternatively, in the semiconductor device of the present invention, the bond between the functional group of the organic molecule constituting the organic material and the functional group of the organic semiconductor molecule can be based on a disulfide bond. (Thiol group, thiol group) can be given as a combination of the functional group of the organic molecule constituting the material and the functional group of the organic semiconductor molecule.

  Alternatively, in the semiconductor device of the present invention, the bond between the functional group of the organic molecule constituting the organic material and the functional group of the organic semiconductor molecule may be based on the bond between the halogenated alkyl group and the alkyne. In this case, as a combination of (functional group of organic molecule constituting organic material, functional group of organic semiconductor molecule), (halogenated alkyl group, alkyne) or (alkyne, halogenated alkyl group) Can be mentioned.

  Alternatively, in the semiconductor device of the present invention, the bond between the functional group of the organic molecule constituting the organic material and the functional group of the organic semiconductor molecule can be based on Claisen condensation. Examples of the combination of the functional group possessed by the organic molecule constituting the material and the functional group possessed by the organic semiconductor molecule include (ester bond, ester bond).

In the semiconductor device of the present invention including the various forms described above, the organic semiconductor molecule preferably has two or more functional groups. Alternatively, in the semiconductor device of the present invention including the various forms described above, the organic semiconductor molecule is an organic semiconductor molecule having a conjugated bond, and a thiol group (—SH), an amino group ( —NH ₂ ), diazonium group (—N ₂ ⁺ ), phenol group (—C ₆ H ₄ OH), phenylamino group (—C ₆ H ₄ NH ₂ ), aldehyde group (—CHO), ketone group (—CO -), phosphorus ylide group _{(= P (C 6 H 5} ) 3), a carboxyl group (-COOH), a hydroxyl (-OH), an acyl halide group (-COX (X: Cl, Br , I)), anhydrous It preferably has a carboxyl group (—COOCO—), an isocyanate group (—NCO), an isothiocyanate group (—NCS), an alkyne (—C≡C—H), or an ester bond (—COO—). Note that it is preferable that the π-conjugated system in the organic semiconductor molecule is maintained in a state where the functional group of the organic molecule constituting the organic material and the functional group of the organic semiconductor molecule are bonded. Further, examples of the functional group possessed by the organic molecule constituting the organic material include the above functional group possessed by the organic semiconductor molecule.

  Specifically, as an organic semiconductor molecule, for example, 4,4′-biphenyldithiol (BPDT) of the structural formula (1), benzidine (biphenyl-4,4′-diamine) of the structural formula (2), structural formula ( 3) biphenyl-4,4′-dicarboxylic acid, 1,4-di (4-thiophenylethynyl) -2-ethylbenzene of structural formula (4), or Bovine Serum Albumin, Horse Radish Peroxidase, and antibody-antigen. It can be illustrated. These are all π-conjugated molecules and preferably have functional groups that chemically bond to the fine particles in at least two places. Further, as an organic semiconductor molecule, a dendrimer represented by the structural formula (5), 2,2 ″ -dihydroxy-1,1 ′: 4 ′, 1 ″ -terphenyl, 4,4′-biphenyldietanal, 4 4,4'-biphenyldiol, 4,4'-biphenyl diisocyanate, 1,4-diacetinylbenzene, diethylbiphenyl-4,4'-dicarboxylate can also be used.

Structural formula (1): 4,4′-biphenyldithiol

Structural formula (2): benzidine (biphenyl-4,4′-diamine)

Structural formula (3): Biphenyl-4,4′-dicarboxylic acid

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

Structural formula (5): Dendrimer

  In the semiconductor device of the present invention including the various forms described above, the conductive path can be used as a wiring or an electrode, and the conductivity of the conductive path is controlled by the electric field applied to the conductive path. You can also In the latter case, the semiconductor device of the present invention includes a field effect transistor (FET) having a gate electrode, a gate insulating layer, a channel formation region, and a source / drain electrode, and the channel formation region is configured by a conductive path. The structure can be made. In such a structure, it is possible to operate as an optical sensor or the like by using a dye that absorbs light near the visible region as an organic semiconductor molecule having a conjugated system.

As a more specific configuration of the field effect transistor,
(A) a gate electrode formed on a support;
(B) a gate insulating layer (corresponding to a substrate) formed on the support and the gate electrode;
(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;
A so-called bottom-gate / bottom-contact field effect transistor can be given.

Alternatively,
(A) a gate electrode formed on a support;
(B) a gate insulating layer (corresponding to a substrate) formed on the support and the gate electrode;
(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,
A so-called bottom-gate / top-contact field effect transistor including the above can be given.

Alternatively,
(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;
A so-called top gate / bottom contact type field effect transistor can be given.

Alternatively,
(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;
A so-called top-gate / top-contact field effect transistor can be given.

In the present invention, poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid [PEDOT / PSS] represented by Structural Formula (21), Structural Formula (22) as the organic material constituting the fine particles as the conductor. In the polyaniline represented by the structural formula (23), polypyrrole represented by the structural formula (24), poly (p-phenylene) [PPP] represented by the structural formula (25), and the structural formula (26). And polyphenylene vinylene [PPV] represented by the structural formula (28) can be exemplified as an organic material constituting fine particles as a semiconductor. And the phthalocyanine represented by the structural formula (30). 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 ⁻⁶ Ω · cm) or less. The fine particles as a semiconductor are fine particles made of a material having a volume resistivity of the order of 10 ⁻⁴ Ω · m (10 ⁻⁶ Ω · cm) to 10 ¹² Ω · m (10 ¹⁰ Ω · cm). Point to. The introduction of the above-mentioned various functional groups into the above-mentioned various organic materials (including the cases where the various organic materials themselves have and modifications) is performed before the preparation of the fine particles and before the doping. Just do it.

Structural formula (21): Poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid [PEDOT / PSS]

Structural formula (22): Polyaniline

Structural formula (23): Polythiophene

Structural formula (24): Polypyrrole

Structural formula (25): poly (p-phenylene) [PPP]

Structural formula (26): Polyacene

Structural formula (27): Polyacetylene

Structural formula (28) polyphenylene vinylene [PPV]

Structural formula (29) Fullerene [C ₆₀ ]

Structural formula (30): phthalocyanine

  In addition to the well-known suspension polymerization method, emulsion polymerization method, dispersion polymerization method, spray drying method, reprecipitation method (H. Kasai et al., Jpn. J. Appl) Phys., 31, L1132 (1992)). The organic molecule constituting the organic material needs to have a functional group capable of chemically bonding with the organic semiconductor molecule, but the organic molecule constituting the organic material does not have such a functional group itself. In some cases, a functional group is introduced by chemically modifying organic molecules constituting the organic material in advance.

  In the semiconductor device of the present invention, after the fine particles are arranged (arranged) on the base (that is, after the fine particle layer is formed on the base), the organic semiconductor molecules are brought into contact (more specifically, for example, organic Soaking in a solution containing semiconductor molecules or applying a solution containing organic semiconductor molecules by spin coating or the like), the functional groups of the organic molecules constituting the organic material (or modifying the organic molecules constituting the organic material) The functional group) and the functional group of the organic semiconductor molecule react and bond. The reaction and bonding may require external energy such as heat and ultraviolet light, and reagents such as catalysts, acids and bases.

  In order to obtain fine particles as a conductor (in some cases, as a semiconductor), it may be necessary to introduce carriers into the fine particles by doping. As a doping method, a chemical doping method using a doping material such as a halogen such as iodine or bromine, a Lewis acid, or an alkali metal (a method of chemically reacting an organic material constituting a fine particle with a doping material), electro A method such as a chemical doping method (a method in which fine particles are immersed in an electrolyte solution and electrochemically doped with electrolyte ions [doping material, dopant]) can be used. The fine particle layer is preferably formed in a state in which the fine particles have conductivity, that is, it is preferable to dope the fine particles at the time of particle preparation, but the doping may be performed before the fine particle layer formation and after the fine particle layer formation. .

  Alternatively, in order to form fine particles as a conductor (in some cases as a semiconductor), when it is necessary to perform polymerization after the production of the fine particles, the polymerization may be performed based on heat, ultraviolet light, or the like. The polymerization step can be carried out at any stage, such as during particle preparation, before formation of the fine particle layer, and after formation of the fine particle layer.

In the semiconductor device of the present invention, it is preferable that σ / r _AVE ≦ 0.5 is satisfied, where r _AVE is the average particle size of the fine particles and σ is the standard deviation of the particle size of the fine particles. The r _AVE range is 5.0 × 10 ⁻¹⁰ m ≦ r _AVE ≦ 1.0 × 10 ⁻⁶ m, preferably 5.0 × 10 ⁻¹⁰ m ≦ r _AVE ≦ 1.0 × 10 ^−8. m is desirable. Examples of the shape of the fine particles include a spherical shape, but the present invention is not limited to this. The average particle diameter 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 the average particle diameter of the fine particles. And it is sufficient.

  In the semiconductor device of the present invention, the fine particles are arranged (arranged) on the substrate. Here, the fine particles are preferably arranged two-dimensionally regularly and in a packed state in a plane substantially parallel to the surface of the substrate. Such a state can be achieved by, for example, forming a thin film made of a solution containing fine particles on a substrate based on a dipping method, a casting method, a spin coating method, and the like, and then evaporating the solvent contained in the solution. it can. Here, if there is a large variation in the size of the fine particles, voids are formed in the two-dimensional array, and it becomes impossible to arrange in a packed state. In this case, in the step of evaporating the solvent contained in the solution, it is desirable to evaporate the solvent contained in the solution while controlling the evaporation rate. If the evaporation rate of the solvent is too fast, the fine particles are left in place before the two-dimensional regular arrangement by self-organization is achieved, and the substrate cannot move freely. Alternatively, in this case, it is desirable to perform surface treatment of the substrate before forming a thin film made of a solution containing fine particles. Alternatively, in this case, it is desirable to control the wettability between the solution containing fine particles and the substrate in the step of forming a thin film made of the solution containing fine particles. Alternatively, such a state is achieved by a method similar to a so-called LB (Langmuir-Blodgett) method in which a thin film is formed based on a solution containing fine particles and then the thin film is transferred onto a substrate. Is preferable from the viewpoint of two-dimensional regular arrangement in a packed state. Specifically, fine particles having a hydrophobic surface are floated on a hydrophilic solvent (for example, water) so as to have a two-dimensional regular arrangement in a single layer, or conversely, a hydrophilic surface is formed on a hydrophobic solvent. A method of floating fine particles having a single layer so as to have a two-dimensional regular arrangement and transferring the fine particles onto a substrate as in the LB method may be employed. Alternatively, a method in which a concave portion is formed in advance on the surface of the substrate by lithography technology or the like, a solution containing fine particles is dropped on the surface of the substrate including the concave portion, and the solvent is evaporated, or an O-ring placed on the surface of the substrate, etc. It is also possible to adopt a method in which a solution containing fine particles is dropped on the surface portion of the substrate surrounded by the substrate, and the solvent is evaporated. By adopting these methods, the solvent from the periphery of the droplets generally found can be used. Unlike evaporation of (3), as a result of evaporation of the solvent from the center, a uniform fine particle layer can be formed.

  In the semiconductor device of the present invention, it is more desirable that the fine particles are arranged in a close packed state. More specifically, “fine particles are arranged in a packed state” means that a conductive path composed of organic semiconductor molecules bonded to the fine particles is formed at least between the source / drain electrodes, for example. 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 the closest packing 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 which is doing. However, here, since the organic semiconductor molecules 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 of the organic semiconductor molecule used in the major axis direction. If the distance between the fine particles is longer than the total length of the organic semiconductor molecules, and the fine particles are fixed on the substrate and cannot move, the conductive path will be broken there. The number of conductive paths constituted by the fine particles is reduced, leading to deterioration of the characteristics of the semiconductor device. When an attempt is made to obtain a semiconductor device having excellent characteristics, when this semiconductor device is composed of, for example, a field effect transistor (FET), there is no break from one source / drain electrode to the other source / drain electrode. The conductive path needs to be connected. In addition, the number of conductive paths greatly affects the improvement of FET characteristics. In order to increase the number of conductive paths, it is desirable that the fine particles are adjacent to each other at a distance closer than the length of the organic semiconductor molecule, and further, the fine particles are two-dimensionally arranged in a hexagonal close packed manner.

  Furthermore, in the semiconductor device of the present invention, more specifically, even though the two-dimensionally ordered layers are single layers, they exist in multiple layers in a three-dimensional close-packed state. May be. “Two-dimensionally regularly arranged” means that fine particles having a uniform particle size are arranged in a packed state, preferably in a close packed state, in a space that is at least approximately one layer thick. 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.

  In the semiconductor device of the present invention, it is preferable that the functional group possessed by the organic semiconductor molecule at the terminal is bonded to the functional group possessed by the organic molecule constituting the organic material. In this case, the organic semiconductor molecules and the fine particles are chemically (alternately) bonded by the bond between the functional groups of the organic semiconductor molecules at both ends and the functional groups of the organic molecules constituting the organic material. It is preferable that a network-like conductive path is constructed, and further, it is preferable that the conductive path is constituted by a single layer of a combination of fine particles and organic semiconductor molecules. Alternatively, in this case, the organic semiconductor molecules and the fine particles are chemically (alternately) three-dimensionally by bonding between the functional groups of the organic semiconductor molecules at both ends and the functional groups of the organic molecules constituting the organic material. It is preferable that a network-like conductive path is constructed by bonding, and further, it is preferable that the conductive path is constituted by a laminated structure of a combination of fine particles and organic semiconductor molecules.

  In the semiconductor device of the present invention, by constructing a network-like conductive path in this way, charge movement in the conductive path occurs predominantly in the molecular axial direction along the main chain of the organic semiconductor molecule. As a result of the structure, the mobility in the axial direction of the molecule, for example, high mobility due to delocalized π electrons, can be utilized to the maximum, so that unprecedented high mobility comparable to monolayer transistors The degree can be realized.

In the semiconductor layer of the present invention, the substrate is made 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 It can consist of 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 a substrate other than the above-described substrates, polymethyl methacrylate (polymethyl methacrylate, PMMA), polyvinyl alcohol (PVA), polyvinylphenol (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 polymer material having flexibility is used, for example, a semiconductor device can be incorporated or integrated into a display device or electronic device having a curved shape. Alternatively, as the substrate (or support), various glass substrates, various glass substrates with an insulating film formed on the surface, quartz substrates, a quartz substrate with an insulating film formed on the surface, and an insulating film 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 a metal such as gold or highly oriented graphite). Further, depending on the configuration and structure of the semiconductor device, the semiconductor device may be provided on the support, but this support can also be formed from the above-described materials.

  In the present invention, when a semiconductor device is a field effect transistor (FET), as a material constituting a gate electrode, a source / drain electrode, and various wirings, platinum (Pt), gold (Au), palladium (Pd), Chromium (Cr), nickel (Ni), molybdenum (Mo), niobium (Nb), neodymium (Nd), rubidium (Rb), rhodium (Rh), aluminum (Al), silver (Ag), tantalum (Ta), Metals such as tungsten (W), copper (Cu), titanium (Ti), indium (In), tin (Sn), or alloys containing these metal elements, conductive particles made of these metals, these metals Conductive particles of alloys containing copper, polysilicon and amorphous silicon containing impurities, tin oxide, indium oxide, indium tin oxide (ITO), etc. It may be mentioned a conductive material may be a stacked structure of layers 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. The material constituting the gate electrode, source / drain electrode, and various wirings may be the same material as the fine particles, or may be a different material.

  Depending on the material constituting the gate electrode, source / drain electrode, and wiring, the physical vapor deposition method (PVD method) exemplified by vacuum deposition method and sputtering method; various types including MOCVD method Chemical vapor deposition method (CVD method); Spin coating method; Various printing methods such as screen printing method, inkjet printing method, offset printing method, gravure printing method; air doctor coater method, blade coater method, rod coater method, knife Various coating methods such as coater method, squeeze 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, dipping method; stamp method Lift-off method Doumasuku 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 physical vapor phase growth method (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, DC sputtering method, DC magnetron sputtering method, high frequency sputtering method, magnetron sputtering method, ion beam sputtering method, bias sputtering method and other various sputtering methods, (d) DC (direct current) method, RF method, multi-cathode method, activation Various ion plating methods such as a reaction method, a field evaporation method, a high frequency ion plating method, and a reactive ion plating method can be given.

In the present invention, when the semiconductor device is a field effect transistor (FET), silicon oxide-based material, silicon nitride (SiN _Y ), Al ₂ O ₃ , HfO ₂ , metal oxide In addition to inorganic insulating materials exemplified by dielectric insulating films, polymethyl methacrylate (PMMA), polyvinyl phenol (PVP), polyvinyl alcohol (PVA), polyethylene terephthalate (PET), polyoxymethylene (POM), polychlorinated Examples thereof include organic insulating materials exemplified by vinyl, polyvinylidene fluoride, polysulfone, polycarbonate (PC), and polyimide, and combinations thereof can also be used. As silicon oxide materials, silicon dioxide (SiO _x ), BPSG, PSG, BSG, AsSG, PbSG, silicon oxynitride (SiON), SOG (spin on glass), low dielectric constant SiO ₂ materials (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 the gate insulating layer, any of the above-described various PVD methods; various CVD methods; spin coating methods; various printing methods described above; various coating methods described above; dipping methods; 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, a chemical bond is formed with the gate electrode, such as a linear hydrocarbon modified with a mercapto group at one end, an alkanethiol, or a silanol derivative (silane coupling agent). An insulating film can also be formed on the surface of the gate electrode by coating the surface of the gate electrode with an insulating molecule having a functional group capable of self-organizing by a method such as an immersion method.

  When the semiconductor device of the present invention 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 semiconductor devices are integrated on a support, or each semiconductor device may be cut and individualized to provide discrete components. It may be used as a part. Further, the electronic device or the semiconductor device may be sealed with resin.

  In the present invention, the conductive path is composed of fine particles made of an organic material, which are conductors or semiconductors, and organic semiconductor molecules, so that by introducing a functional group into the organic molecules constituting the organic material, The properties and characteristics of the fine particles can be changed, the organic material constituting the fine particles can be optimized to improve the performance of the conductive path, and the packing structure of the organic molecules can be changed. It is possible to optimize the arrangement (arrangement) state of the fine particles. In addition, if the organic material is appropriately selected, flexibility can be imparted to the entire conductive path. Moreover, since the functional group which the organic molecule which comprises an organic material has, and the functional group which an organic-semiconductor molecule has are couple | bonded, a firm conductive path can be formed reliably.

  Moreover, since the conductive path can be formed one layer at a time in a low temperature process of 200 ° C. or less under normal pressure, a conductive path having a desired thickness can be easily formed, and a semiconductor device can be manufactured at low cost. Can be made. Also, in the semiconductor device of the present invention, all the components including the channel formation region can be constructed with organic materials and organic materials, and the cost can be reduced by using inexpensive organic materials and organic materials. Is possible.

  Furthermore, it is possible to form a network-like conductive path in which a conductive path along a molecular skeleton in an organic molecule constituting an organic material and a conductive path along a molecular skeleton in an organic semiconductor molecule are connected. Accordingly, a structure in which charge transfer in the conductive path occurs predominantly in the axial direction of the molecule along the main chain of the molecule is obtained. Since the conduction path does not include electron transfer between molecules, the mobility is not limited by the electron transfer between molecules, which is a cause of low mobility in a semiconductor device using a conventional organic semiconductor material. Therefore, the charge transfer in the axial direction in the organic semiconductor molecule can be utilized to the maximum extent. For example, when a molecule having a conjugated system formed along the main chain is used as an organic semiconductor molecule, high mobility due to delocalized π electrons can be used.

  In addition, since fine particles made of an organic material do not require protective film molecules such as metal fine particles, the conductive path can be a simple system in which no extra material is mixed.

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

  Example 1 relates to a semiconductor device of the present invention. A conceptual diagram in which the semiconductor device of Example 1 is partially cut is shown in FIG. 1A, and a conceptual diagram of the conductive path 20 is shown in FIG.

  In the semiconductor device of Example 1, as shown in conceptual diagrams in FIGS. 1A and 1B, fine particles 21 (shown in a circle) made of an organic material, which are conductors, and organic semiconductor molecules 22 (two A conductive path 20 is formed on the substrate (specifically, the gate insulating layer 13). And the functional group which the organic molecule (organic polymer) which comprises an organic material has, and the functional group which an organic-semiconductor molecule has have couple | bonded. The combined state is indicated by a zigzag figure. Here, the conductivity of the conductive path 20 is controlled by the electric field applied to the conductive path 20. A conceptual diagram of charge transfer is indicated by an arrow in FIG. The fine particles 21 are preferably arranged in a two-dimensional regular and filled state in a plane substantially parallel to the surface of the substrate (gate insulating layer 13). Specifically, the semiconductor device of Example 1 is a bottom gate type and a kind of bottom contact type FET (TFT).

More specifically, in the semiconductor device of Example 1, as shown in a schematic partial cross-sectional view in FIG.
(A) a gate electrode 12 formed on the support 11;
(B) a gate insulating layer 13 (corresponding to a substrate) formed on the support 11 and the gate electrode 12;
(C) a source / drain electrode 14 formed on the gate insulating layer 13, and
(D) a channel forming region 15 formed between the source / drain electrodes 14 and on the gate insulating layer 13 and constituted by the conductive path 20;
It is composed of

In Example 1, the fine particles 21 made of a conductor were prepared from an organic material in which a diazonium group (—N ⁺ ≡N) was introduced into part of the polythiophene represented by the structural formula (23) doped with iodine as a dopant. 2,2 ″ -dihydroxy-1,1 ′: 4 ′, 1 ″ -terphenyl, which is an organic semiconductor molecule having a conjugated bond as the organic semiconductor molecule 22 and having phenol groups at both ends of the molecule. Is used. The bond between the functional group of the organic molecule (organic polymer) constituting the organic material and the functional group of the organic semiconductor molecule is a covalent bond, and further, the functional group of the organic molecule constituting the organic material is The bond with the functional group of the organic semiconductor molecule is based on a diazo coupling reaction. The combination of (functional group possessed by organic molecule constituting organic material, functional group possessed by organic semiconductor molecule) is (diazonium group, phenol group). The base is made of a gate insulating layer 13 (specifically, SiO ₂ ).

  The channel forming region 15 may be a single layer of a combination of the fine particles 21 and the organic semiconductor molecules 22 or may be a laminated structure of a combination of two or more layers and about ten layers. The thickness of one layer is approximately the same as the particle size (several nm) of the fine particles. When the average particle diameter of the fine particles 21 is assumed to be about 10 nm, and the laminated structure of 10 layers is combined, the thickness of the channel forming region 15 is approximately 100 nm. In addition, since the channel formation region 15 can be obtained by forming each layer of the bonded body independently, the material or the fine particles constituting the fine particles 21 for each bonded body or for each stacked structure of the bonded body The characteristics of the channel forming region 15 may be controlled by changing the average particle size 21 and the organic semiconductor molecules 22.

  Hereinafter, with reference to FIGS. 2A to 2D, an outline of a method of manufacturing the semiconductor device of Example 1 will be described.

[Step-100]
First, the gate electrode 12 is formed on the support 11. Specifically, a resist layer (not shown) from which a portion where the gate electrode 12 is to be formed has been removed on a support 11 made of a glass substrate having an insulating film made of SiO ₂ formed on the surface, is applied to a lithography technique. Form based on. Thereafter, a titanium (Ti) layer (not shown) as an adhesion layer and a gold (Au) layer as a gate electrode 12 are sequentially formed on the entire surface by vacuum deposition, and then the resist layer is removed. To do. Thus, the gate electrode 12 can be obtained based on a so-called lift-off method.

[Step-110]
Next, the gate insulating layer 13 is formed on the support 11 including the gate electrode 12. Specifically, the gate insulating layer 13 made of SiO ₂ is formed on the gate electrode 12 and the support 11 based on the sputtering method. When forming the gate insulating layer 13, by covering a part of the gate electrode 12 with a hard mask, an extraction portion (not shown) of the gate electrode 12 can be formed without a photolithography process.

[Step-120]
Next, a source / drain electrode 14 made of a gold (Au) layer is formed on the gate insulating layer 13. Specifically, a resist layer from which a portion where the source / drain electrode 14 is to be formed is removed is formed on the gate insulating layer 13 based on the lithography technique. Then, similarly to [Step-100], a titanium (Ti) layer (not shown) as an adhesion layer and gold (Au) as a source / drain electrode 14 on the resist layer and the gate insulating layer 13. The layers are sequentially formed by vacuum deposition, and then the resist layer is removed. In this way, the source / drain electrode 14 can be obtained based on the so-called lift-off method (see FIG. 2A).

[Step-130]
Thereafter, after forming a thin film made of a solution containing the fine particles 21, the solvent contained in the solution is evaporated. In the step of evaporating the solvent contained in the solution, the solvent contained in the solution is evaporated while controlling the evaporation rate, so that the fine particles 21 are in a plane substantially parallel to the surface of the substrate (gate insulating layer 13). They can be arranged two-dimensionally and in a filled state. This state is schematically shown in FIG.

[Step-140]
Next, the whole including the gate insulating layer 13 is immersed in a solution in which the organic semiconductor molecules 22 are dissolved in dilute sulfuric acid having a pH of 3, and then washed with toluene to replace the solution. Thereafter, the solvent is evaporated. At this time, the functional group which the organic molecule which comprises the organic material in the fine particle 21 has, and the functional group which the organic-semiconductor molecule 22 has couple | bond together. A large number of organic semiconductor molecules 22 are bonded to the surface of one fine particle 21 so as to enclose the fine particle 21. A part of them is also bonded to the functional group of the organic molecule constituting the organic material in the other fine particle 21 by the functional group at the other molecular end. A first combined body layer 23 connected in a dimensional network is formed. This state is schematically shown in FIG. In addition, two general reaction formulas and specific reaction formulas are shown below. (R ₁ , R ₂ ) is (organic semiconductor molecule, organic material) or (organic material, organic semiconductor molecule) Indicates.

  Thus, the organic semiconductor molecules 22 and the fine particles 21 are chemically (alternatively) bonded to each other by the functional groups of the organic semiconductor molecules 22 at both ends, whereby the network-like conductive path 20 is constructed. In the state shown in FIG. 2C, the conductive path 20 is constructed by a single layer of a combination of the fine particles 21 and the organic semiconductor molecules 22.

[Step-150]
Next, [Step-130] and [Step-140] are repeated as many times as necessary. Thus, the organic semiconductor molecules 22 and the fine particles 21 are three-dimensionally and chemically (alternatively) bonded by the functional groups of the organic semiconductor molecules 22 at both ends, whereby the network-like conductive path 20 is constructed, and the fine particles 21 are formed. It is possible to obtain a structure in which the conductive path 20 is configured by a laminated structure of a combination of the organic semiconductor molecule 22 and the organic semiconductor molecule 22. In FIG. 2D, [Step-140] and [Step-150] are repeated three times to obtain a state where a three-layer laminated structure of a combination of the fine particles 21 and the organic semiconductor molecules 22 is obtained. Show.

[Step-160]
Finally, an insulating layer (not shown) as a passivation film is formed on the entire surface, an opening is formed in the insulating layer above the source / drain electrode 14, and a wiring material layer is formed on the entire surface including the inside of the opening. Then, by patterning the wiring material layer, the semiconductor device (field effect transistor) of Example 1 in which the wiring (not shown) connected to the source / drain electrode 14 is formed on the insulating layer can be completed. it can.

  The second embodiment is a modification of the first embodiment. The semiconductor device of Example 2 is a bottom gate type and a kind of top contact type FET (TFT).

More specifically, in the semiconductor device of Example 2, as shown in a schematic partial cross-sectional view in FIG.
(A) a gate electrode 12 formed on the support 11;
(B) a gate insulating layer 13 (corresponding to a substrate) formed on the support 11 and the gate electrode 12;
(C) a channel formation region constituting layer 15A including the channel formation region 15 formed on the gate insulating layer 13 and constituted by the conductive path 20, and
(D) source / drain electrodes 14 formed on the channel formation region constituting layer 15A;
It has.

  Also in the second embodiment, the conductive path 20 is configured by the fine particles 21 made of a conductor and the organic semiconductor molecules 22 as in the first embodiment, and the functional groups of the organic molecules constituting the organic material and the organic A functional group of the semiconductor molecule 22 is bonded. Then, the conductivity of the conductive path 20 is controlled by the electric field applied to the conductive path 20 based on the gate voltage applied to the gate electrode 12.

  Hereinafter, with reference to FIGS. 3A and 3B, an outline of a method for manufacturing the semiconductor device of Example 2 will be described.

[Step-200]
First, after forming the gate electrode 12 on the support 11 in the same manner as [Step-100] in Example 1, the support including the gate electrode 12 in the same manner as [Step-110] in Example 1. A gate insulating layer 13 is formed on 11.

[Step-210]
Next, [Step-130] to [Step-140] of Example 1 are executed to chemically bond the fine particles 21 and the organic semiconductor molecules 22. Thus, the conductive path 20 composed of the first combined body layer 23 in which the fine particles 21 are connected in a two-dimensional network by the organic semiconductor molecules 22 can be formed, and the channel forming region constituting layer 15A can be obtained. That is, the channel formation region 15 can be formed on the portion of the gate insulating layer 13 where the source / drain electrode 14 is to be formed. This state is schematically shown in FIG. Furthermore, if necessary, [Step-130] and [Step-140] of Example 1 are repeated a desired number of times in the same manner as [Step-150] of Example 1.

[Step-220]
After that, the source / drain electrodes 14 are formed on the channel formation region constituting layer 15A so as to sandwich the channel formation region 15 (see FIG. 3B). Specifically, a titanium (Ti) layer (not shown) as an adhesion layer and a gold (Au) layer as a source / drain electrode 14 are sequentially formed based on a vacuum deposition method. When the source / drain electrode 14 is formed, the source / drain electrode 14 can be formed without a photolithography process by covering a part of the channel formation region constituting layer 15A with a hard mask.

[Step-230]
Finally, an insulating layer (not shown) as a passivation film is formed on the entire surface, an opening is formed in the insulating layer above the source / drain electrode 14, and a wiring material layer is formed on the entire surface including the inside of the opening. Then, by patterning the wiring material layer, the semiconductor device (field effect transistor) of Example 2 in which the wiring (not shown) connected to the source / drain electrode 14 is formed on the insulating layer is completed. it can.

Example 3 is also a modification of Example 1, and the semiconductor device of Example 3 is a top gate type as shown in a schematic partial cross-sectional view in FIG. Contact type FET (more specifically, TFT),
(A) a source / drain electrode 14 formed on a support 11 corresponding to a substrate;
(B) a channel forming region 15 formed on the substrate (support 11) between the source / drain electrodes 14 and configured by the conductive path 20;
(C) a gate insulating layer 13 formed on the source / drain electrode 14 and the channel formation region 15, and
(D) a gate electrode 12 formed on the gate insulating layer 13;
It has.

  Here, the conductive path 20 is composed of the fine particles 21 made of a conductor and the organic semiconductor molecules 22 as in the first embodiment, and the functional groups of the organic molecules (organic polymer) constituting the organic material The functional group of the organic semiconductor molecule 22 is bonded. Then, the conductivity of the conductive path 20 is controlled by the electric field applied to the conductive path 20 based on the gate voltage applied to the gate electrode 12.

  Hereinafter, with reference to FIGS. 4A to 4C, a method of manufacturing the semiconductor device of Example 3 will be described.

[Step-300]
First, a source / drain electrode 14 is formed on a support 11 corresponding to a substrate made of cleaved mica (see FIG. 4A). Specifically, a gold (Au) layer as the source / drain electrode 14 is formed on the support 11 based on a vacuum deposition method. When the source / drain electrode 14 is formed, the source / drain electrode 14 can be formed without a photolithography process by covering a part of the support 11 with a hard mask. In addition, since the adhesiveness between a mica and a gold layer is favorable, formation of an adhesive layer is unnecessary.

[Step-310]
Thereafter, the channel forming region 15 constituted by the conductive path 20 is formed on the support 11 between the source / drain electrodes 14. Specifically, by performing [Step-130] to [Step-140] of Example 1, the first combined layer in which the fine particles 21 are connected in a two-dimensional network form by the organic semiconductor molecules 22 is used. A conductive path 20 can be formed. That is, the channel forming region 15 can be formed on the support 11 between the source / drain electrodes 14. This state is schematically shown in FIG. Furthermore, if necessary, [Step-130] and [Step-140] of Example 1 are repeated a desired number of times in the same manner as [Step-150] of Example 1.

[Step-320]
Next, the gate insulating layer 13 is formed on the source / drain electrodes 14 and the channel formation region 15. Specifically, the gate insulating layer 13 can be obtained by depositing PVA on the entire surface by spin coating.

[Step-330]
Thereafter, the gate electrode 12 is formed on the gate insulating layer 13. Specifically, a titanium (Ti) layer (not shown) as an adhesion layer and a gold (Au) layer as a gate electrode 12 are sequentially formed by vacuum deposition. When the gate electrode 12 is formed, the gate electrode 12 can be formed without a photolithography process by covering a part of the gate insulating layer 13 with a hard mask. Thus, the structure shown in FIG. 4C can be obtained.

[Step-340]
Finally, an insulating layer (not shown) as a passivation film is formed on the entire surface, an opening is formed in the insulating layer above the source / drain electrode 14, and a wiring material layer is formed on the entire surface including the inside of the opening. Then, by patterning the wiring material layer, the semiconductor device (field effect transistor) of Example 3 in which the wiring (not shown) connected to the source / drain electrode 14 is formed on the insulating layer can be completed. it can.

The fourth embodiment is also a modification of the first embodiment. The semiconductor device of Example 4 is a top gate type, and is a kind of top contact type FET (more specifically, TFT), as shown in a schematic partial sectional view in FIG. And
(A) a channel formation region constituting layer 15A including a channel formation region 15 formed on the support 11 corresponding to the base and constituted by the conductive path 20;
(B) source / drain electrodes 14 formed on the channel formation region constituting layer 15A;
(C) a gate insulating layer 13 formed on the source / drain electrode 14 and the channel formation region 15, and
(D) a gate electrode 12 formed on the gate insulating layer 13;
It has.

  Here, the conductive path 20 is composed of the fine particles 21 made of a conductor and the organic semiconductor molecules 22 as in the first embodiment, and the functional groups of the organic molecules (organic polymer) constituting the organic material The functional group of the organic semiconductor molecule 22 is bonded. Then, the conductivity of the conductive path 20 is controlled by the electric field applied to the conductive path 20 based on the gate voltage applied to the gate electrode 12.

  Hereinafter, with reference to FIGS. 5A to 5C, a method of manufacturing the semiconductor device of Example 4 will be described.

[Step-400]
First, a channel formation region constituting layer 15A constituting the channel formation region 15 is formed on a support 11 corresponding to a substrate made of cleaved mica. Specifically, by performing [Step-130] to [Step-140] of Example 1, the first combined layer in which the fine particles 21 are connected in a two-dimensional network form by the organic semiconductor molecules 22 is used. A conductive path 20 can be formed. That is, the channel formation region constituting layer 15 </ b> A constituting the channel formation region 15 can be formed on the support 11. This state is schematically shown in FIG. Furthermore, if necessary, [Step-130] and [Step-140] of Example 1 are repeated a desired number of times in the same manner as [Step-150] of Example 1.

[Step-410]
Thereafter, the source / drain electrodes 14 are formed on the channel formation region constituting layer 15A so as to sandwich the channel formation region 15. Specifically, a titanium (Ti) layer (not shown) as an adhesion layer and a gold (Au) layer as a source / drain electrode 14 are sequentially formed based on a vacuum deposition method (( B)). When the source / drain electrode 14 is formed, the source / drain electrode 14 can be formed without a photolithography process by covering a part of the channel formation region constituting layer 15A with a hard mask.

[Step-420]
Next, the gate insulating layer 13 is formed on the source / drain electrodes 14 and the channel formation region 15 in the same manner as in [Step-320] of the third embodiment.

[Step-430]
Thereafter, the gate electrode 12 is formed on the gate insulating layer 13. Specifically, a titanium (Ti) layer (not shown) as an adhesion layer and a gold (Au) layer as a gate electrode 12 are sequentially formed by vacuum deposition. When the gate electrode 12 is formed, the gate electrode 12 can be formed without a photolithography process by covering a part of the gate insulating layer 13 with a hard mask. Thus, the structure shown in FIG. 5C can be obtained.

[Step-440]
Finally, an insulating layer (not shown) as a passivation film is formed on the entire surface, an opening is formed in the insulating layer above the source / drain electrode 14, and a wiring material layer is formed on the entire surface including the inside of the opening. Then, by patterning the wiring material layer, the semiconductor device (field effect transistor) of Example 4 in which the wiring (not shown) connected to the source / drain electrode 14 is formed on the insulating layer is completed. it can.

The fifth embodiment is also a modification of the first embodiment. In Example 5, the bond between the functional group of the organic molecule (organic polymer) constituting the organic material and the functional group of the organic semiconductor molecule is a covalent bond, and further, the organic molecule constituting the organic material is The bond between the functional group possessed and the functional group possessed by the organic semiconductor molecule is based on aldol condensation. Specifically, fine particles made of an organic material in which an aldehyde group (—CHO) is introduced into a part of the polythiophene represented by the structural formula (23) doped with iodine as a dopant are used as the fine particles 21 made of a conductor. As the organic semiconductor molecule 22, 4,4′-biphenyldiethanol is an organic semiconductor molecule having a conjugated bond and having aldehyde groups at both ends of the molecule. The combination of (functional group possessed by organic molecule constituting organic material, functional group possessed by organic semiconductor molecule)
(Aldehyde group, aldehyde group).

In Example 5, the functional group possessed by the organic molecule constituting the organic material and the functional group possessed by the organic semiconductor molecule are bonded to each other, and this bonding is performed according to [Step-140] of Example 1. In the same step, it can be achieved by dissolving organic semiconductor molecules in a sodium hydroxide solution and heating to about 100 ° C. when the support 11 is immersed. Two general reaction formulas and specific reaction formulas are shown below. R ₁ , R _1a and R _1b represent organic semiconductor molecules, and R ₂ , R _2a and R _2b represent organic materials. An organic molecule is shown.

  The fine particles and organic semiconductor molecules described in Example 5 can also be applied to Examples 2 to 4.

  The sixth embodiment is also a modification of the first embodiment. In Example 6, the bond between the functional group of the organic molecule (organic polymer) constituting the organic material and the functional group of the organic semiconductor molecule is a covalent bond, and further, the organic molecule constituting the organic material is The bond between the functional group possessed and the functional group possessed by the organic semiconductor molecule is based on an ester bond. Specifically, fine particles made of an organic material in which a carboxyl group (—COOH) is introduced into a part of the polythiophene represented by the structural formula (23) doped with iodine as a dopant are used as the fine particles 21 made of a conductor. As the organic semiconductor molecule 22, 4,4′-biphenyldiol which is an organic semiconductor molecule having a conjugated bond and having a conjugated bond at both ends of the molecule and having hydroxyl groups at both ends is used. A combination of (functional group of organic molecule constituting organic material, functional group of organic semiconductor molecule) is (carboxyl group, hydroxyl group).

In Example 6, the functional group possessed by the organic molecule constituting the organic material and the functional group possessed by the organic semiconductor molecule are bonded to each other, and this bonding is performed according to [Step-140] of Example 1. In a similar step, it can be achieved by heating the solution in aqueous sulfuric acid. Three general reaction formulas and specific reaction formulas are shown below. R ₁ , R _1a , and R _1b represent organic molecules constituting the organic material, and R ₂ represents an organic semiconductor molecule. .

  The fine particles and organic semiconductor molecules described in Example 6 can also be applied to Examples 2 to 4.

  The seventh embodiment is also a modification of the first embodiment. In Example 7, the bond between the functional group of the organic molecule (organic polymer) constituting the organic material and the functional group of the organic semiconductor molecule is a covalent bond, and further, the organic molecule constituting the organic material is The bond between the functional group possessed and the functional group possessed by the organic semiconductor molecule is based on an amide bond. Specifically, fine particles made of an organic material in which a carboxyl group (—COOH) is introduced into a part of the polythiophene represented by the structural formula (23) doped with iodine as a dopant are used as the fine particles 21 made of a conductor. The organic semiconductor molecule 22 is an organic semiconductor molecule having a conjugated bond, which is an organic semiconductor molecule having a conjugated bond at both ends of the molecule and having an amino group at both ends. A combination of (functional group of organic molecule constituting organic material, functional group of organic semiconductor molecule) is (carboxyl group, amino group).

In Example 7, the functional group possessed by the organic molecule constituting the organic material and the functional group possessed by the organic semiconductor molecule are bonded. This bond is the same as [Step-140] in Example 1. In a similar step, it can be achieved by heating in a basic solution. Three general reaction formulas and specific reaction formulas are shown below. R ₁ , R _1a , and R _1b represent organic molecules constituting the organic material, and R ₂ represents an organic semiconductor molecule. .

  The fine particles and organic semiconductor molecules described in Example 7 can also be applied to Examples 2 to 4.

  The eighth embodiment is also a modification of the first embodiment. In Example 8, the bond between the functional group of the organic molecule (organic polymer) constituting the organic material and the functional group of the organic semiconductor molecule is a covalent bond, and further, the organic molecule constituting the organic material is The bond between the functional group possessed and the functional group possessed by the organic semiconductor molecule is based on a urethane bond. Specifically, fine particles made of an organic material in which a hydroxyl group or a thiol group is introduced into a part of the polythiophene represented by the structural formula (23) doped with iodine as a dopant are used as the fine particles 21 made of a conductor. As the organic semiconductor molecule 22, 4,4′-biphenyl diisocyanate, which is an organic semiconductor molecule having a conjugated bond and having an conjugated bond at both ends of the molecule and having an isocyanate group at both ends, is used. The combination of (functional group possessed by organic molecule constituting organic material, functional group possessed by organic semiconductor molecule) is (hydroxyl group, isocyanate group) or (thiol group, isocyanate group).

In Example 8, the functional group possessed by the organic molecule constituting the organic material and the functional group possessed by the organic semiconductor molecule are bonded to each other, and this bonding is performed according to [Step-140] of Example 1. In a similar step, it can be achieved by dissolving in ethanol and immersing the support 11. Four general reaction formulas and specific reaction formulas are shown below. R ₂ represents an organic semiconductor molecule, and R ₁ represents an organic molecule constituting the organic material.

  The fine particles and organic semiconductor molecules described in Example 8 can also be applied to Examples 2 to 4.

  The ninth embodiment is also a modification of the first embodiment. In Example 9, the bond between the functional group of the organic molecule (organic polymer) constituting the organic material and the functional group of the organic semiconductor molecule is a covalent bond, and further, the organic molecule constituting the organic material is The bond between the functional group possessed and the functional group possessed by the organic semiconductor molecule is based on a disulfide bond. Specifically, fine particles made of an organic material in which a thiol group is introduced into a part of the polythiophene represented by the structural formula (23) doped with iodine as a dopant are used as the fine particles 21 made of a conductor. 22 is an organic semiconductor molecule having a conjugated bond, and is an organic semiconductor molecule having a conjugated bond at both ends of the molecule and 4,4′-biphenyldithiol having a thiol group at both ends. The combination of (functional group possessed by organic molecule constituting organic material, functional group possessed by organic semiconductor molecule) is (thiol group, thiol group).

In Example 9, the functional group possessed by the organic molecule constituting the organic material and the functional group possessed by the organic semiconductor molecule are bonded. This bond is the same as [Step-140] in Example 1. In a similar step, it can be achieved by dissolving in ethanol and immersing the support and then adding iodine as the oxidizing agent. A general reaction formula and a specific reaction formula are shown below. (R ₁ , R ₂ ) is (organic semiconductor molecule, organic molecule constituting organic material) or (organic constituting organic material) Molecule, organic semiconductor molecule).

  The fine particles and organic semiconductor molecules described in Example 9 can also be applied to Examples 2 to 4.

  The tenth embodiment is also a modification of the first embodiment. In Example 10, the bond between the functional group of the organic molecule (organic polymer) constituting the organic material and the functional group of the organic semiconductor molecule is a covalent bond, and further, the organic molecule constituting the organic material is The bond between the functional group possessed and the functional group possessed by the organic semiconductor molecule is based on the bond between the halogenated alkyl group and the alkyne. Specifically, fine particles 21 made of an organic material in which a methyl group is introduced into a part of polythiophene represented by the structural formula (23) doped with iodine as a dopant are used as the fine particles 21 made of a conductor. 22 is an organic semiconductor molecule having a conjugated bond, which is an organic semiconductor molecule having a conjugated bond at both ends of the molecule and having acetylinyl groups at both ends. The combination of (functional group of organic molecule constituting organic material, functional group of organic semiconductor molecule) is (methyl chloride group, acetylinyl group).

  In Example 10, the functional group possessed by the organic molecule constituting the organic material and the functional group possessed by the organic semiconductor molecule are bonded to each other, and this bonding is performed according to [Step-140] of Example 1. In a similar step, this can be achieved by dissolving the semiconductor molecules in liquid ammonium, adding sodium amide, and then immersing the support. A general reaction formula and a specific reaction formula are shown below.

  The fine particles and organic semiconductor molecules described in Example 10 can also be applied to Examples 2 to 4.

  The eleventh embodiment is also a modification of the first embodiment. In Example 11, the bond between the functional group of the organic molecule (organic polymer) constituting the organic material and the functional group of the organic semiconductor molecule is a covalent bond, and further, the organic molecule constituting the organic material is The bond between the functional group possessed and the functional group possessed by the organic semiconductor molecule is based on Claisen condensation. Specifically, fine particles 21 made of an organic material in which an ester bond is introduced into a part of polythiophene represented by the structural formula (23) doped with iodine as a dopant are used as the fine particles 21 made of a conductor. As an organic semiconductor molecule 22 having a conjugated bond, an organic semiconductor molecule having a conjugated bond at both ends of the molecule and having an ester bond at both ends, diethylbiphenyl-4,4′-dicarboxylate is used. The combination of (functional group of organic molecule constituting organic material, functional group of organic semiconductor molecule) is (ester bond, ester bond).

  In Example 11, the functional group possessed by the organic molecule constituting the organic material and the functional group possessed by the organic semiconductor molecule are bonded to each other, and this bonding is performed according to [Step-140] of Example 1. In a similar step, it can be achieved by dissolving in ethanol, immersing the support and then adding sodium ethoxide. A general reaction formula and a specific reaction formula are shown below.

  The fine particles and organic semiconductor molecules described in Example 11 can also be applied to Examples 2 to 4.

  As mentioned above, although this invention was demonstrated based on the preferable Example, this invention is not limited to these Examples. The structure, configuration, and manufacturing conditions of the semiconductor device are examples, and can be changed as appropriate. When the semiconductor device (TFT) obtained by the present invention 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 TFTs are integrated on a support or a support member. It may be cut and individualized and used as a discrete part.

FIG. 1A is a conceptual diagram in which the semiconductor device of Example 1 is partially cut, and FIG. 1B is a conceptual diagram of a conductive path constituted by fine particles and organic semiconductor molecules. . 2A to 2D are schematic partial cross-sectional views of a support and the like for explaining the method for manufacturing the semiconductor device of Example 1. FIG. 3A and 3B are schematic partial cross-sectional views of a support and the like for describing the method for manufacturing the semiconductor device of Example 2. FIG. 4A to 4C are schematic partial cross-sectional views of a support and the like for explaining the method for manufacturing the semiconductor device of Example 3. FIG. 5A to 5C are schematic partial cross-sectional views of a support and the like for explaining the method for manufacturing a semiconductor device of Example 4. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 11 ... Support body, 12 ... Gate electrode, 13 ... Gate insulating layer, 14 ... Source / drain electrode, 15 ... Channel formation area, 15A ... Channel formation area structure layer, 20 ... Conductive path, 21 ... fine particles, 22 ... organic semiconductor molecules, 23 ... combined layer

Claims (23)

A semiconductor device in which a conductive path composed of fine particles made of an organic material and a conductor or a semiconductor and organic semiconductor molecules is formed on a substrate,
A semiconductor device, wherein a functional group of an organic molecule constituting an organic material is bonded to a functional group of an organic semiconductor molecule.   The semiconductor device according to claim 1, wherein the bond between the functional group of the organic molecule constituting the organic material and the functional group of the organic semiconductor molecule is a covalent bond.   The semiconductor device according to claim 1, wherein the bond between the functional group of the organic molecule constituting the organic material and the functional group of the organic semiconductor molecule is based on a diazo coupling reaction.   The combinations of (functional groups of organic molecules constituting organic materials, functional groups of organic semiconductor molecules) are (diazonium group, phenol group), (diazonium group, phenylamino group), (phenol group, diazonium group), Alternatively, the semiconductor device according to claim 3, wherein the semiconductor device is (phenylamino group, diazonium group).   The semiconductor device according to claim 1, wherein the bond between the functional group of the organic molecule constituting the organic material and the functional group of the organic semiconductor molecule is based on aldol condensation.   The combinations of (functional group of organic molecule constituting organic material, functional group of organic semiconductor molecule) are (aldehyde group, aldehyde group), (aldehyde group, phosphorus ylide group), (ketone group, phosphorus ylide group), ( 6. The semiconductor device according to claim 5, wherein the semiconductor device is (phosphorus ylide group, aldehyde group) or (phosphorus ylide group, ketone group).   The semiconductor device according to claim 1, wherein the bond between the functional group of the organic molecule constituting the organic material and the functional group of the organic semiconductor molecule is based on an ester bond.   The combination of (functional group of organic molecule constituting organic material, functional group of organic semiconductor molecule) is (carboxyl group, hydroxyl group), (halogenated acyl group, hydroxyl group), (anhydrous carboxyl group, hydroxyl group) 8. The semiconductor device according to claim 7, which is (hydroxyl group, carboxyl group), (hydroxyl group, acyl halide group), or (hydroxyl group, anhydrous carboxyl group).   The semiconductor device according to claim 1, wherein the bond between the functional group of the organic molecule constituting the organic material and the functional group of the organic semiconductor molecule is based on an amide bond.   The combination of (functional group of organic molecule constituting organic material, functional group of organic semiconductor molecule) is (carboxyl group, amino group), (halogenated acyl group, amino group), (anhydrous carboxyl group, amino group) The semiconductor device according to claim 9, wherein the semiconductor device is (amino group, carboxyl group), (amino group, acyl halide group), or (amino group, anhydrous carboxyl group).   2. The semiconductor device according to claim 1, wherein the bond between the functional group of the organic molecule constituting the organic material and the functional group of the organic semiconductor molecule is based on a urethane bond.   The combinations of (functional group of organic molecule constituting organic material, functional group of organic semiconductor molecule) are (isocyanate group, hydroxyl group), (hydroxyl group, isocyanate group), (isocyanate group, thiol group), ( It is characterized by being (thiol group, isocyanate group), (isothiocyanate group, hydroxyl group), (hydroxyl group, isothiocyanate group), (isothiocyanate group, thiol group), or (thiol group, isothiocyanate group). The semiconductor device according to claim 11.   The semiconductor device according to claim 1, wherein the bond between the functional group of the organic molecule constituting the organic material and the functional group of the organic semiconductor molecule is based on a disulfide bond.   14. The semiconductor device according to claim 13, wherein the combination of (functional group of organic molecule constituting organic material, functional group of organic semiconductor molecule) is (thiol group, thiol group).   2. The semiconductor device according to claim 1, wherein the bond between the functional group of the organic molecule constituting the organic material and the functional group of the organic semiconductor molecule is based on the bond between the halogenated alkyl group and the alkyne.   The combination of (functional group of organic molecule constituting organic material, functional group of organic semiconductor molecule) is (halogenated alkyl group, alkyne) or (alkyne, halogenated alkyl group). The semiconductor device according to claim 15.   2. The semiconductor device according to claim 1, wherein the bond between the functional group of the organic molecule constituting the organic material and the functional group of the organic semiconductor molecule is based on Claisen condensation.   18. The semiconductor device according to claim 17, wherein the combination of (functional group of organic molecule constituting organic material and functional group of organic semiconductor molecule) is (ester bond, ester bond).   The semiconductor device according to claim 1, wherein the organic semiconductor molecule has two or more functional groups. An organic semiconductor molecule is an organic semiconductor molecule having a conjugated bond, and has a thiol group (—SH), an amino group (—NH ₂ ), a diazonium group (—N ₂ ⁺ ), a phenol group (—C) at both ends of the molecule. ₆ H ₄ OH), phenylamino group _{(-C 6 H 4 NH 2)} , aldehyde group (-CHO), ketone group (-CO-), phosphorus ylide group _{(= P (C 6 H 5} ) 3), a carboxyl group (—COOH), hydroxyl group (—OH), acyl halide group (—COX (X: Cl, Br, I)), anhydrous carboxyl group (—COOCO—), isocyanate group (—NCO), isothiocyanate group ( The semiconductor device according to claim 1, which has an —NCS), an alkyne (—C≡C—H), or an ester bond (—COO—). The functional groups of the organic molecules constituting the organic material are thiol group (—SH), amino group (—NH ₂ ), diazonium group (—N ₂ ⁺ ), phenol group (—C ₆ H ₄ OH), phenylamino Group (—C ₆ H ₄ NH ₂ ), aldehyde group (—CHO), ketone group (—CO—), phosphorus ylide group (═P (C ₆ H ₅ ) ₃ ), carboxyl group (—COOH), hydroxyl group ( -OH), acyl halide groups (-COX (X: Cl, Br, I)), anhydrous carboxyl groups (-COOCO-), isocyanate groups (-NCO), isothiocyanate groups (-NCS), alkynes (-C 2. The semiconductor device according to claim 1, wherein ≡C—H) or an ester bond (—COO—).   2. The semiconductor device according to claim 1, wherein conductivity of the conductive path is controlled by an electric field applied to the conductive path. A field effect transistor having a gate electrode, a gate insulating layer, a channel formation region, and a source / drain electrode;
23. The semiconductor device according to claim 22, wherein a channel formation region is constituted by the conductive path.

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