WO2008062843A1 - Matériau de recouvrement d'électrode, structure d'électrode et dispositif semi-conducteur - Google Patents
Matériau de recouvrement d'électrode, structure d'électrode et dispositif semi-conducteur Download PDFInfo
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- WO2008062843A1 WO2008062843A1 PCT/JP2007/072581 JP2007072581W WO2008062843A1 WO 2008062843 A1 WO2008062843 A1 WO 2008062843A1 JP 2007072581 W JP2007072581 W JP 2007072581W WO 2008062843 A1 WO2008062843 A1 WO 2008062843A1
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Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/791—Starburst compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
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- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
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- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
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- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
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- H10K10/80—Constructional details
- H10K10/82—Electrodes
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- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
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- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
- H10K10/466—Lateral bottom-gate IGFETs comprising only a single gate
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- Y10T428/31533—Of polythioether
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- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31692—Next to addition polymer from unsaturated monomers
Definitions
- Electrode coating material Electrode coating material, electrode structure, and semiconductor device
- the present invention relates to an electrode coating material, an electrode structure, and a semiconductor device.
- the organic semiconductor material layer constituting the channel formation region is in direct contact with the source / drain electrodes made of metal. Therefore, in such a form, electron transfer at the interface between the metal and the organic semiconductor material layer involves a significant energy loss. That is, the electron transfer at the junction interface between the metal and the organic semiconductor material is performed by the distance between the metal interface where free electrons exist, the interface between the organic semiconductor material layer having a quantized space, and the junction interface. It is very inefficient at present because it is greatly affected by differences in orientation. As a result, there are problems that the contact resistance value is large and the mobility is low.
- an object of the present invention is to provide an electrode coating that makes it possible to obtain a low contact resistance value. It is an object of the present invention to provide a material and an electrode structure, and a semiconductor device capable of achieving low contact resistance and high mobility.
- a semiconductor device includes a channel formation region including a gate electrode, a gate insulating layer, and an organic semiconductor material layer, and This is a semiconductor device comprising a field effect transistor having a source / drain electrode made of metal, and the portion of the source / drain electrode in contact with the organic semiconductor material layer constituting the channel formation region is covered with an electrode coating material.
- the electrode structure according to the first to fourth aspects of the present invention for achieving the above object comprises an electrode and an electrode coating material for covering the surface of the electrode.
- the electrode coating material according to the first aspect of the present invention is composed of an organic molecule represented by the formula (1), and the functional group Y in the formula (1) is bonded to the surface of the metal electrode (or source / drain electrode). It is characterized by.
- the electrode coating material according to the second aspect of the present invention is composed of an organic molecule represented by the formula (1), and the functional group Y in the formula (1) is bonded to the surface of the electrode (or source / drain electrode) made of metal,
- One type is characterized by binding to a metal ion to form a chelate.
- the electrode coating material according to the second aspect of the present invention, the semiconductor device according to the second aspect of the present invention, or the electrode structure according to the second aspect of the present invention (hereinafter referred to as these May be simply referred to as the second aspect of the present invention)
- a nitrogen atom in formula (1) binds to a metal ion to form a chelate
- a functional group R in formula (1) binds to a metal ion to form a chelate
- the functional group R in formula (1) binds to a metal ion to form a chelate, or alternatively • The nitrogen atom and functional group R in formula (1) bind to the metal ion to form a chelate,
- the electrode coating material according to the third aspect of the present invention is an electrode covering material comprising a first organic molecule and a second organic molecule,
- the first organic molecule consists of the organic molecule represented by formula (1),
- the second organic molecule consists of the organic molecule represented by formula (6),
- the functional group Y in formula (1) binds to the surface of a metal electrode (or source / drain electrode),
- One type binds to a metal ion to form a chelate
- At least one selected from the group binds to a metal ion to form a chelate and / or from the functional group R ′, the functional group R ′, and the nitrogen atom adjacent to the functional group R ′ in formula (6)
- At least one selected from the group consisting of binds to a metal ion to form a chelate.
- the electrode coating material according to the third aspect of the present invention, the semiconductor device according to the third aspect of the present invention, or the electrode structure according to the third aspect of the present invention (hereinafter referred to as these) May be simply referred to as the third aspect of the present invention)
- a nitrogen atom in formula (1) binds to a metal ion to form a chelate
- a functional group R in formula (1) binds to a metal ion to form a chelate
- the functional group in formula (1) binds to a metal ion to form a chelate, or alternatively • the nitrogen atom and functional group R in formula (1) bind to a metal ion to form a chelate,
- Binds to metal ions to form chelates or
- Binds to metal ions to form chelates or
- At least one kind binds to a metal ion to form a chelate, and further from such a metal ion and a nitrogen atom adjacent to the functional group R ′, the functional group R ′, and the functional group R ′ in the formula (6). From the group of
- the first organic molecule and the second organic molecule are bonded by binding at least one selected type to form a chelate.
- the functional group R ′, the functional group R ′ and the functional group in the formula (6) are bonded by binding at least one selected type to form a chelate.
- At least one selected from the group consisting of nitrogen atoms adjacent to R ′ is bonded to a metal ion.
- the second organic molecule and the second organic molecule are bonded to each other, and the conjugate of the second organic molecule is extended.
- the electrode coating material according to the fourth aspect of the present invention, the electrode coating material in the semiconductor device according to the fourth aspect of the present invention, the fourth aspect of the present invention is characterized by comprising an organic molecule having a functional group capable of binding to a metal ion and a functional group binding to an electrode made of metal (or a source / drain electrode).
- the electrode coating material according to the fourth aspect of the present invention, the semiconductor device according to the fourth aspect of the present invention, or the electrode structure according to the fourth aspect of the present invention (hereinafter collectively referred to as these).
- a chelate can be formed by the bond between the functional group capable of binding to the metal ion and the metal ion, or
- the functional group capable of binding to a metal ion is pyridine or a derivative thereof, biviridine or a derivative thereof, or terpyridine or a derivative thereof, and is bonded to an electrode made of metal (or a source / drain electrode).
- the functional group may be a thiol group, or may be a carboxyl group, a cyano group, a thiocyanato group, an amino group, a silanol group, a hydroxyl group, a pyridine, a thiophene, or the like.
- R in the formula (1) is any one of the following formulas (41) to (419), Z is any one of the following formulas (5-1) to (5-18),
- Z is one of the following formulas (5-1) to (5-18), • Z is one of the following formulas (51) to (5--18),
- n and m are integers greater than or equal to 1.
- X in the formula (1) has a molecular structure composed of a ⁇ -conjugated system or a ⁇ -conjugated system
- ⁇ -conjugated systems include the ability to list carbon-based unsaturated groups such as phenyl groups and bur groups (etul groups), and examples of ⁇ -conjugated systems include the ability to list sulfide groups, disulfide groups, and silyl groups.
- a composite system of a ⁇ -conjugated system and a ⁇ -conjugated system may be used.
- X in formula (1) preferably has no degree of freedom other than rotation with respect to the binding sites on both sides from the viewpoint of assuming that the organic molecule is a rigid ⁇ -conjugated structure.
- an alkali metal or alkaline earth is widely used as the metal constituting the metal ion.
- Metal, transition metal, and rare earth metal Specifically, for example, iron (Fe), cobalt (Co), copper (Cu), nickel (Ni), silver (Ag), platinum (Pt), Examples include palladium (Pd), ruthenium (Ru), titanium (Ti), zinc (Zn), magnesium (Mg), and manganese (Mn).
- the electrode (there! / Is the source) As a method of coating the surface of the electrode / drain electrode) with an electrode coating material, for example, the functional group Y having a substituent such as a thiol group can be bonded to the surface of the electrode (or source / drain electrode) Examples include a method of forming a layer made of an electrode coating material as a self-assembled monomolecular film on the surface of the electrode (or source / drain electrode).
- a method of forming a chelate by immersing it in a metal ion solution after forming a bond with the group Y can be mentioned.
- Examples include alloys containing elements, conductive particles made of these metals, conductive particles of alloys containing these metals, and the source / drain electrodes have a laminated structure of layers containing these elements.
- the semiconductor device in addition to these materials, polysilicon containing impurities, etc.
- examples thereof include organic materials (conductive polymers) such as poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid [PEDOT / PSS], and carbon-based materials.
- the materials constituting the source / drain electrode, gate electrode, and various wirings may be the same material or different materials.
- PVD method physical vapor deposition
- CVD method various chemical vapor deposition methods including MOCVD method (CVD method); spin coating method
- various printing methods such as screen printing method, inkjet printing method, offset printing method, gravure printing method
- PVD methods include (a) various electron beam evaporation methods such as electron beam heating method, resistance heating method, flash evaporation, (b) plasma evaporation method, (c) bipolar sputtering method, DC sputtering method, DC magnetron sputtering.
- High frequency sputtering method magnetron sputtering method, ion beam sputtering method, various sputtering methods such as noise sputtering method, (d) DC (direct current) method, RF method, multi-cathode method, activation reaction method , Field evaporation, high frequency ion plating, reactivity
- various ion plating methods such as an on plating method, can be mentioned.
- a silicon oxide-based material As a material constituting the gate insulating layer, a silicon oxide-based material, a silicon nitride (SiN), a metal
- Organic insulating materials such as polymethylmetatalate (PMMA), polybutanol (PVP), and polybulualcohol (PVA), which are made of only inorganic insulating materials such as oxide high dielectric insulating films Or a combination of these.
- SiO 2 materials eg polyaryl ether, cycloperfluorocarbon polymer and benzocyclobutene, cyclic fluororesin, polytetra Fluoroethylene, fluorinated ether, fluorinated polyimide, amorphous carbon, organic SOG
- 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.
- oxidizing the surface of the gate electrode although depending on the material constituting the gate electrode, an oxidation method using O plasma and an anodic oxidation method can be exemplified.
- a nitriding method using N plasma can be exemplified.
- an Au electrode 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-organizing manner by a method such as a method.
- the portion of the source / drain electrode in contact with the organic semiconductor material layer constituting the channel formation region is covered with the electrode coating material.
- the side surface of the source / drain electrode is the electrode coating material. Covered with! /
- the side surface and the top surface of the source / drain electrode may be coated with an electrode coating material.
- the side surface of the source / drain electrode is coated with an electrode coating material, and the top surface of the source / drain electrode is described later. It may be covered with an insulating material that constitutes an insulating film.
- the organic semiconductor material constituting the organic semiconductor material layer as the channel formation region is an organic semiconductor molecule having a conjugated bond, and has a thiol group (one SH), an amino group (NH), an isocyano group at both ends of the molecule. It preferably has a group (NC), a cyano group (CN), a thioacetoxyl group (SCOCH 3), or a carboxy group (COOH).
- the functional groups located at both ends of the molecule are different.
- an organic semiconductor material constituting an organic semiconductor material layer as a channel formation region pentacene and its derivatives (such as TIPS pentacene), naphthacene and its derivatives (rubrene, hexapropylnaphthacene), P3HT, PQT, F8T2, Structural formula (1 1) 4, 4, -biphenyldithiol (BPDT), Structural formula (12) 4, 4'-diisocyanobiphenyl, Structural formula (13) 4, 4'-diisocyanano p terphenyl , And 2,5 bis (5, -thioacetyl-2, -thiophenenole) thiophene of structural formula (14), 4,4'-diisocyananophenyl of structural formula (15), benzidine of structural formula (16) ( Biphenyl 4,4'-diamine), TCNQ (tetracyanquinodimethane) in structural formula
- an organic molecule represented by the structural formula (22) can also be used as the organic semiconductor material.
- “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 (2 3-4).
- Each of “Y” and “ ⁇ ” in formula (22) is represented by formula (24-1
- X is a unit in which units represented by formula (23-1), formula (23-2), formula (23-3), or formula (23-4) are repeatedly bonded one or more times. Yes, with different units Including repetition. Furthermore, the side chains Z 1, Z 2, Z 3 and Z are different during the repetition.
- the organic semiconductor material layer can be formed based on a CVD method, a stamp method, a vapor deposition method, a coating method, a spin coating method, an ink jet method, an immersion method, and the like.
- a single-layer or multilayer organic semiconductor material layer based on a ⁇ -conjugated complex oligomer or a ⁇ -conjugated complex polymer can be formed.
- the thickness S of the organic semiconductor material layer is expressed by the force S indicating f rows of several tens of nm to several ⁇ m.
- the semiconductor device is composed of a top-gate / bottom-contact field effect transistor (FET)
- FET top-gate / bottom-contact field effect transistor
- various glass substrates various glass substrates with an insulating film formed on the surface, stone substrates, quartz substrates with an insulating film formed on the surface, and silicon substrates with an insulating film formed on the surface are used. I can power up.
- polymethyl methacrylate polymethyl methacrylate
- PMMA polybulal alcohol
- PVA polybutanol
- PEN polyethylene naphthalate
- PSF polyethersulfone
- PES polyethylene
- PET polyethylene terephthalate
- S flexible plastic 'films and plastics' composed of polymer materials, plastic sheets, and plastic substrates
- a conductive substrate (a substrate made of a metal such as gold or a highly oriented graphite) as a support. Further, depending on the configuration and structure of the semiconductor device, the force with which the semiconductor device is provided on the support member.
- This support member can also be made of the above-described materials.
- silicon-containing materials SiO 2, SiN, etc.
- aluminum oxide metal oxide
- Examples thereof include insulators such as oxides and metal salts, or organic polymers such as polymethylmetatalylate (PMMA) and polybutanol (PVP).
- PMMA polymethylmetatalylate
- PVP polybutanol
- the surface of the support is preferably smooth, but there is no problem even if there is roughness that does not contribute to the conductivity of the organic semiconductor material layer.
- a silane cup may be used as an adhesion layer on the support surface. It is preferable to form a silanol derivative by a ring method, or to form a metal salt / metal complex thin film of an insulator by a CVD method or the like.
- the channel formation region is composed of an organic semiconductor material layer.
- the organic semiconductor material layer includes fine particles made of a conductor or a semiconductor! /, Or may /!
- the channel forming region may be constituted of fine particles made of a conductor or a semiconductor and organic semiconductor molecules bonded to the fine particles.
- the functional group that the organic semiconductor molecule has at the end is chemically bonded to the fine particles.
- the organic semiconductor molecule and the fine particles are bonded to each other by the functional group that the organic semiconductor molecule has at both ends. It is preferable that a network-like conductive path is constructed by chemically (alternatingly) bonding.
- the conductive path may be constituted by a single layer of a combination of fine particles and organic semiconductor molecules, and a three-dimensional network-like conductive path may be formed by a laminated structure of the combination of fine particles and organic semiconductor molecules. It may be configured.
- a network-like conductive path By constructing a network-like conductive path in this way, charge transfer in the conductive path occurs predominantly in the direction of the molecular axis along the main chain of the organic semiconductor molecule, and inter-electron electrons are generated in the conductive path.
- the mobility is not limited by electron movement between molecules, which is the cause of low mobility in semiconductor devices using conventional organic semiconductor materials.
- the fine particles are gold (Au), silver (Ag), platinum (Pt), copper (Cu), aluminum (A1), palladium (Pd), chromium (Cr), nickel (Ni), iron as conductors. (Fe) and!
- CdS cadmium sulfide
- CdSe cadmium selenide
- CdTe gallium arsenide
- TiO 2 titanium oxide
- Si silicon force
- the fine particles as a conductor refers to microparticles made of a material of the order or less of a volume resistivity of 10- 4 ⁇ ⁇ ⁇ (10- 2 ⁇ 'cm).
- the fine particles of a semiconductor a material or made fine particles of the order of a volume resistivity of 10- 4 ⁇ ⁇ m (10- 2 ⁇ ⁇ cm) to 10 12 ⁇ ⁇ m (10 14 ⁇ ⁇ cm) Point to.
- the range of the average particle size R of the fine particles is 5.0 X 10— 1Q m ⁇ R, preferably
- OX 10 10 m ⁇ R ⁇ 1. 0 X 10 _6 m, more preferably 5. OX 10" 10 m ⁇ R ⁇ 1
- a force that can give a spherical shape as the shape of the fine particles Other than this, for example, a triangle, a tetrahedron, a cube, a rectangular parallelepiped, a cone, a cylinder (rod), a triangular prism, a fiber, a pill-like fiber, etc. be able to .
- the average particle size R of the fine particles when the shape of the fine particles is other than a spherical shape is the fine particle size other than the spherical shape.
- the average value of the diameters of the spheres may be the average particle size R of the fine particles.
- the average particle diameter R of the fine particles is, for example, transmission electron
- the semiconductor device of the present invention 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. It may be individualized and used as a discrete part. Further, the semiconductor device may be sealed with resin.
- an expression representing an electrode coating material bonded to the surface of the electrode made of metal that is, an electrode coating material before bonding to the surface of the electrode made of metal
- the formula representing the electrode coating material after bonding to the electrode surface may be different because the electrode coating material bonds to the electrode surface.
- the above-described various expressions are expressions representing the electrode coating material before being bonded to the surface of the electrode made of metal.
- an intermediate compound between an inorganic substance and an organic substance for example, an organic-inorganic hybrid compound having a rigid ⁇ synergistic system is used as an electrode coating material.
- the electrode coating material to the electrode (or source / drain electrode)
- the organic semiconductor material constituting the organic semiconductor material layer and the source / drain electrode are bonded via the electrode coating material. This facilitates electron transfer between the organic semiconductor material constituting the semiconductor material layer and the source / drain electrodes, and as a result, for example, high mobility and low contact resistance can be achieved in the semiconductor device.
- a metal ligand bond can be formed with a high probability by appropriately combining the two.
- an organic ligand having two or more functional groups capable of coordinate bonding with a metal ion is reacted with a metal ion, the reaction proceeds sequentially, so that a polymer in which metal ions are arranged on the main chain. Use force S to form a complex.
- Alkane molecule ( ⁇ bond) Alkene alkyne molecule ( ⁇ bond)
- FIG. 1 is a schematic partial cross-sectional view of a semiconductor device of Example 1
- FIG. 1C is a semiconductor device of Example 1.
- FIG. FIG. 3 is a conceptual diagram of a channel forming region and its vicinity.
- FIG. 2 is a schematic partial cross-sectional view of the semiconductor device of Example 2.
- FIG. 3 (B) and (B) in FIG. 3 are conceptual diagrams of a channel formation region of the semiconductor device of Example 3 and Example 4 and the vicinity thereof, respectively.
- FIG. 4 is a view showing a synthesis scheme of a ⁇ -conjugated iron polymer in Example 4.
- FIG. 5 is a graph showing the relationship between mobility and channel length in the bottom gate / bottom contact type TFT prototypes of Example 1 and Example 3.
- Example 1 relates to the electrode coating material according to the first aspect of the present invention, the electrode structure according to the first aspect of the present invention, and the semiconductor device according to the first aspect of the present invention.
- the semiconductor device of Example 1, or the semiconductor devices of Examples 2 to 4 described later includes a channel forming region 16 composed of a gate electrode 13, a gate insulating layer 14, and an organic semiconductor material layer 17, and And a field effect transistor having source / drain electrodes 15 made of metal.
- the portion of the source / drain electrode 15 in contact with the organic semiconductor material layer 17 constituting the channel formation region 16 is covered with electrode coating materials 21, 121, and 221.
- the electrode structures of Example 1 or Examples 2 to 4 described later include an electrode 15 and electrode coating materials 21, 121, and 221 that coat the surface of the electrode 15.
- the semiconductor device of Example 1 includes a bottom gate / bottom contact field effect transistor (FET), more specifically, a thin film transistor (TFT). / Bottom contact type TFT, as shown in the schematic partial cross-section in Fig. 1 (B),
- the electrode coating material 21 is composed of an organic molecule represented by the formula (1), the functional group Y force S in the formula (1), and the surface of the electrode 15 (or source / drain electrode 15) composed of metal. Combine with.
- Example 1 X in the formula (1) is absent, and Y in the formula (1) is the formula (3-1), that is, “one SH”, and the formula (1
- Each of R and R in 1) is the formula (41), and Z, Z, Z, Z
- Electrode coating material 21 is each the formula (51), that is, “one H”.
- the gate electrode 13 is made of an aluminum (A1) layer
- the gate insulating layer 14 is also made of SiO force
- the source / drain electrode 15 is made of gold (Au) layer force
- the channel forming region 16 is made of pentacene.
- FIG. 1C A conceptual diagram of the channel forming region 16 and the vicinity thereof is shown in FIG. 1C, and the surface of the source / drain electrode 15 is covered with an electrode covering material 21.
- the organic molecule represented by the formula (31) is schematically indicated by a circle.
- Example 1 An outline of a method for manufacturing the semiconductor device of Example 1 will be described.
- the gate electrode 13 is formed on the support 10. Specifically, a resist layer (not shown) from which a portion where the gate electrode 13 is to be formed is removed is formed on the insulating film 12 having a SiO force formed on the surface of the glass substrate 11 based on the lithography technique. . Thereafter, a chromium (Cr) layer (not shown) having a thickness of 0.5 nm as an adhesion layer and an aluminum (A1) layer having a thickness of 25 nm as a gate electrode 13 are sequentially formed on the entire surface by vacuum deposition. Then, the resist layer is removed. Thus, the gate electrode 13 can be obtained based on the so-called lift-off method.
- the gate insulating layer 14 is formed on the support 10 including the gate electrode 13 (more specifically, the insulating film 12 formed on the surface of the glass substrate 11). Specifically, a gate insulating layer 14 having a SiO force with a thickness of 150 nm is formed on the gate electrode 13 and the insulating film 12 based on a sputtering method. When depositing the gate insulating layer 14, by covering a part of the gate electrode 13 with a hard mask, it is possible to form an extraction part (not shown) of the gate electrode 13 without a photolithography process. . [0075] [Step 120]
- a source / drain electrode 15 made of a gold (Au) layer is formed on the gate insulating layer 14. 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 a source / drain electrode 15 are sequentially formed. It is formed based on the vacuum deposition method. When depositing these layers, the source S / drain electrode 15 can be formed without a photolithography process by covering a part of the gate insulating layer 14 with a mask and a mask S.
- HMDS hexamethyldisilazane
- the surface of the electrode (source / drain electrode 15) is covered with an electrode covering material 21 (see (A) in FIG. 1).
- a terpyridine thiol self-assembled monolayer is obtained by immersing the whole in a black mouth form solution of terbilidine disulfide represented by the formula (31) of 0.1 millimol / liter for 18 hours.
- the surface of the electrode (source / drain electrode 15) was covered with an electrode coating material 21.
- pentacene was deposited on the entire surface by using a vacuum evaporation apparatus to form a channel formation region 16 (see FIG. 1B).
- the thickness of the channel forming region 16 above the gate insulating layer 14 located between the source / drain electrodes 15 was set to 50 nm.
- a bottom gate / bottom contact type FET (specifically, a TFT) can be obtained by forming a passivation film (not shown) on the entire surface.
- the second embodiment is a modification of the first embodiment.
- the semiconductor device The gate / bottom contact type FET (specifically, TFT) was used. That is, the top gate / bottom contact type TFT, which is the semiconductor device of Example 2, shows a schematic partial cross-sectional view in FIG.
- the surface of the source / drain electrode 15 is covered with an electrode covering material 21.
- the source / drain electrode 15 is formed on the insulating film 12 by the same method as in [Step 120] of Example 1.
- a single layer film of HMDS is formed on the surface of the support beam, specifically the insulating film 12).
- a top gate / bottom contact type FET (specifically, TFT) can be obtained by forming a passivation film (not shown) on the entire surface.
- Example 3 relates to the electrode coating material according to the second aspect of the present invention, the electrode structure according to the second aspect of the present invention, and the semiconductor device according to the second aspect of the present invention. Furthermore, the present invention relates to an electrode coating material according to the fourth aspect of the present invention, an electrode structure according to the fourth aspect of the present invention, and a semiconductor device according to the fourth aspect of the present invention. More specifically, the semiconductor device of Example 3 is composed of a bottom gate / bottom contact type FET. This bottom gate / bottom contact type FET beam, specifically, TFT) is shown in FIG. 1 (B) has the same configuration and structure as shown in the schematic partial sectional view.
- the semiconductor device of Example 3 is more specifically composed of a top gate / bottom contact type FET, and the top gate / bottom contact type FET beam, specifically, TFT) is FIG. 2B has the same configuration and structure as the schematic partial cross-sectional view shown in FIG. Therefore, the description of the specific configuration and structure of the semiconductor device of Example 3 is omitted.
- the electrode coating material 121 is made of an organic molecule represented by the formula (1), and the functional group Y in the formula (1) is a surface of the electrode 15 (or the source / drain electrode 15) made of metal. And at least 1 selected from the group consisting of nitrogen atom, functional group R and functional group R in formula (1)
- Z 1, Z and Z are each of the formula (51), ie “one H”, and the metal ion is iron (Fe
- the electrode coating material 121 is made of an organic molecule represented by the formula (32). And the nitrogen atom, functional group R and functional group R in formula (1) are bonded to the metal ion.
- the electrode coating material 121 also has an organic molecular force having a functional group capable of binding to a metal ion and a functional group binding to an electrode made of a metal (or the source / drain electrode 15). Then, chelate is formed by the bond between the functional group capable of binding to the metal ion and the metal ion.
- the functional group capable of binding to the metal ion is terpyridine
- the functional group binding to the metal electrode (or the source / drain electrode 15) is a thiol group.
- the gate electrode 13 is made of an aluminum (A1) layer, the gate insulating layer 14 is also made of SiO, the source / drain electrode 15 is made of gold (Au), and the channel forming region 16 is made of pentacene. .
- a conceptual diagram of the channel forming region 16 and the vicinity thereof is shown in FIG. 3A.
- the surface of the source / drain electrode 15 is covered with an electrode covering material 121.
- the organic molecule represented by the formula (32) is schematically shown by a rhombus.
- the semiconductor device of Example 3 can be obtained by performing the following process following [Step 140] of Example 1 or following [Step I 220] of Example 2.
- the semiconductor device of Example 3 can be manufactured based on the method of manufacturing a semiconductor device described in Example 1 or Example 2, and thus detailed description thereof is omitted.
- Example 4 relates to the electrode coating material according to the third aspect of the present invention, the electrode structure according to the third aspect of the present invention, and the semiconductor device according to the third aspect of the present invention, Furthermore, this departure The present invention relates to an electrode coating material according to a fourth aspect, an electrode structure according to a fourth aspect of the present invention, and a semiconductor device according to the fourth aspect of the present invention. More specifically, the semiconductor device of Example 4 is composed of a bottom gate / bottom contact type FET, and this bottom gate / bottom contact type FET beam (specifically, TFT) is shown in FIG. 1 (B) has the same configuration and structure as shown in the schematic partial sectional view.
- TFT bottom gate / bottom contact type FET beam
- the semiconductor device of Example 4 is more specifically composed of a top gate / bottom contact type FET, and this top gate / bottom contact type FET beam, specifically, TFT) is FIG. 2B has the same configuration and structure as the schematic partial cross-sectional view shown in FIG. Therefore, the description of the specific configuration and structure of the semiconductor device of Example 4 is omitted.
- the electrode coating material 221 is composed of a first organic molecule and a second organic molecule.
- the first organic molecule is composed of an organic molecule represented by the formula (1)
- the second organic molecule is It consists of an organic molecule represented by formula (6).
- the functional group Y in the formula (1) is bonded to the surface of the metal electrode (or source / drain electrode), and the nitrogen atom, the functional group R, and the functional group in the formula (1) are bonded.
- At least one type selected from the group consisting of 1 group R force binds to a metal ion to form a chelate, and is adjacent to functional group R ′, functional group R ′ and functional group R ′ in formula (6) Nitrogen atom (next door
- At least one selected from the group consisting of B) binds to a metal ion to form a chelate.
- X in formula (1) is none
- Y in formula (1) is formula (31), that is, "one SH”
- R in formula (1) And R are the equations (41), and Z, Z, Z, Z, Z and Z
- the first organic molecule is specifically composed of the organic molecule represented by the formula (32) described in Example 3.
- Each of 1 2 3 and R ' is the formula (8 1), and each of ⁇ ', ⁇ ', ⁇ ', ⁇ ', ⁇ ' and ⁇ ' This is the formula (9-1), that is, “one H”, and the metal ion is an iron (Fe) ion.
- the second organic molecule specifically consists of an organic molecule represented by the formula (33) shown on the right side of FIG.
- the electrode coating material 221 is an organic molecule having a functional group capable of binding to a metal ion and a functional group binding to an electrode made of metal (or source / drain electrode 15). Consists of. And a chelate is formed by the coupling
- the functional group capable of binding to the metal ion is terpyridine, and the functional group binding to the electrode made of metal (or the source / drain electrode 15) is a thiol group.
- the gate electrode 13 is made of an aluminum (A1) layer, the gate insulating layer 14 is also made of SiO, the source / drain electrode 15 is made of gold (Au), and the channel forming region 16 is made of pentacene. .
- a conceptual diagram of the channel forming region 16 and its vicinity is shown in FIG. 3B, and the surface of the source / drain electrode 15 is covered with an electrode covering material 221.
- a ⁇ -conjugated iron polymer ⁇ [Fe—BL] 2+ -2BF— ⁇ is prepared in advance. Specifically, Tetra
- the semiconductor device of Example 4 can be obtained by performing the following process following [Step 140] of Example 1 or following [Step 220] of Example 2.
- the semiconductor device of Example 4 can be manufactured based on the manufacturing method of the semiconductor device described in Example 1 or Example 2, and thus detailed description thereof is omitted.
- Example 1 Example 3, and Example 4, a bottom gate / bottom contact type TFT was fabricated.
- five types of TFTs with channel lengths of 10 ⁇ ⁇ 20 ⁇ m, 50 ⁇ m, 70 ⁇ m, and 100 ⁇ m were prototyped.
- the channel width was 5.6 mm for all prototypes.
- the measurement results of mobility ⁇ in the linear region of Example 3 are shown.
- the black circles indicated by “C” indicate the measurement results of mobility in the saturation region of Example 1, and the black triangles indicated by “D” are
- Example 1 For comparison, in Example 1, a bottom gate / bottom contact type TFT without [Step 140] was prototyped and measured for contact resistance. As a result, the contact resistance was 30 k Q to 40 k Q, which was very high. Value. Also, the values of ⁇ and 11 are
- Electrode covering material assists the electron transfer between the source / drain electrode made of metal and the channel formation region composed of the organic semiconductor material layer, resulting in a significant reduction in contact resistance and high mobility We were able to.
- conjugated complex polymers have been shown to move faster in the main chain than normal organic conductive polymers, and a sufficient improvement in conductivity is theoretically supported. It has been.
- Figure 5 also shows that mobility does not decrease much even when the channel length is 10 m.
- the present invention has been described based on the preferred embodiments.
- the present invention is not limited to these embodiments.
- the structure, configuration, formation conditions, and manufacturing conditions of the semiconductor device are examples and can be changed as appropriate.
- FET field effect transistor
- the field effect transistor (FET) 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 FETs are integrated on a support or a support member. However, each FET may be cut and individualized and used as a discrete component.
- the force electrode in which the electrode is exclusively the source / drain electrode is not limited to the source / drain electrode, but is formed in a layer made of an organic conductive polymer (conductive material) or an organic semiconductor material.
- the electrode coating material of the present invention can be widely applied to electrodes in fields where current is applied from an electrode or voltage is required to be applied.
- the electrode coating material can be composed of the first organic molecule and the third organic molecule.
- the first organic molecule is composed of an organic molecule represented by the formula (1).
- the third organic molecule is composed of an organic molecule represented by formula (100-1), formula (100-2), or formula (1003). Then, the functional group Y in the formula (1) is bonded to the surface of the electrode made of metal, and the group consisting of the nitrogen atom, the functional group R, and the functional group R in the formula (1)
- At least one selected from the above binds to a metal ion to form a chelate, and the functional group Y,, functional of the formula (100-0-1), the formula (100-2), or the formula (1003) Group ⁇ , functional group Y 'and
- At least one selected from the group consisting of 1 2 3 and functional group Y ′ binds to a metal ion.
- X in the formula (1) is any one of the formulas (2-1) to (2-10) as described above.
- Y in the formula (1) is any one of the formulas (31) to (312), and each of R and R in the formula (1) is represented by the formulas (41) to ( 4 19), Z, Z, Z,
- X ′′ in 100-1), formula (100-2), or formula (1003) is any one of formulas (2-1) to (2-10) as described above.
- Each of Y “, Y", ⁇ "and ⁇ " in formula (100-2) or formula (100 3) is represented by the following formulas (101-1) to (101-15)
- N and m are integers of 1 or more.
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Description
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US12/515,585 US8895960B2 (en) | 2006-11-22 | 2007-11-21 | Electrode covering material, electrode structure and semiconductor device |
KR1020097010423A KR101413208B1 (ko) | 2006-11-22 | 2007-11-21 | 전극 피복 재료, 전극 구조체 및 반도체 장치 |
CN2007800435177A CN101542698B (zh) | 2006-11-22 | 2007-11-21 | 电极覆盖材料、电极结构和半导体装置 |
EP07832311.0A EP2091077B1 (en) | 2006-11-22 | 2007-11-21 | Electrode coating material, electrode structure and semiconductor device |
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JP2006315845A JP5151122B2 (ja) | 2006-11-22 | 2006-11-22 | 電極被覆材料、電極構造体、及び、半導体装置 |
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US (1) | US8895960B2 (ja) |
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JP (1) | JP5151122B2 (ja) |
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CN (1) | CN101542698B (ja) |
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JP5532553B2 (ja) * | 2008-06-11 | 2014-06-25 | 凸版印刷株式会社 | 薄膜トランジスタ、薄膜トランジスタの製造方法、薄膜トランジスタアレイ及び画像表示装置 |
JP2010040897A (ja) * | 2008-08-07 | 2010-02-18 | Sony Corp | 有機薄膜トランジスタ、有機薄膜トランジスタの製造方法、および電子機器 |
JP5549073B2 (ja) * | 2008-12-12 | 2014-07-16 | ソニー株式会社 | 有機半導体装置およびその製造方法 |
EP2494617A1 (en) | 2009-10-26 | 2012-09-05 | Imec | Method for fabricating organic devices |
JP2011216647A (ja) * | 2010-03-31 | 2011-10-27 | Dainippon Printing Co Ltd | パターン形成体の製造方法、機能性素子の製造方法および半導体素子の製造方法 |
FR2960703B1 (fr) * | 2010-05-28 | 2012-05-18 | Commissariat Energie Atomique | Dispositif optoelectronique avec electrode enterree |
CN102610756B (zh) * | 2012-03-31 | 2014-07-16 | 上海交通大学 | 一种溶液法低电压高性能有机薄膜晶体管及其制备方法 |
WO2014208442A1 (ja) * | 2013-06-26 | 2014-12-31 | シャープ株式会社 | 薄膜トランジスタ |
CN106062982B (zh) | 2014-02-19 | 2019-04-26 | 默克专利股份有限公司 | 环胺表面改性剂和包含这样的环胺表面改性剂的有机电子器件 |
JP6330408B2 (ja) * | 2014-03-20 | 2018-05-30 | 凸版印刷株式会社 | 薄膜トランジスタ及びその製造方法 |
KR102439505B1 (ko) | 2015-06-11 | 2022-09-02 | 삼성디스플레이 주식회사 | 박막 트랜지스터 기판 |
CN105185835A (zh) * | 2015-07-30 | 2015-12-23 | 京东方科技集团股份有限公司 | 一种薄膜晶体管及其制作方法、阵列基板、显示装置 |
CN107316815B (zh) * | 2017-06-30 | 2019-12-20 | 京东方科技集团股份有限公司 | 薄膜晶体管及其制备方法、阵列基板和显示装置 |
KR102469279B1 (ko) * | 2017-11-28 | 2022-11-22 | 주식회사 엘지화학 | 기상 증착 장치 및 이를 이용한 증착 방법 |
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CN101542698B (zh) | 2011-06-08 |
US8895960B2 (en) | 2014-11-25 |
TW200838006A (en) | 2008-09-16 |
US20100314611A1 (en) | 2010-12-16 |
EP2091077B1 (en) | 2014-01-29 |
KR20090082419A (ko) | 2009-07-30 |
EP2091077A4 (en) | 2011-08-10 |
KR101413208B1 (ko) | 2014-06-27 |
JP5151122B2 (ja) | 2013-02-27 |
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