US20150318077A1 - Composition, laminate, method of manufacturing laminate, transistor, and method of manufacturing transistor - Google Patents
Composition, laminate, method of manufacturing laminate, transistor, and method of manufacturing transistor Download PDFInfo
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- US20150318077A1 US20150318077A1 US14/748,927 US201514748927A US2015318077A1 US 20150318077 A1 US20150318077 A1 US 20150318077A1 US 201514748927 A US201514748927 A US 201514748927A US 2015318077 A1 US2015318077 A1 US 2015318077A1
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- electrode
- manufacturing
- base film
- transistor
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Images
Classifications
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- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/46—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes silicones
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3254—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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- C08G59/621—Phenols
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/687—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing sulfur
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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- G—PHYSICS
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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- G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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- G—PHYSICS
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
- H01L21/02126—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
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- H01L51/0002—
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- H01L51/0015—
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- H01L51/0023—
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- H01L51/052—
-
- H01L51/0545—
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
- H10K10/466—Lateral bottom-gate IGFETs comprising only a single gate
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
- H10K10/468—Insulated gate field-effect transistors [IGFETs] characterised by the gate dielectrics
- H10K10/471—Insulated gate field-effect transistors [IGFETs] characterised by the gate dielectrics the gate dielectric comprising only organic materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/20—Changing the shape of the active layer in the devices, e.g. patterning
- H10K71/211—Changing the shape of the active layer in the devices, e.g. patterning by selective transformation of an existing layer
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/621—Providing a shape to conductive layers, e.g. patterning or selective deposition
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
Definitions
- the present invention relates to a composition, a laminate, a method of manufacturing a laminate, a transistor, and a method of manufacturing a transistor.
- the laminate having such a laminated structure is used, for example, to achieve the miniaturization and high integration of electronic circuits.
- this laminate is used for a printed circuit board, a condenser, a transistor, and the like, each having a multilayer wiring structure.
- the laminate using an organic insulator is advantageous, compared to a laminate using a conventional insulator layer using SiO 2 as a formation material, in that an insulator layer can be formed in a liquid phase and in that a laminated structure can be formed at a lower temperature without requiring a vacuum process.
- a developer used for patterning an insulator layer may dissolve or swell the resin substrate.
- an alkaline solution it is known that it is possible to prevent the resin substrate from being dissolved or swelled, but a material in use for an insulator layer developable by an alkaline solution has been limited.
- An object of an aspect of the present invention is to provide a composition developable by an alkaline solution and capable of forming an insulator layer.
- Another object of an aspect of the present invention is to provide a method of manufacturing a laminate using the composition, a manufactured laminate, a method of manufacturing a transistor, and a manufactured transistor.
- composition according to an aspect of the present invention includes:
- a first cross-linking agent that is at least one organic silicon compound selected from the group including
- a method of manufacturing a laminate according to another aspect of the present invention includes: applying a solution containing the above-described composition over a conductive layer to form a coating film; selectively irradiating the coating film with light including light having an absorption wavelength of the photocationic polymerization initiator included in the coating film to form a latent image in the light-irradiated region of the coating film; and developing the coating film with an alkaline solution to form an insulator layer.
- a laminate according to another aspect of the present invention includes: a conductive layer; and an insulator layer formed by cationic-polymerization of the above-described composition.
- a method of manufacturing a transistor according to another aspect of the present invention includes: forming a gate electrode on a substrate; applying a solution including the above-described composition over the gate electrode to form a coating film; selectively irradiating the coating film with light including light having an absorption wavelength of a photocationic polymerization initiator included in the coating film to form a latent image in the light-irradiated region of the coating film; developing the coating film with an alkaline solution to form an insulator layer; and forming a source electrode and a drain electrode on the surface of a layer including the insulator layer.
- a transistor according to another aspect of the present invention includes: a source electrode and a drain electrode; a gate electrode provided corresponding to a channel between the source electrode and the drain electrode; a semiconductor layer provided in contact with the source electrode and the drain electrode; and an insulator layer disposed between the source electrode and the gate electrode and between the drain electrode and the gate electrode, wherein the insulator layer is formed by cationic polymerization of the above-described composition.
- composition developable by an alkaline solution and capable of forming an insulator layer.
- method of manufacturing a laminate using the composition, a manufactured laminate, a method of manufacturing a transistor, and a manufactured transistor.
- FIG. 1A is a process view showing a method of manufacturing a laminate according to a first embodiment.
- FIG. 1B is a process view showing the method of manufacturing a laminate according to the first embodiment.
- FIG. 1C is a process view showing the method of manufacturing a laminate according to the first embodiment.
- FIG. 2 is a schematic cross-sectional view showing a transistor of a second embodiment.
- FIG. 3A is a process view showing a manufacturing method of the second embodiment.
- FIG. 3B is a process view showing the manufacturing method of the second embodiment.
- FIG. 3C is a process view showing the manufacturing method of the second embodiment.
- FIG. 3D is a process view showing the manufacturing method of the second embodiment.
- FIG. 3E is a process view showing the manufacturing method of the second embodiment.
- FIG. 3F is a process view showing the manufacturing method of the second embodiment.
- FIG. 3G is a process view showing the manufacturing method of the second embodiment.
- FIG. 3H is a process view showing the manufacturing method of the second embodiment.
- FIG. 3I is a process view showing the manufacturing method of the second embodiment.
- FIG. 3J is a process view showing the manufacturing method of the second embodiment.
- FIG. 3K is a process view showing the manufacturing method of the second embodiment.
- FIG. 3L is a process view showing the manufacturing method of the second embodiment.
- FIG. 3M is a process view showing the manufacturing method of the second embodiment.
- FIG. 3N is a process view showing the manufacturing method of the second embodiment.
- FIG. 3O is a process view showing the manufacturing method of the second embodiment.
- FIG. 3P is a process view showing the manufacturing method of the second embodiment.
- FIG. 3Q is a process view showing the manufacturing method of the second embodiment.
- FIG. 4A is a view showing a drive status of the transistor of the second embodiment.
- FIG. 4B is a view showing a drive status of the transistor of the second embodiment.
- FIG. 5 is a schematic cross-sectional view of a transistor of a third embodiment.
- FIG. 6A is a process view showing a manufacturing method of the third embodiment.
- FIG. 6B is a process view showing the manufacturing method of the third embodiment.
- FIG. 6C is a process view showing the manufacturing method of the third embodiment.
- FIG. 6D is a process view showing the manufacturing method of the third embodiment.
- FIG. 6E is a process view showing the manufacturing method of the third embodiment.
- FIG. 6F is a process view showing the manufacturing method of the third embodiment.
- FIG. 6G is a process view showing the manufacturing method of the third embodiment.
- FIG. 7 shows photographs showing the results of Example 1.
- FIG. 8A is a view showing a manufacturing process of a sandwich cell evaluated in Example 2.
- FIG. 8B is a view showing the manufacturing process of the sandwich cell evaluated in Example 2.
- FIG. 8C is a view showing the manufacturing process of the sandwich cell evaluated in Example 2.
- FIG. 9 is a graph showing the frequency dependence of dielectric constant of an insulator layer of Example 2.
- FIG. 10 is a graph showing an evaluation result of insulating property of the insulator layer of Example 2.
- FIG. 11 shows photographs showing the results of Example 3.
- FIG. 12 shows photographs showing the results of Example 3.
- FIG. 13 shows photographs showing the results of Example 3.
- FIG. 14 shows a photograph showing the result of Example 3.
- FIG. 15 shows a graph showing the result of Example 3.
- a composition of the present embodiment includes the following (a) to (c):
- a first cross-linking agent that is at least one organic silicon compound selected from the group including
- composition of the present invention is not limited to the curable composition.
- the curable composition of the present embodiment is soluble in an alkaline solution.
- an alkaline solution an alkaline developer which is commonly used in a field such as photolithography can be used.
- materials of the developer include an aqueous TMAH (tetramethylammonium hydroxide) solution and an aqueous NaOH (sodium hydroxide) solution.
- soluble in an alkaline solution refers to that when a coating film formed in a film thickness of 1 ⁇ m is immersed in 2.38 mass % of an aqueous TMAH (tetramethylammonium hydroxide) at 25° C. for 2 minutes, the immersed portion of the coating film is completely dissolved and removed.
- TMAH tetramethylammonium hydroxide
- coating film completely dissolved refers to that when the aqueous TMAH solution after the test is filtered by a membrane filter (pore size 0.1 ⁇ m), a solid form of the coating film is not visually confirmed on the membrane filter.
- cyclic ether group refers to a group obtained by removing one hydrogen atom included in the cyclic ether.
- the one hydrogen atom to be removed may be an atom connected directly to the ring structure of the cyclic ether or may be an atom included in a substituent connected to the ring structure.
- siloxane bond refers to a Si—O—Si bond
- the number of siloxane bonds refers to the number of oxygen atoms that constitute the siloxane bond.
- the number of siloxane bonds is 2.
- chain organic silicon compound refers to an organic silicon compound in which the skeleton having the siloxane bond is chainlike.
- cyclic organic silicon compound refers to an organic silicon compound in which the skeleton having a siloxane unit (D unit) represented by R 1 R 2 SiO 2/2 or a siloxane unit (T unit) represented by R 3 SiO 3/2 constitutes the ring structure.
- cyclic includes “monocyclic”, “polycyclic”, “cross-linked structure”, and “spirocyclic structure”.
- the organic compound (a) As the organic compound (a), a commonly known organic compound can be used as long as the organic compound has an insulation property.
- the organic compound (a) can include a phenolic hydroxy group.
- examples of such an organic compound include polyvinyl phenol (PVP), and poly(2-hydroxyethyl methacrylate).
- PVP polyvinyl phenol
- poly(2-hydroxyethyl methacrylate) Specifically, polyvinyl phenol (436224, manufactured by Sigma-Aldrich Corporation), and poly(2-hydroxyethyl methacrylate) (529265, manufactured by Sigma-Aldrich Corporation) can be used.
- the cyclic ether group included in the first cross-linking agent (b) may be a group that has a ring opened by a cation under a cationic polymerization environment and that is bondable to the organic compound (a).
- Examples of such a group include a 3 to 4-membered oxa cycloalkyl group, or a group having such an oxa cycloalkyl group.
- the oxa cycloalkyl group may include a condensed ring structure.
- Such an oxa cycloalkyl group can be a group having an epoxy ring as a three-membered ring or a group having an oxetanyl ring as a four-membered ring. Since the epoxy ring and the oxetanyl ring have strain in the ring structure, the epoxy ring and the oxetanyl ring have a high reactivity, and the ring is easily opened. Therefore, the epoxy ring and the oxetanyl ring are capable of forming a bond to the organic compound (a).
- Examples of the cyclic ether group included in the first cross-linking agent (b) include: (1) a 3 to 4-membered oxa cycloalkyl group; (2) a group formed by substituting a 3 to 4-membered oxa cycloalkyl group for a hydrogen atom included in one group selected from the group including: a straight-chain, branched, or cyclic alkyl group of 1 to 20 carbon atoms; an alkoxyalkyl group formed by substituting a straight-chain, branched, or cyclic alkoxy group of 1 to 10 carbon atoms for a hydrogen atom included in a straight-chain, branched, or cyclic alkyl group of 1 to 10 carbon atoms; and an aromatic group; and (3) a condensed ring group of a 3 to 4-membered oxa cycloalkyl group and one selected from the group including: a straight-chain, branched, or cyclic alkyl group of 1 to 20 carbon
- the cyclic ether groups may be identical to each other or may be different from each other.
- the cyclic ether groups may be identical to each other or may be different from each other. Further, in the chain organic silicon compound (b-2), the two or more siloxane bonds may be in a straight chain form or may have a branched structure.
- chain organic silicon compound (b-2) can include a compound represented by Formula (B21) below, and a compound (Tris(glycidoxypropyldimethylsiloxy)phenylsilane (SIT8715.6, manufactured by Gelest Inc.) represented by Formula (B22) below.
- the cyclic organic silicon compound (b-3) including a siloxane unit (D unit) represented by R 1 R 2 SiO 2/2 in the molecule, any one of or both of R 1 and R 2 being a cyclic ether group, and having four or more cyclic ether groups bonded to a silicon atom of the D unit in the molecule, the cyclic ether groups may be identical to each other or may be different from each other. Further, in a case where a plurality of D units are included, R 1 s included in the D units may be identical to each other or may be different from each other, and R 2 s included in the D units may be identical to each other or may be different from each other.
- the D units may be bonded to each other to form a monocyclic structure surrounded by a Si—O—Si bond, or may further include a siloxane unit of a T unit that does not have a cyclic ether group to thereby form a cage-shaped structure surrounded by a Si—O—Si bond.
- the cyclic organic silicon compound (b-3) may have a structure in which a silicon atom is not bonded to the other end of an oxygen atom that constitutes a Si—O bond and part of the cage-shaped structure is not surrounded by a Si—O—Si bond.
- the cyclic organic silicon compound (b-4) including a siloxane unit (T unit) represented by R 3 SiO 3/2 in the molecule, R 3 being a cyclic ether group, and having two or more cyclic ether groups in the molecule the cyclic ether groups may be identical to each other or may be different from each other. Further, in a case where a plurality of T units are included, R 3 s included in the T units may be identical to each other or may be different from each other.
- the T units may be bonded to each other to form a cage-shaped structure surrounded by a Si—O—Si bond, or in an unit structure of part of T units, a structure may be formed in which a silicon atom is not bonded to the other end of an oxygen atom that constitutes a Si—O bond and part of the cage-shaped structure is not surrounded by a Si—O—Si bond.
- the cyclic organic silicon compound (b-4) may include a siloxane unit of a D unit.
- a specific example of such a cyclic organic silicon compound (b-4) can include a compound (PSS-Octa[(3-glycidyloxypropyl)dimethylsiloxy]substituted (593869, manufactured by Sigma-Aldrich Corporation)) represented by Formula (B41) below.
- a cyclic organic silicon compound (b-3) or (b-4) in which Si—O bonds are aggregated is preferably used.
- the photocationic polymerization initiator (c) is a compound that initiates the cationic polymerization reaction of a curable composition using the cationic species or Lewis acid generated by the absorption of light (for example, ultraviolet light) energy.
- known photocationic polymerization initiators such as aromatic diazonium salts, aromatic sulfonium salts, aromatic iodonium salts, metallocene compounds, phosphonium salts, and silanol-aluminum complexes, can be used. These compounds may be used alone or in a mixture of two or more.
- a specific example of the photocationic polymerization initiator (c) may include OMPH076 manufactured by Glest Inc., which is an aromatic sulfonium salt.
- a photosensitizer that accelerates the reaction of the photocationic polymerization initiator (c) by absorbing light and transferring the absorbed energy to the photocationic polymerization initiator (c) may be added to the curable composition.
- the curable composition of the present embodiment may further include a second cross-linking agent (d) that is an organic compound having two or more cyclic ether groups.
- a second cross-linking agent (d) that is an organic compound having two or more cyclic ether groups.
- the second cross-linking agent can be a compound having an aromatic ring and is preferably a compound represented by Formula (d1) below.
- R 2 and R 3 are each a cyclic ether group. R 2 and R 3 may be identical to each other or may be different from each other.
- the cyclic ether group represented as R 2 and R 3 can be a group formed by substituting a 3 to 4-membered oxa cycloalkyl group for a hydrogen atom included in one selected from the group including: a straight-chain, branched, or cyclic alkyl group of 1 to 20 carbon atoms; an alkoxyalkyl group formed by substituting a straight-chain, branched, or cyclic alkoxy group of 1 to 10 carbon atoms for a hydrogen atom included in a straight-chain, branched, or cyclic alkyl group of 1 to 10 carbon atoms; and an aromatic group.
- the oxa cycloalkyl group included in the group represented as R 2 and R 3 can be a group having an epoxy ring that is a three-membered ring or a group having an oxetanyl ring that is a four-membered ring. Since the epoxy ring and the oxetanyl ring have strain in the ring structure, the epoxy ring and the oxetanyl ring have a high reactivity, and the ring is easily opened such that a cationic polymerization reaction occurs.
- a specific example of the second cross-linking agent (d) can include a bisphenol A epoxy monomer (RE310S, manufactured by Nippon Kayaku Co., Ltd.) represented by Formula (d2) below.
- RE310S bisphenol A epoxy monomer
- the ratio of the sum of the mass of the first cross-linking agent (b) and the second cross-linking agent (d) to the total sum of the mass of the organic compound (a) having a hydroxy group, the first cross-linking agent (b), and the second cross-linking agent (d) can be 40 mass % to 90 mass %, and the ratio of the mass of the second cross-linking agent (d) to the total sum of (a), (b) and (d) can be 5 mass % to 30 mass %.
- second cross-linking agents (d) are insoluble in an alkaline solution, when such a combination is used, it is possible to add physical properties due to the second cross-linking agent to the insulator in a state where the entire curable composition is soluble in an alkaline solution.
- the curable composition of the present embodiment may be used in combination with various fillers within a range that does not impair the advantages of the present invention.
- the curable composition When the curable composition is used in combination with a filler, the curable composition functions as the binder of the filler, and physical properties due to the filler can be further imparted to an insulator, which will be formed.
- the curable composition as described above is developable by an alkaline solution and is capable of forming an insulator layer. Therefore, it is possible to reduce a manufacturing load.
- FIGS. 1A to 1C a method of manufacturing a laminate according to the present embodiment and a laminate will be described with reference to FIGS. 1A to 1C .
- FIGS. 1A to 1C a method of manufacturing a laminate according to the present embodiment and a laminate.
- FIGS. 1A to 1C are process views showing a method of manufacturing a laminate according to the present embodiment.
- a solution in which the aforementioned curable composition is dissolved in an organic solvent (hereinafter, referred to as “a raw material solution”) is applied over a conductive layer 200 formed on a substrate 100 , and the solvent is removed. Thereby, a coating film 300 is formed.
- Examples of the formation material of the substrate 100 may include: inorganic materials, such as glass, quartz glass, and silicon nitride; and organic materials (resin materials), such as acrylic resins, polycarbonate resins, polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT).
- inorganic materials such as glass, quartz glass, and silicon nitride
- organic materials such as acrylic resins, polycarbonate resins, polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT).
- the conductive layer 200 wirings and electrodes can be exemplified.
- the formation material of the conductive layer 200 may include conductive polymers, metals such as Al, Ag and Au, and alloys. Generally known formation materials can be used in addition to these formation materials.
- the coating film 300 is formed by applying the raw material solution and then removing the solvent.
- the method of applying the raw material solution generally known methods, such as spin coating, dip coating, spray coating, roll coating, brushing, flexographic printing, inkjet printing, and screen printing, may be exemplified.
- organic solvents can be used as the solvent dissolving the curable composition.
- the organic solvent may include: alcohols, such as methanol, ethanol, 1-propanol, and 2-propanol (isopropyl alcohol (IPA)); ethers, such as propylene glycol monomethyl ether acetate (PGMEA); aromatic hydrocarbons, such as toluene and xylene; nitriles such as acetonitrile; esters such as acetic acid ester; ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
- alcohols such as methanol, ethanol, 1-propanol, and 2-propanol (isopropyl alcohol (IPA)
- ethers such as propylene glycol monomethyl ether acetate (PGMEA)
- aromatic hydrocarbons such as toluene and xylene
- nitriles such as ace
- a method of volatilizing the solvent using generally known operations such as heating, air blow and depressurization can be used. These operations may be used in a combination of two or more.
- the film obtained by removing a solvent from the raw material solution is prebaked. Thereby, the non-patterned coating film 300 is formed.
- the prebaking is performed, for example, by heating the film obtained by removing a solvent from the raw material solution at 105° C. for 5 minutes.
- the coating film 300 is irradiated with ultraviolet L (light) through a mask M provided with an opening Ma in a region overlapping the conductive layer 200 in a plan view and having a light shielding portion Mb around the opening Ma, so as to allow the coating film 300 to be exposed to light.
- the ultraviolet L is light having an absorption wavelength of the photocationic polymerization initiator included in the curable composition.
- ultraviolet of i-line ray 365 nm
- a photocationic polymerization reaction proceeds in the coating film 300 , and the latent image of an insulator layer 310 is formed on the coating film 300 .
- a heat treatment may be performed in a temperature range of 100° C. to 120° C. for 10 minutes. This heat treatment may be performed simultaneously with the irradiation of ultraviolet L and may also be performed after the irradiation of ultraviolet L.
- the coating film 300 subjected to mask exposure as shown in FIG. 1B is developed using an alkaline solution as a developer S.
- a developer S for example, 2.38 mass % of an aqueous TMAH solution can be used, and the developing time, for example, may be set to 1 minute.
- the solubility of the exposed region (insulator layer 310 ) of the coating film 300 in the developer S relatively decreases compared to that of the non-exposed region in the coating film 300 , because photocationic polymerization proceeds and the molecular weight increases. Therefore, the non-exposed region of the coating film 300 is dissolved and developed by the developer S, and thereby it is possible to form a laminate 1000 having the insulator layer 310 covering the conductive layer 200 .
- a surface treatment may be applied on at least a region in which the insulator layer 310 will be formed by using a silane coupling agent (first silane coupling agent) having a cyclic ether group.
- a silane coupling agent includes 3-glycidoxypropyl triethoxysilane (KBM-403, manufactured by Shin-Etsu Silicone Co., Ltd.).
- KBM-403 3-glycidoxypropyl triethoxysilane
- the cyclic ether group included in the silane coupling agent reacts and bonds to an organic compound included in the curable composition during a photocationic polymerization reaction. Therefore, an adhesion power between the insulator layer 310 to be formed and the substrate 100 and an adhesion power between the insulator layer 310 to be formed and the conductive layer 200 are enhanced, and it is possible to suppress damage to the laminate 1000 .
- the method of manufacturing a laminate as described above uses a curable composition that is developable by an alkaline solution and is capable of forming an insulator layer. Therefore, it is possible to provide a manufacturing process in which a manufacturing load is reduced.
- the laminate as described above uses a curable composition that is developable by an alkaline solution and is capable of forming an insulator layer. Therefore, even when a resin substrate is used, it is possible to preventing the substrate from being dissolved or swelled.
- the laminate 1000 having a laminated structure manufactured in this way a wiring board, a condenser, and the like, each having a multi-layer interconnect structure, are exemplified.
- FIG. 2 is a schematic cross-sectional view showing a transistor manufactured by the method of manufacturing a transistor according to the present embodiment, and a transistor according to the present embodiment.
- a transistor 1 A is a so-called bottom-contact type transistor.
- the present invention is also applicable to an inorganic transistor using an inorganic semiconductor as the formation material of a semiconductor layer.
- the transistor 1 A includes a substrate 2 , base films 3 and 13 , electroless plating catalysts 5 and 15 , a gate electrode 6 , an insulator layer 7 , a source electrode 16 , a drain electrode 17 , and an organic semiconductor layer (semiconductor layer) 20 .
- the layer of a combination of the insulator layer 7 and the base film 13 refers to “a layer containing an insulator layer”.
- the substrate 2 any of a substrate having optical transparency and a substrate not having optical transparency can be used.
- the substrate 2 can be made of any one of: inorganic materials such as glass, quartz glass, and silicon nitride; and organic polymers (resins), such as acrylic resins, polycarbonate resins, and polyester resins (for example, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and the like).
- inorganic materials such as glass, quartz glass, and silicon nitride
- organic polymers (res) such as acrylic resins, polycarbonate resins, and polyester resins (for example, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and the like).
- the formation material of these substrates 2 does not form a metallic bond together with a metal-made plating film formed as a result of electroless plating. For this reason, in the present embodiment, the formation material of these substrates 2 is treated as a poor plating material on which a plating film is not easily formed directly, and the formed plating film is easily stripped. Due to the similar reason, if the plating film is made of an easily-strippable material, for example, a composite material of the above-mentioned material and the like can also be similarly used as the formation material of the substrate 2 .
- the base film 3 is a gate base film in the present invention.
- the base film 3 is formed over the entire surface of the main side of the substrate 2 , and part of the surface of the base film 3 is selectively provided with a catalyst (electroless plating catalyst) 5 .
- the catalyst 5 is a catalyst for reducing metal ions contained in a plating solution for electroless plating.
- As the catalyst silver, metal palladium, and the like are exemplified. In the present embodiment, metal palladium is used.
- the base film 3 is a film capable of capturing a metal that is the above-mentioned catalyst 5 , and a silane coupling agent (second silane coupling agent) having a group capable of capturing the metal is used as the formation material of the base film 3 .
- the base film 3 is formed by applying a liquid product containing such a silane coupling agent onto the main side of the substrate 2 .
- the “group capable of capturing the metal” refers to a group that can capture the metal (catalyst 5 ) or ions of this metal, for example, by an ion bond or a coordinate bond.
- a group having a nitrogen atom or a sulfur atom is exemplified.
- the group having a nitrogen atom or a sulfur atom may include an amino group, a urea group, a thiol group (or a mercapto group), a thiocarbonyl group, a thiourea group, and a group obtained by removing one or more hydrogen atoms bonded to a heterocyclic compound containing a nitrogen atom or a sulfur atom.
- heterocyclic compound containing a nitrogen atom or a sulfur atom examples include: monocyclic aromatic heterocyclic compounds, such as pyrrole, imidazole, pyridine, pyrimidine, and thiophene; polycyclic aromatic heterocyclic compounds, such as indole and benzothiophene; and non-aromatic heterocyclic compounds in which two or more carbon atoms in an aromatic ring of each of these aromatic compounds are hydrogenated.
- a hydroxyl group and an alkoxy group of 1 to 6 carbon atoms are exemplified.
- the compound that can be used as the formation material of the base film 3 may include N-cyclohexyl-aminopropyltrimethoxysilane, bis(3-(trimethoxysilyl)propyl)ethylenediamine, 1-(3-(trimethoxysilylpropyl))urea, bis(3-trimethoxysilylpropyl))urea, 2,2-dimethoxy-1,6-diaza-2-silacyclooctane, N-(3-(trimethoxysilyl propyl))-4,5-dihydroimidazole, bis(3-(trimethoxysilyl)propyl)thiourea, 3-trimethoxysilylpropanethiol, and polyethyleneimine modified with a trimethoxysilylpropyl group.
- silane coupling agent a silane coupling agent having an amino group as the “group capable of capturing metal” is preferable, and a silane coupling agent, which is a primary amine or a secondary amine (“group capable of capturing metal” is a group represented by —NH 2 or —NH—), is more preferable.
- group capable of capturing metal is a group represented by —NH 2 or —NH—
- base film 3 a base film formed by using a silane coupling agent as a primary amine will be described.
- the gate electrode 6 is a metal electrode formed on the surface of the catalyst 5 , and, as described later, is formed of a metal deposited on the surface of the catalyst 5 by electroless plating.
- As the material of the gate electrode 6 nickel phosphorus (NiP) or copper (Cu) is exemplified.
- the insulator layer 7 electrically insulates the gate electrode 6 having insulating properties from the source electrode 16 and the drain electrode 17 .
- the above-mentioned curable composition in the first embodiment is used as a formation material.
- the base film 13 is formed on the entire upper surface of the insulator layer 7 .
- the base film 13 is a source base film and is a drain base film in the present invention, and the source base film and the drain base film are formed as a continuous film.
- the base film 13 is formed over the entire surface of the main side of the substrate 2 , and part of the surface of the base film 13 is selectively provided with a catalyst (catalyst for electroless catalyst) 15 .
- the formation material of the catalyst 15 may be the same as that of the above-mentioned catalyst 5 .
- the formation material of the base film 13 is the same as that of the above-mentioned base film 3 , but the formation materials of the base film 3 and the base film 13 may be different from each other.
- the base film 13 is formed by using a silane coupling agent as a primary amine which is the same as that used for the base film 3 will be described.
- the base film 13 is formed on the entire upper surface of the insulator layer 7 , but the base film 13 may be selectively formed on only a location where the catalyst 15 is provided.
- a silane coupling agent which is a formation material of the base film 13 , is selectively applied to the upper surface of the insulator layer 7 using a generally known method, and thereby it is possible to selectively form the base film 13 .
- the silane coupling agent may be applied to a region larger than the region forming the base film 13 , and then a film formed at a portion protruding from the region forming the base film 13 may be irradiated with ultraviolet to thereby decompose and remove the silane coupling agent to selectively form the base film 13 .
- the source electrode 16 and the drain electrode 17 are metal electrodes formed on the surface of the catalyst 15 .
- the source electrode 16 has a first electrode 161 and a second electrode 162 covering the surface of the first electrode 161 .
- the drain electrode 17 has a third electrode 171 and a fourth electrode 172 covering the surface of the third electrode 171 .
- the first electrode 161 and the third electrode 171 are formed by electroless plating.
- As the material of each of the first electrode 161 and the third electrode 171 nickel phosphorus (NiP) or copper (Cu) is exemplified. In the present embodiment, it is described that nickel phosphorus (work function: 5.5 eV) is used as the formation material of each of the first electrode 161 and the third electrode 171 .
- the first electrode 161 and the third electrode 171 may each be formed using a different material.
- the second electrode 162 and the fourth electrode 172 are metal plating layers, each being formed over the entire surface of each of the first electrode 161 and the third electrode 171 , the surface not being in contact with the catalyst 15 . That is, the second electrode 162 is provided to cover a lateral side 16 a in the source electrode 16 . The fourth electrode 172 is provided to cover a lateral side 17 a in the drain electrode 17 . The lateral sides 16 a and 17 a (opposing surfaces) face each other.
- each of the second electrode 162 and the fourth electrode 172 As the formation material of each of the second electrode 162 and the fourth electrode 172 , a metal material having a work function in which electron transfer (or hole transfer) is easy in relation to the HOMO/LUMO level of the formation material of a semiconductor layer 20 to be described later is used. In the present embodiment, it is described that gold (work function: 5.4 eV) is used as the formation material of each of the second electrode 162 and the fourth electrode 172 .
- the second electrode 162 and the fourth electrode 172 may each be formed using a different material.
- the semiconductor layer 20 is provided on the surface of the base film 13 between the source electrode 16 and the drain electrode 17 , and is formed in contact with the source electrode 16 and the drain electrode 17 . Specifically, the semiconductor layer 20 is provided in contact with the lateral side 16 a of the source electrode 16 and the lateral side 17 a of the drain electrode 17 , and is in contact with the second electrode 162 and the fourth electrode 172 .
- the semiconductor materials may include: p-type semiconductors, such as copper phthalocyanine (CuPc), pentacene, rubrene, tetracene, and P3HT (poly(3-hexylthiophene-2,5-diyl)); and n-type semiconductors, such as fullerenes such as C 60 and perylene derivatives such as PTCDI-C8H (N,N′-dioctyl-3,4,9,10-perylene tetracarboxylic diimide).
- CuPc copper phthalocyanine
- P3HT poly(3-hexylthiophene-2,5-diyl)
- n-type semiconductors such as fullerenes such as C 60 and perylene derivatives such as PTCDI-C8H (N,N′-dioctyl-3,4,9,10-perylene tetracarboxylic diimide).
- soluble pentacene such as TIPS pentacene (6,13-bis(triisopropylsilylethynyl)pentacene) or an organic semiconductor polymer such as P3HT is soluble in an organic solvent such as toluene and can be used in forming the semiconductor layer 20 by a wet process, which is preferable.
- TIPS pentacene HOMO level: 5.2 eV
- P3HT organic semiconductor polymer
- the formation material of the semiconductor layer 20 is not limited to organic semiconductor materials, and generally known inorganic semiconductor materials can also be used as the formation material of the semiconductor layer 20 .
- the gate electrode 6 , the source electrode 16 , and the drain electrode 17 which are formed by electroless plating, are formed on the base films 3 and 13 (gate base film, source base film, and drain base film), which are formed by using a silane coupling agent as a formation material.
- the base films 3 and 13 gate base film, source base film, and drain base film
- a silane coupling agent as a formation material.
- the distance between the electrodes laminated through an insulator layer is not constant, and there is a possibility that the insulation is damaged and leak current is generated at the position where the distance between the gate electrode and the source electrode or the distance between the gate electrode and the drain electrode becomes closer to each other.
- the base has an uneven shape
- an uneven shape is imparted even to the channel region (represented by AR in FIG. 2 ) of the semiconductor layer overlapping the gate electrode in a plan view, and the migration distance of a carrier in the channel region becomes longer, thereby deteriorating the performance of the transistor 1 A.
- the base films 3 and 13 are formed by using a silane coupling agent as a formation material and a base film containing a filler component capable of roughening the surface of the substrate is not used, these base films become smooth films. Therefore, uneven shapes are not formed by forming the base films 3 and 13 , and the problems caused by the uneven shapes do not occur, and therefore the transistor 1 A becomes a high-performance transistor.
- a liquid product which is obtained, if necessary, by diluting the above-mentioned silane coupling agent with an organic solvent, is applied onto the surface of a substrate 2 to form a coating film 3 A.
- a method of applying the liquid product generally known methods, such as spin coating, dip coating, spray coating, roll coating, brushing, flexographic printing, and screen printing, may be exemplified.
- silane coupling agent 3-aminopropyltriethoxysilane, which is a primary amine, is used as the silane coupling agent.
- organic solvent various organic solvents can be used as long as the solvents are capable of dissolving the silane coupling agent.
- a polar solvent can be preferably used.
- the solvent that can be used may include: alcohols, such as methanol, ethanol, 1-propanol, and 2-propanol (isopropyl alcohol (IPA)); ethers, such as propylene glycol monomethyl ether acetate (PGMEA); aromatic hydrocarbons, such as toluene; nitriles such as acetonitrile; esters such as acetic acid ester; and ketones, such as acetone, methyl ethyl ketone, and methyl isobutyl ketone.
- alcohols such as methanol, ethanol, 1-propanol, and 2-propanol (isopropyl alcohol (IPA)
- ethers such as propylene glycol monomethyl ether acetate (PGMEA)
- aromatic hydrocarbons such as toluene
- the organic solvent is volatilized and removed by a heat treatment to form a base film 3 .
- the base film 3 formed in this manner is a silane coupling agent layer having an extremely thin film thickness, and therefore becomes a transparent film in which light scattering does not easily occur. Therefore, for example, if the transistor manufactured by the method of the present embodiment is provided on a substrate having optical transparency, it is possible to maintain the optical transparency as a combination of the substrate 2 and the base film 3 even when the base film 3 is formed on the entire surface of the substrate 2 , and it is possible to easily form the film.
- a resist material is applied onto the base film 3 , and is then prebaked to thereby form a resist layer 4 A that is not patterned.
- a positive photoresist is used as the resist material.
- the resist layer 4 A is irradiated with ultraviolet L through a mask M 1 including an opening Ma provided at the position corresponding to the region forming a metal electrode and including a light shielding portion Mb provided in the region not forming the metal electrode, so as to expose the resist layer 4 A to light.
- the resist layer irradiated with ultraviolet is developed by a developer that dissolves the resist layer to thereby form a resist layer 4 provided with an opening 4 a.
- a catalyst 5 used in electroless plating is captured on the surface of the base film 3 exposed through the opening 4 a formed in the resist layer 4 .
- a metal which is the catalyst 5
- a general electroless plating process of a resin proceeds in the order of washing, etching, catalyst imparting, and then electroless plating.
- the “catalyst imparting” is a process of attaching a metal such as palladium (Pd), serving as an electroless plating reaction initiator (catalyst), to the surface of the region for carrying out plating.
- the “catalyst imparting” includes a process of bringing a colloidal solution of a divalent palladium salt and a divalent tin (Sn) salt into contact with a substrate to be attached by palladium and then immersing the substrate coated with the colloidal solution into an acid or alkali solution, called an accelerator. Thereby, the divalent palladium is reduced to zero-valent palladium, and the catalyst is activated.
- the silane coupling agent which is a formation material of a base film
- the silane coupling agent which is a formation material of a base film
- the reduction treatment using the above-mentioned accelerator is not required (which will be described later). Therefore, when a primary amine or a secondary amine is used as the silane coupling agent, the operation of electroless plating is simplified.
- the silane coupling agent is a tertiary amine or a silicon compound having another “group capable of capturing a metal”
- a colloidal solution of a divalent palladium salt is applied, and then a normal treatment (activating process) using the above-mentioned accelerator is performed.
- a normal treatment (activating process) using the above-mentioned accelerator is performed.
- an electroless plating solution is brought into contact with the catalyst 5 .
- metal ions dissolved in the electroless plating solution is reduced and deposited on the surface of the catalyst 5 , and a gate electrode 6 containing nickel phosphorus as a formation material is selectively formed in the opening 4 a .
- the silane coupling agent is a primary amine or a secondary amine
- the catalyst 5 is immersed in the electroless plating solution without performing the activation using the accelerator, and thereby the surface of the catalyst 5 is plated. Therefore, it can be indirectly confirmed that metal palladium is captured on the surface of the base film 3 .
- the entire surface of the remaining resist layer is exposed to ultraviolet, and then the resist layer is removed by a generally known developer. In this way, the gate electrode 6 is formed.
- a solution (raw material solution), in which the curable composition of the first embodiment is dissolved in an organic solvent, is applied to the surface of the base film 3 to cover the gate electrode 6 .
- the application method the above-mentioned method can be used.
- the viscosity of the entire raw material solution can be adjusted, and the thickness of the coating film 7 A of the raw material solution can be controlled.
- the photoresist is thickly applied such that the thickness of the coating film 7 A is about several hundreds of nanometers.
- the thickness of the coating film 7 A is not limited thereto.
- the coating film 7 A is irradiated with ultraviolet L through a mask M 2 provided with an opening corresponding to the region forming an insulator layer 7 to cure the curable composition, thereby forming the insulator layer 7 .
- a heat treatment can be performed simultaneously with the ultraviolet irradiation or after the ultraviolet irradiation.
- the coating film 7 A is developed by an alkaline solution (developer S) that dissolves the coating film 7 A to thereby remove the uncured coating film and form an insulator layer 7 that is patterned.
- developer S an alkaline solution
- the silane coupling agent may be applied to cover the surface including the gate electrode 6 before the application of the raw material solution.
- a liquid product which is obtained, if necessary, by diluting the above-mentioned silane coupling agent with an organic solvent, is applied onto the entire upper surface of the insulator layer 7 , and then a heat treatment is performed to volatilize and remove the organic solvent, so as to form a base film 13 .
- the silane coupling agent and the organic solvent may be the same as those used in the formation of the base film 3 described above.
- a resist material is applied over the insulator layer 7 and the base film 13 and is then prebaked. Thereby, a resist layer 14 A that is not patterned is formed.
- a positive photoresist is used as the resist material.
- the resist layer 14 A is irradiated with ultraviolet L through a mask M 3 provided with an opening corresponding to the region forming a source electrode and a drain electrode, so as to expose the resist layer 14 A to light.
- the resist layer irradiated with ultraviolet is developed by a developer that dissolves the resist layer to thereby form a resist layer 14 provided with an opening 14 a.
- a colloidal solution of a divalent palladium salt is made to come into contact with the base film 13 exposed through the opening 14 a .
- the catalyst 15 used in electroless plating is captured to the surface of the base film 13 .
- an electroless plating solution is made to come into contact with the catalyst 15 .
- metal ions dissolved in the electroless plating solution are reduced and deposited on the surface of the catalyst 15 , and a first electrode 161 and a third electrode 171 made of nickel phosphorus are selectively formed in the opening 14 a.
- the entire surface of the remaining resist layer is exposed to ultraviolet, and then the resist layer is removed by a generally known developer. In this way, the first electrode 161 and the third electrode 171 are formed.
- the entire body is immersed into a gold plating bath for substitution to allow the surface of the first electrode 161 and the third electrode 171 to be substituted and deposited with gold, and is further immersed into a gold plating bath for reduction to thereby form a second electrode 162 and a fourth electrode 172 , which are plated with gold, on the surface of the first electrode 161 and the third electrode 171 .
- a source electrode 16 and a drain electrode 17 are formed.
- a surface treatment may be applied on at least a region in which the insulator layer 7 will be formed by using a silane coupling agent having a cyclic ether group.
- a specific example of such a silane coupling agent includes 3-glycidoxypropyl triethoxysilane (KBM-403, manufactured by Shin-Etsu Silicone Co., Ltd.).
- KBM-403 3-glycidoxypropyl triethoxysilane
- the cyclic ether group included in the silane coupling agent reacts and bonds to an organic compound included in the curable composition during a photocationic polymerization reaction. Therefore, an adhesion power between the insulator layer 7 to be formed and the substrate 2 (base film 3 ) and an adhesion power between the insulator layer 7 to be formed and the gate electrode 6 are enhanced, and it is possible to suppress damage to the transistor 1 A.
- a curable composition that is developable by an alkaline solution and is capable of forming an insulator layer is used. Therefore, it is possible to provide a manufacturing process in which a manufacturing load is reduced.
- the insulator layer 7 is formed by using a curable composition that is developable by an alkaline solution. Therefore, even when a resin substrate is used, it is possible to prevent the substrate from being dissolved or swelled by a developer, and it is possible to form a transistor with reduced degradation during manufacturing.
- the base films 3 and 13 are formed by using a silane coupling agent as a formation material and are smooth films, problems caused by the uneven shapes of the base films do not occur, and a high-performance transistor can be obtained.
- the second electrode 162 and the fourth electrode 172 can be surely formed even on the lateral side 16 a of the source electrode 16 and the lateral side 17 a of the drain electrode 17 . Therefore, in the manufactured transistor 1 A, electric current easily flows between the semiconductor layer 20 and the source electrode 16 (or between the semiconductor layer 20 and the drain electrode 17 ) at the time of driving, and the transistor 1 A can be well driven.
- first electrode 161 is covered with the second electrode 162
- third electrode 171 is covered with the fourth electrode 172 .
- FIGS. 4A and 4B are schematic views showing the drive status of a transistor.
- FIG. 4A is a view showing a transistor 1 x which has the same configuration as the transistor 1 A except that the transistor 1 x does not have the second electrode.
- FIG. 4B is a view showing the transistor 1 A manufactured by the method of the present embodiment.
- the phrase “energy level of molecular orbital used in electron transfer in the formation material of an organic semiconductor layer” refers to the energy level of HOMO in the case where the organic semiconductor layer is made of a p-type semiconductor, and refers to the energy level of LUMO in the case where the organic semiconductor layer is made of an n-type semiconductor.
- the transistor 1 x shown in FIG. 4A when the transistor 1 x has a configuration which does not include the second electrode, since the gap (energy level difference) between the energy level of HOMO of the semiconductor layer 20 and the work function of the first electrode 161 becomes large, Schottky barrier occurs, and electric current hardly flows. Therefore, for example, as shown by an arrow A in FIG. 4A , it is easy to form the flow of electric current through the highly-resistant semiconductor layer 20 , and it is difficult to secure a good conduction.
- a channel region AR having a thickness of several nanometers (nm) is formed in the semiconductor layer 20 around the interface between the semiconductor layer 20 and the base film 13 , enabling the conduction between the source electrode 16 and the drain electrode (not shown).
- the surface of the source electrode 16 is provided with the second electrode 162 , which is formed using a metal material having a work function (energy level difference with HOMO of the semiconductor layer 20 is small) at which electron transfer is easier between the second electrode 162 and the formation material of the semiconductor layer 20 compared to between the second electrode 162 and the first electrode 161 , and the Shottky barrier is reduced, so that electric current easily flows into the channel region AR through the first electrode 161 and the second electrode 162 .
- FIG. 4B shows the flow of electric current using an arrow B. Therefore, it is possible to realize a high-performance transistor 1 A.
- FIG. 5 is a schematic cross-sectional view of a transistor 1 B, which is manufactured by the manufacturing method of a transistor according to a third embodiment of the present invention.
- the transistor 1 B of the present embodiment is partially in common with the transistor 1 A of the second embodiment.
- the difference between the transistor 1 A and the transistor 1 B is that the transistor of the second embodiment is a bottom contact transistor, and the transistor 1 B of the present embodiment is a top contact transistor. Accordingly, in the present embodiment, the same reference numerals for the components in common with the second embodiment are used, and detailed description of the components will be omitted.
- the transistor 1 B includes a semiconductor layer 20 disposed on an insulator layer 7 and having a surface on which a source electrode 16 and a drain electrode 17 are formed.
- a semiconductor layer 20 is formed on the entire upper surface of an insulator layer 7
- a base film 13 is formed on the entire upper surface of the semiconductor layer 20 .
- the layer of a combination of the insulator layer 7 , the semiconductor layer 20 , and the base film 13 refers to a “layer containing an insulator layer”.
- a catalyst 15 is selectively provided on the upper surface of the base film 13 , and a source electrode 16 including a first electrode 161 and a second electrode 162 , and a drain electrode 17 including a third electrode 171 and a fourth electrode 172 are formed on the upper surface.
- a source electrode 16 including a first electrode 161 and a second electrode 162 and a drain electrode 17 including a third electrode 171 and a fourth electrode 172 are formed on the upper surface.
- the region located in the vicinity of the upper surface of the semiconductor layer and sandwiched between the source electrode 16 and the drain electrode 17 becomes a channel region AR.
- a base film 3 , a catalyst 5 , a gate electrode 6 , and an insulator layer 7 are laminated on the upper surface of a substrate 2 .
- a solution S 1 in which an organic semiconductor soluble in an organic solvent is dissolved in the organic solvent is applied onto the insulator layer 7 , and then dried to thereby form the semiconductor layer 20 .
- a liquid product which is obtained, if necessary, by diluting the above-mentioned silane coupling agent with an organic solvent, is applied onto the entire upper surface of the semiconductor layer 20 , and then is heat-treated to volatilize and remove the organic solvent, thereby forming a base film 13 .
- a resist material is applied over the insulator layer 7 , the semiconductor layer 20 , and the base film 13 , and is then prebaked to thereby form a resist layer 14 A that is not patterned. Thereafter, the resist layer 14 A is irradiated with ultraviolet L through a mask M 3 provided with an opening corresponding to the region forming a source electrode and a drain electrode, so as to expose the resist layer 14 A to light.
- the resist layer irradiated with ultraviolet is developed by a developer dissolving the resist layer to thereby form a resist layer 14 provided with an opening 14 a.
- a colloidal solution of a divalent palladium salt is made to come into contact with the base film 13 exposed through the opening 14 a , thereby capturing the catalyst 15 used in electroless plating to the surface of the base film 13 .
- an electroless plating solution is made to come into contact with the catalyst 15 .
- metal ions dissolved in the electroless plating solution is reduced and deposited on the surface of the catalyst 15 , and a first electrode 161 and a third electrode 171 made of nickel phosphorus are formed selectively in the opening 14 a (first electroless plating).
- the entire surface of the remaining resist layer is exposed to ultraviolet, and then the resist layer is removed by a generally known developer. In this way, the first electrode 161 and the third electrode 171 are formed.
- the entire body is immersed into a gold plating bath for substitution to allow the surface of the first electrode 161 and the third electrode 171 to be substituted and deposited with gold, and is further immersed into a gold plating bath for reduction to thereby form a second electrode 162 and a fourth electrode 172 , which are plated with gold, on the surface of the first electrode 161 and the third electrode 171 (second electroless plating).
- a source electrode 16 and a drain electrode 17 are formed.
- the insulator layer 7 is formed by using a curable composition that is developable by an alkaline solution. Therefore, even when a resin substrate is used, it is possible to prevent the substrate from being dissolved or swelled by a developer, and it is possible to form a transistor with reduced degradation during manufacturing.
- the base films 3 and 13 are formed by using a silane coupling agent as a formation material, and are smooth films. Therefore, problems caused by the uneven shapes of the base films do not occur, and it is possible to easily manufacture a high-performance transistor.
- the second electrode 162 is formed using a metal material having a work function (energy level difference with HOMO of the semiconductor layer 20 is small) at which electron transfer is easier between the formation material of the semiconductor layer 20 and the second electrode 162 compared to between the first electrode 161 and the second electrode 162 .
- the fourth electrode 172 is formed using a metal material having a work function (energy level difference with HOMO of the semiconductor layer 20 is small) at which electron transfer is easier between the formation material of the semiconductor layer 20 and the fourth electrode 172 compared to between the third electrode 171 and the fourth electrode 172 .
- a reference numeral a electric current easily flows into the channel region AR from the second electrode 162 and the fourth electrode 172 , and therefore it is possible to realize a high-performance transistor 1 B.
- the first electrode 161 is covered with the second electrode 162 and the third electrode 171 is covered with the fourth electrode 172 , the temporal corrosion of the first electrode 161 and the third electrode 171 is suppressed, and there is also an advantage in that the performance of the transistor can be stably maintained.
- the transistor of the present embodiment is configured such that the semiconductor layer 20 is not in contact directly with the source electrode 16 and the drain electrode 17 but is in contact with the source electrode 16 and the drain electrode 17 through the base film 13 , but the base film 13 is formed in a very thin layer having a thickness of several nanometers (nm). Therefore, the effect of the base film 13 influencing transistor characteristics is small, and electric current flows well between the semiconductor layer 20 and the source electrode 16 and between the semiconductor layer 20 and the drain electrode 17 .
- a substrate can be made of a non-metallic material.
- a plurality of plating members in each of which a base film is formed on a PET substrate (non-metallic substrate) are prepared.
- the plating members are conveyed, and simultaneously a transistor is manufactured using the above-mentioned manufacturing method in the conveying process. Thereby, it is possible to form a high-performance transistor on the PET substrate.
- a roll to roll process in which a plating member in which a base film is formed on a long PET film having flexibility, as a substrate, is rolled, the rolled plating member is conveyed while unrolling, transistors are continuously manufactured using the above-mentioned manufacturing method, and then the manufactured transistors are rolled, it is possible to form a transistor on the PET film.
- a base film is formed using a silane coupling agent as a formation material, a catalyst for electroless plating is captured on the base film, and then electroless plating is performed, so as to form a gate electrode, a source electrode and a drain electrode.
- these electrodes may also be formed by forming any one or two electrodes of these electrodes using the above-mentioned method and forming the remaining electrodes using another method.
- the gate electrode may be formed using a generally known patterning method, and the source electrode and drain electrode, which are formed in the same layer, may be formed using the above-mentioned manufacturing method.
- Example 1 a solution of the following combination was used for a raw material solution in which a curable composition is dissolved.
- first cross-linking agent 5 mass % of (Tris(glycidoxypropyldimethylsiloxy)phenylsilane (SIT8715.6, manufactured by Gelest Inc.)
- photocationic polymerization initiator 0.5 mass % of (thiophenoxyphenyl)diphenylsulfonium hexafluorophosphate-bis(diphenylsulfonium)diphenylthioether hexafluorophosphate blend, 50% in propylene carbonate (OMPH076, manufactured by Gelest Inc.)
- Raw material solution 2 was prepared in the same manner as raw material solution 1, except that PSS-Octa[(3-glycidyloxypropyl)dimethylsiloxy]substituted (593869, manufactured by Sigma-Aldrich Corporation) was used as the first cross-linking agent (b).
- Raw material solution 3 was prepared in the same manner as raw material solution 1, except that tetraphenylol ethane glycidyl ether (412961, manufactured by Sigma-Aldrich Corporation) represented by Formula (100) below was used as the first cross-linking agent (b).
- Raw material solution 4 was prepared in the same manner as raw material solution 1, except that poly(2-hydroxyethyl methacrylate) (529265, manufactured by Sigma-Aldrich Corporation) was used as the organic compound (a) having a hydroxy group.
- poly(2-hydroxyethyl methacrylate) 529265, manufactured by Sigma-Aldrich Corporation
- the raw material solution was applied on a PET substrate (Model number: A-4100 (no coat), manufactured by Toyobo Co., Ltd.) by spin coating (1500 rpm ⁇ 30 seconds). Then, the substrate was heated at 105° C. for 5 minutes to volatilize cyclohexanone as a solvent to form a coating film of a curable composition on the PET substrate.
- FIG. 7 shows optical microscope images of insulator layers after the development.
- FIG. 7( a ) shows a result when raw material solution 1 was used.
- FIG. 7( b ) shows a result when raw material solution 2 was used.
- FIG. 7( c ) shows a result when raw material solution 3 was used.
- FIG. 7( d ) shows a result when raw material solution 4 was used.
- FIGS. 8A to 8C are views showing a process of manufacturing the sandwich cell evaluated in Example 2.
- an insulator layer and a base film were laminated (refer to FIG. 8B ) on a silicon substrate (n-type abrasive product, ⁇ 0.003 ⁇ cm, manufactured by Nakayama Semiconductor Co., Ltd.) (refer to FIG. 8A ) by the following method.
- raw material solution 2 of Example 1 described above was applied onto the silicon substrate by spin coating (1000 rpm ⁇ 30 seconds). Then, the substrate was heated at 105° C. for 5 minutes to volatilize cyclohexanone (solvent), and a coating film of a curable composition was formed on the silicon substrate.
- the coating film was irradiated with i-line ray (365 nm) at an irradiation intensity of 700 mJ/cm 2 through a photomask, was further heated (post-baked) at 120° C. for 10 minutes, and then immersed in 2.38 mass % of an aqueous TMAH solution for 1 minute to be developed, so as to form an insulator layer.
- silane coupling agent which is a formation material of a base film for electroless plating
- a silane coupling agent which is a formation material of a base film for electroless plating
- silane coupling agent 3-aminopropyltriethoxysilane having a primary amino group (KBE-903, manufactured by Shin-Etsu Silicone Co., Ltd.) was used.
- the silane coupling agent was dissolved in methyl isobutyl ketone to have a content of 0.2 mass % to obtain a liquid product, and then the liquid product was applied onto the substrate by spin coating (4000 rpm ⁇ 30 seconds). Thereafter, the substrate coated with the liquid product was heated at 120° C. for 5 minutes to volatilize methyl isobutyl ketone (solvent), so as to form a base film.
- HMDS hexamethyldisiloxane
- an upper electrode was formed on the base film, and a sandwich cell was fabricated.
- a photoresist (SUMIRESIST PFI-34A, manufactured by Sumitomo Chemical Co., Ltd.) was applied to the surface of the base film coated with HMDS by spin coating (1000 rpm ⁇ 30 seconds), and heated at 90° C. for 5 minutes, so as to form a resist layer.
- the resist layer was irradiated with light emitted from a low-pressure mercury lamp through a quartz photomask for 5 minutes, heated (post-baked) at 110° C. for 5 minutes, and then immersed into 2.38 mass % of an aqueous TMAH solution for 90 seconds to thereby develop the resist layer, so as to form an opening in the resist layer.
- the substrate provided with the resist layer having the opening was washed with water at room temperature for 30 seconds, and then immersed into a catalyst colloid solution for electroless plating (Melplate activator 7331, manufactured by Meltex Corporation) at room temperature for 60 seconds, so as to adhere a catalyst to the base film exposed through the opening of the resist layer.
- a catalyst colloid solution for electroless plating (Melplate activator 7331, manufactured by Meltex Corporation) at room temperature for 60 seconds, so as to adhere a catalyst to the base film exposed through the opening of the resist layer.
- the surface of the base film was washed with water, and then immersed into an electroless plating solution (Melplate NI-867, manufactured by Meltex Corporation) at 70° C. for 180 seconds to deposit nickel phosphorus on the catalyst adhered to the opening of the resist layer, so as to perform nickel-phosphorus plating.
- an electroless plating solution (Melplate NI-867, manufactured by Meltex Corporation) at 70° C. for 180 seconds to deposit nickel phosphorus on the catalyst adhered to the opening of the resist layer, so as to perform nickel-phosphorus plating.
- NiP electrode nickel-phosphorus plated portion
- the surface of the upper electrode was water-washed and then dried. Then, the entire surface including the remaining resist layer was irradiated with i-line ray at an irradiation intensity of 300 mJ/cm 2 , and then immersed into 2.38 mass % of an aqueous TMAH solution to remove the resist layer. The resulting product was water-washed and dried to thereby fabricate a sandwich cell.
- the dielectric constant and insulation characteristics of the insulator layer were measured using the fabricated sandwich cell by the following method.
- the measurement of capacitance of the fabricated insulator layer was performed in a frequency range of 100 Hz to 1 MHz using an LCR meter (4284A, manufactured by Agilent Technologies).
- FIG. 9 is a graph showing the frequency dependency of dielectric constant calculated from capacitance of the insulator layer of the fabricated sandwich cell.
- the horizontal axis indicates the measurement frequency (unit: Hz), and the vertical axis indicates the measured dielectric constant.
- FIG. 10 is a graph showing the evaluation result of insulating characteristics of the insulator layer of the fabricated sandwich cell.
- the horizontal axis indicates the measurement voltage (unit: MV/cm)
- the vertical axis indicates the measured current density (A/cm 2 ).
- Example 3 3-aminopropyltriethoxysilane (KBE903, manufactured by Shin-Etsu Silicone Co., Ltd.), which is an amine-based silane coupling agent, was dissolved in methyl isobutyl ketone (hereinafter, sometimes referred to as MIBK) to have 0.2 mass % to prepare a liquid product, and this liquid product was used in forming a base film.
- MIBK methyl isobutyl ketone
- the surface of a PET substrate (Model number: A-4100 (no coat), manufactured by Toyobo Co., Ltd.) was cleaned with atmospheric-pressure oxygen plasma, and then the above liquid product was applied onto the PET substrate by spin coating (4000 rpm ⁇ 30 seconds). Thereafter, the PET substrate coated with the liquid product was heated at 120° C. for 10 minutes, so as to form a base film.
- a resist material (SUMIRESIST PFI-34A6, manufactured by Sumitomo Chemical Co., Ltd.) was applied to the surface of the substrate provided with the base film by spin coating, and then heated (prebaked) at 90° C. for 5 minutes, so as to form a resist layer.
- the spin coating was performed under a condition of 1000 rpm and 30 seconds, and a resist layer having a thickness of about 1 ⁇ m was formed.
- the resist layer was exposed with ultraviolet having an intensity of 25 mW/cm 2 through a photomask for 5 seconds, heated (post-baked) at 110° C. for 5 minutes, and then immersed into 2.38 mass % of an aqueous TMAH solution for 2 minutes to thereby develop a mask pattern on the resist layer, so as to form an opening.
- the substrate provided with the resist layer having the opening was ultrasonically water-washed at room temperature for 30 seconds, and then immersed into a catalyst colloid solution for electroless plating (Melplate activator 7331, manufactured by Meltex Corporation) at room temperature for 60 seconds, so as to adhere a catalyst (Pd metal) to the base film exposed through the opening of the resist layer.
- a catalyst colloid solution for electroless plating (Melplate activator 7331, manufactured by Meltex Corporation) at room temperature for 60 seconds, so as to adhere a catalyst (Pd metal) to the base film exposed through the opening of the resist layer.
- the surface of the base film was washed with water, and then immersed into an electroless plating solution (Melplate NI-867, manufactured by Meltex Corporation) at 73° C. for 60 seconds to deposit nickel phosphorus on the catalyst adhered to the opening of the resist layer, so as to perform nickel-phosphorus plating.
- an electroless plating solution (Melplate NI-867, manufactured by Meltex Corporation) at 73° C. for 60 seconds to deposit nickel phosphorus on the catalyst adhered to the opening of the resist layer, so as to perform nickel-phosphorus plating.
- the surface of the resulting product was water-washed and then dried. Then, the entire surface including the remaining resist layer was exposed to ultraviolet having an intensity of 25 mW/cm 2 for 1 minute, and then immersed into ethanol for 1 minute to thereby remove the resist layer, so as to fabricate a gate electrode.
- FIG. 11 shows photographs of the gate electrode.
- FIG. 11 ( a ) is an overall photograph of the substrate provided with the gate electrode.
- FIG. 11 ( b ) is an enlarged photograph of the gate electrode using an optical microscope. From FIG. 11 , it is found that a slightly uneven flat gate electrode is formed.
- the substrate provided with the gate electrode was immersed into an aqueous NaOH solution of 50 g/L, and a degreasing process of the surface was performed.
- an aqueous solution of a silane coupling agent (3-glycidoxypropyl triethoxysilane, KBM-403, manufactured by Shin-Etsu Silicone Co., Ltd.) was applied to the whole surface, on which the gate electrode was formed, of the PET substrate by spin coating, and the substrate was heated at 120° C. for 10 minutes. Thereafter, the raw material solution 2 of Example 1 was applied onto the surface by spin coating (1000 rpm ⁇ 30 seconds). Then, the resulting product was heated at 105° C. for 5 minutes to volatilize cyclohexanone (solvent), so as to form a coating film of a curable composition.
- a silane coupling agent 3-glycidoxypropyl triethoxysilane, KBM-403, manufactured by Shin-Etsu Silicone Co., Ltd.
- the coating film was irradiated with ultraviolet for 25 seconds through a mask having an opening in the portion forming an insulator layer.
- the ultraviolet-irradiated coating film was heated at 120° C. for 10 minutes, and then immersed into 2.38 mass % of an aqueous TMAH solution for 1 minute to form a patterned film. Then, the patterned film was heat-treated at 120° C. for 30 minutes to form an insulator layer.
- FIG. 12 is a photograph of the insulator layer.
- FIG. 12 ( a ) is an overall photograph of the substrate provided with the insulator layer.
- FIG. 12 ( b ) is an enlarged photograph of the insulator layer of the region surrounded by the dash line of FIG. 12 ( a ).
- the insulator layer was formed without unevenness and a slightly uneven flat insulator layer was formed by development with an alkaline solution.
- the fabrication and electroless plating of the base film and the resist layer were performed on the entire surface of the side where the insulator layer was formed on the PET substrate in the same manner as the above-mentioned process (fabrication of the gate electrode), so as to form a patterned NiP electrode on the insulator layer.
- the NiP electrode corresponds to the first electrode and the third electrode described in the embodiment.
- the NiP electrode was immersed into a gold plating bath for substitution for 1 minute and further immersed into a plating bath for reduction for 3 minutes to thereby perform electroless gold plating to coat the surface of the NiP electrode with gold, so as to fabricate a source electrode and a drain electrode.
- the gold film coating the surface of the NiP electrode corresponds to the second electrode and the fourth electrode described in the embodiment.
- FIG. 13 shows the photographs of the source electrode and the drain electrode.
- FIG. 13 ( a ) is an overall photograph of the substrate provided with the source electrode and the drain electrode.
- FIG. 13 ( b ) is an enlarged photograph of the source electrode and the drain electrode.
- TIPS pentacene 6,13-bis(triisopropylsilylethynyl)pentacene (716006, manufactured by Sigma-Aldrich, Inc.) was dropped between the source electrode and the drain electrode under a nitrogen atmosphere, and naturally dried to thereby form a semiconductor layer, so as to fabricate a transistor.
- TIPS pentacene 6,13-bis(triisopropylsilylethynyl)pentacene
- FIG. 14 shows an enlarged photograph of the source electrode and the drain electrode having the surface provided with the organic semiconductor layer. It was observed that crystals of TIPS pentacene were formed between the source electrode and the drain electrode.
- the transistor characteristics of the fabricated transistor were evaluated using the Semiconductor Characterization System (4200-SCS, manufactured by KEITHLEY Co., Ltd.).
- FIG. 15 shows a graph showing the transistor characteristics of the transistor fabricated by a wet process using the above-mentioned method.
- the horizontal axis indicates a voltage applied between the source electrode and the drain electrode
- the vertical axis indicates a current value detected by the drain electrode.
- One of the plurality of results shown in FIG. 15 corresponds to each of the gate voltages applied to a gate electrode.
- a gate voltage of 0 V to ⁇ 40 V was applied to the gate electrode of the obtained organic thin film transistor, and a voltage of 0 V to ⁇ 50 V was applied between source and drain to flow electric current.
- a voltage of 0 V to ⁇ 50 V was applied between source and drain to flow electric current.
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Abstract
A composition includes the following (a) to (c).
-
- (a) an organic compound having a hydroxy group;
- (b) a first cross-linking agent that is at least one organic silicon compound selected from the group including
- (b-1) an organic silicon compound including a siloxane bond in the molecule and having three or more cyclic ether groups in the molecule,
- (b-2) a chain organic silicon compound including two or more siloxane bonds in the molecule and having two or more cyclic ether groups in the molecule,
- (b-3) a cyclic organic silicon compound including D unit in the molecule and having four or more cyclic ether groups bonded to a silicon atom of the D unit in the molecule, and
- (b-4) a cyclic organic silicon compound including a T unit in the molecule and having two or more cyclic ether groups in the molecule; and
- (c) a photocationic polymerization initiator.
Description
- This is a Continuation Application of International Application No. PCT/JP2014/050058, filed on Jan. 7, 2014, which claims priority on Japanese Patent Application No. 2013-000631, filed on Jan. 7, 2013. The contents of the aforementioned applications are incorporated herein by reference.
- 1. Field of the Invention
- The present invention relates to a composition, a laminate, a method of manufacturing a laminate, a transistor, and a method of manufacturing a transistor.
- 2. Background
- In the related art, a laminate of a conductive layer and an insulator layer has been used in various electronic circuits.
- The laminate having such a laminated structure is used, for example, to achieve the miniaturization and high integration of electronic circuits. Specifically, this laminate is used for a printed circuit board, a condenser, a transistor, and the like, each having a multilayer wiring structure.
- When forming the above laminate, wirings (conductive layers) to be laminated are insulated from each other by an insulator layer. As the insulator layer, any of an inorganic insulator and an organic insulator may be used (for example, refer to U.S. Pat. No. 5,946,551 and U.S. Pat. No. 6,232,157). Among these, the laminate using an organic insulator is advantageous, compared to a laminate using a conventional insulator layer using SiO2 as a formation material, in that an insulator layer can be formed in a liquid phase and in that a laminated structure can be formed at a lower temperature without requiring a vacuum process.
- In the laminate in which an organic insulator is used in an insulator layer, there is proposed a technology of patterning an insulator layer through a photoresist-free simple method by the combination of polyvinyl phenol (PVP) and an epoxy group-containing compound with a photopolymerization initiator (for example, refer to Japanese Unexamined Patent Application, First Publication No. 2006-28497).
- However, when a laminate is formed using a resin substrate, a developer used for patterning an insulator layer may dissolve or swell the resin substrate. When an alkaline solution is used as a developer, it is known that it is possible to prevent the resin substrate from being dissolved or swelled, but a material in use for an insulator layer developable by an alkaline solution has been limited.
- An object of an aspect of the present invention is to provide a composition developable by an alkaline solution and capable of forming an insulator layer.
- Another object of an aspect of the present invention is to provide a method of manufacturing a laminate using the composition, a manufactured laminate, a method of manufacturing a transistor, and a manufactured transistor.
- A composition according to an aspect of the present invention includes:
- (a) an organic compound having a hydroxy group;
- (b) a first cross-linking agent that is at least one organic silicon compound selected from the group including
-
- (b-1) an organic silicon compound including a siloxane bond in the molecule and having three or more cyclic ether groups in the molecule,
- (b-2) a chain organic silicon compound including two or more siloxane bonds in the molecule and having two or more cyclic ether groups in the molecule,
- (b-3) a cyclic organic silicon compound including a siloxane unit (D unit) represented by R1R2SiO2/2 in the molecule, any one of or both of R1 and R2 being a cyclic ether group, and having four or more cyclic ether groups bonded to a silicon atom of the D unit in the molecule, and
- (b-4) a cyclic organic silicon compound including a siloxane unit (T unit) represented by R3SiO3/2 in the molecule, R3 being a cyclic ether group, and having two or more cyclic ether groups in the molecule; and
- (c) a photocationic polymerization initiator.
- A method of manufacturing a laminate according to another aspect of the present invention includes: applying a solution containing the above-described composition over a conductive layer to form a coating film; selectively irradiating the coating film with light including light having an absorption wavelength of the photocationic polymerization initiator included in the coating film to form a latent image in the light-irradiated region of the coating film; and developing the coating film with an alkaline solution to form an insulator layer.
- A laminate according to another aspect of the present invention includes: a conductive layer; and an insulator layer formed by cationic-polymerization of the above-described composition.
- A method of manufacturing a transistor according to another aspect of the present invention includes: forming a gate electrode on a substrate; applying a solution including the above-described composition over the gate electrode to form a coating film; selectively irradiating the coating film with light including light having an absorption wavelength of a photocationic polymerization initiator included in the coating film to form a latent image in the light-irradiated region of the coating film; developing the coating film with an alkaline solution to form an insulator layer; and forming a source electrode and a drain electrode on the surface of a layer including the insulator layer.
- A transistor according to another aspect of the present invention includes: a source electrode and a drain electrode; a gate electrode provided corresponding to a channel between the source electrode and the drain electrode; a semiconductor layer provided in contact with the source electrode and the drain electrode; and an insulator layer disposed between the source electrode and the gate electrode and between the drain electrode and the gate electrode, wherein the insulator layer is formed by cationic polymerization of the above-described composition.
- According to an aspect of the present invention, it is possible to provide a composition developable by an alkaline solution and capable of forming an insulator layer. According to another aspect of the present invention, it is possible to provide a method of manufacturing a laminate using the composition, a manufactured laminate, a method of manufacturing a transistor, and a manufactured transistor.
-
FIG. 1A is a process view showing a method of manufacturing a laminate according to a first embodiment. -
FIG. 1B is a process view showing the method of manufacturing a laminate according to the first embodiment. -
FIG. 1C is a process view showing the method of manufacturing a laminate according to the first embodiment. -
FIG. 2 is a schematic cross-sectional view showing a transistor of a second embodiment. -
FIG. 3A is a process view showing a manufacturing method of the second embodiment. -
FIG. 3B is a process view showing the manufacturing method of the second embodiment. -
FIG. 3C is a process view showing the manufacturing method of the second embodiment. -
FIG. 3D is a process view showing the manufacturing method of the second embodiment. -
FIG. 3E is a process view showing the manufacturing method of the second embodiment. -
FIG. 3F is a process view showing the manufacturing method of the second embodiment. -
FIG. 3G is a process view showing the manufacturing method of the second embodiment. -
FIG. 3H is a process view showing the manufacturing method of the second embodiment. -
FIG. 3I is a process view showing the manufacturing method of the second embodiment. -
FIG. 3J is a process view showing the manufacturing method of the second embodiment. -
FIG. 3K is a process view showing the manufacturing method of the second embodiment. -
FIG. 3L is a process view showing the manufacturing method of the second embodiment. -
FIG. 3M is a process view showing the manufacturing method of the second embodiment. -
FIG. 3N is a process view showing the manufacturing method of the second embodiment. -
FIG. 3O is a process view showing the manufacturing method of the second embodiment. -
FIG. 3P is a process view showing the manufacturing method of the second embodiment. -
FIG. 3Q is a process view showing the manufacturing method of the second embodiment. -
FIG. 4A is a view showing a drive status of the transistor of the second embodiment. -
FIG. 4B is a view showing a drive status of the transistor of the second embodiment. -
FIG. 5 is a schematic cross-sectional view of a transistor of a third embodiment. -
FIG. 6A is a process view showing a manufacturing method of the third embodiment. -
FIG. 6B is a process view showing the manufacturing method of the third embodiment. -
FIG. 6C is a process view showing the manufacturing method of the third embodiment. -
FIG. 6D is a process view showing the manufacturing method of the third embodiment. -
FIG. 6E is a process view showing the manufacturing method of the third embodiment. -
FIG. 6F is a process view showing the manufacturing method of the third embodiment. -
FIG. 6G is a process view showing the manufacturing method of the third embodiment. -
FIG. 7 shows photographs showing the results of Example 1. -
FIG. 8A is a view showing a manufacturing process of a sandwich cell evaluated in Example 2. -
FIG. 8B is a view showing the manufacturing process of the sandwich cell evaluated in Example 2. -
FIG. 8C is a view showing the manufacturing process of the sandwich cell evaluated in Example 2. -
FIG. 9 is a graph showing the frequency dependence of dielectric constant of an insulator layer of Example 2. -
FIG. 10 is a graph showing an evaluation result of insulating property of the insulator layer of Example 2. -
FIG. 11 shows photographs showing the results of Example 3. -
FIG. 12 shows photographs showing the results of Example 3. -
FIG. 13 shows photographs showing the results of Example 3. -
FIG. 14 shows a photograph showing the result of Example 3. -
FIG. 15 shows a graph showing the result of Example 3. - Hereinafter, a first embodiment of the present invention will be described.
- (Composition)
- A composition of the present embodiment includes the following (a) to (c):
- (a) an organic compound having a hydroxy group;
- (b) a first cross-linking agent that is at least one organic silicon compound selected from the group including
-
- (b-1) an organic silicon compound including a siloxane bond in the molecule and having three or more cyclic ether groups in the molecule,
- (b-2) a chain organic silicon compound including two or more siloxane bonds in the molecule and having two or more cyclic ether groups in the molecule,
- (b-3) a cyclic organic silicon compound including a siloxane unit (D unit) represented by R1R2SiO2/2 in the molecule, any one of or both of R1 and R2 being a cyclic ether group, and having four or more cyclic ether groups bonded to a silicon atom of the D unit in the molecule, and
- (b-4) a cyclic organic silicon compound including a siloxane unit (T unit) represented by R3SiO3/2 in the molecule, R3 being a cyclic ether group, and having two or more cyclic ether groups in the molecule; and
- (c) a photocationic polymerization initiator.
- Hereinafter, there will be described a case that the composition is a curable composition, but the composition of the present invention is not limited to the curable composition.
- The curable composition of the present embodiment is soluble in an alkaline solution. As an alkaline solution, an alkaline developer which is commonly used in a field such as photolithography can be used. Examples of materials of the developer include an aqueous TMAH (tetramethylammonium hydroxide) solution and an aqueous NaOH (sodium hydroxide) solution.
- Note that, the term “soluble in an alkaline solution” refers to that when a coating film formed in a film thickness of 1 μm is immersed in 2.38 mass % of an aqueous TMAH (tetramethylammonium hydroxide) at 25° C. for 2 minutes, the immersed portion of the coating film is completely dissolved and removed.
- Further, the term “coating film completely dissolved” refers to that when the aqueous TMAH solution after the test is filtered by a membrane filter (pore size 0.1 μm), a solid form of the coating film is not visually confirmed on the membrane filter.
- Further, the “cyclic ether group” refers to a group obtained by removing one hydrogen atom included in the cyclic ether. The one hydrogen atom to be removed may be an atom connected directly to the ring structure of the cyclic ether or may be an atom included in a substituent connected to the ring structure.
- Further, the “siloxane bond” refers to a Si—O—Si bond, and the number of siloxane bonds refers to the number of oxygen atoms that constitute the siloxane bond. For example, in the case of the structure of Si—O—Si—O—Si, the number of siloxane bonds is 2.
- Further, the “chain organic silicon compound” refers to an organic silicon compound in which the skeleton having the siloxane bond is chainlike.
- Further, the “cyclic organic silicon compound” refers to an organic silicon compound in which the skeleton having a siloxane unit (D unit) represented by R1R2SiO2/2 or a siloxane unit (T unit) represented by R3SiO3/2 constitutes the ring structure. The term “cyclic” includes “monocyclic”, “polycyclic”, “cross-linked structure”, and “spirocyclic structure”.
- Hereinafter, a compound that constitutes a curable composition used in the method of manufacturing a laminate of the present embodiment will be described. It is determined whether the compound that constitutes the curable composition in the present specification is usable or unusable, not based on whether or not an individual compound is “soluble in an alkaline solution”, but based on whether or not a curable composition constituted by the individual compound is “soluble in an alkaline solution”.
- As the organic compound (a), a commonly known organic compound can be used as long as the organic compound has an insulation property. When a high dielectric property in addition to the insulation property is required, for example, in a case where an insulator layer formed by using the curable composition is used for a gate insulator film of a transistor or a condenser, the organic compound (a) can include a phenolic hydroxy group. Examples of such an organic compound include polyvinyl phenol (PVP), and poly(2-hydroxyethyl methacrylate). Specifically, polyvinyl phenol (436224, manufactured by Sigma-Aldrich Corporation), and poly(2-hydroxyethyl methacrylate) (529265, manufactured by Sigma-Aldrich Corporation) can be used.
- The cyclic ether group included in the first cross-linking agent (b) may be a group that has a ring opened by a cation under a cationic polymerization environment and that is bondable to the organic compound (a). Examples of such a group include a 3 to 4-membered oxa cycloalkyl group, or a group having such an oxa cycloalkyl group. The oxa cycloalkyl group may include a condensed ring structure.
- Such an oxa cycloalkyl group can be a group having an epoxy ring as a three-membered ring or a group having an oxetanyl ring as a four-membered ring. Since the epoxy ring and the oxetanyl ring have strain in the ring structure, the epoxy ring and the oxetanyl ring have a high reactivity, and the ring is easily opened. Therefore, the epoxy ring and the oxetanyl ring are capable of forming a bond to the organic compound (a).
- Examples of the cyclic ether group included in the first cross-linking agent (b) include: (1) a 3 to 4-membered oxa cycloalkyl group; (2) a group formed by substituting a 3 to 4-membered oxa cycloalkyl group for a hydrogen atom included in one group selected from the group including: a straight-chain, branched, or cyclic alkyl group of 1 to 20 carbon atoms; an alkoxyalkyl group formed by substituting a straight-chain, branched, or cyclic alkoxy group of 1 to 10 carbon atoms for a hydrogen atom included in a straight-chain, branched, or cyclic alkyl group of 1 to 10 carbon atoms; and an aromatic group; and (3) a condensed ring group of a 3 to 4-membered oxa cycloalkyl group and one selected from the group including: a straight-chain, branched, or cyclic alkyl group of 1 to 20 carbon atoms; an alkoxyalkyl group formed by substituting a straight-chain, branched, or cyclic alkoxy group of 1 to 10 carbon atoms for a hydrogen atom included in a straight-chain, branched, or cyclic alkyl group of 1 to 10 carbon atoms; and an aromatic group.
- In the organic silicon compound (b-1) including a siloxane bond in the molecule and having three or more cyclic ether groups in the molecule, the cyclic ether groups may be identical to each other or may be different from each other.
- In the chain organic silicon compound (b-2) including two or more siloxane bonds in the molecule and having two or more cyclic ether groups in the molecule, the cyclic ether groups may be identical to each other or may be different from each other. Further, in the chain organic silicon compound (b-2), the two or more siloxane bonds may be in a straight chain form or may have a branched structure.
- Specific examples of such a chain organic silicon compound (b-2) can include a compound represented by Formula (B21) below, and a compound (Tris(glycidoxypropyldimethylsiloxy)phenylsilane (SIT8715.6, manufactured by Gelest Inc.) represented by Formula (B22) below.
- In the cyclic organic silicon compound (b-3) including a siloxane unit (D unit) represented by R1R2SiO2/2 in the molecule, any one of or both of R1 and R2 being a cyclic ether group, and having four or more cyclic ether groups bonded to a silicon atom of the D unit in the molecule, the cyclic ether groups may be identical to each other or may be different from each other. Further, in a case where a plurality of D units are included, R1s included in the D units may be identical to each other or may be different from each other, and R2s included in the D units may be identical to each other or may be different from each other.
- In the cyclic organic silicon compound (b-3), the D units may be bonded to each other to form a monocyclic structure surrounded by a Si—O—Si bond, or may further include a siloxane unit of a T unit that does not have a cyclic ether group to thereby form a cage-shaped structure surrounded by a Si—O—Si bond. Further, in a case where the T unit is included, the cyclic organic silicon compound (b-3) may have a structure in which a silicon atom is not bonded to the other end of an oxygen atom that constitutes a Si—O bond and part of the cage-shaped structure is not surrounded by a Si—O—Si bond.
- In the cyclic organic silicon compound (b-4) including a siloxane unit (T unit) represented by R3SiO3/2 in the molecule, R3 being a cyclic ether group, and having two or more cyclic ether groups in the molecule, the cyclic ether groups may be identical to each other or may be different from each other. Further, in a case where a plurality of T units are included, R3s included in the T units may be identical to each other or may be different from each other.
- In the cyclic organic silicon compound (b-4), the T units may be bonded to each other to form a cage-shaped structure surrounded by a Si—O—Si bond, or in an unit structure of part of T units, a structure may be formed in which a silicon atom is not bonded to the other end of an oxygen atom that constitutes a Si—O bond and part of the cage-shaped structure is not surrounded by a Si—O—Si bond. Further, the cyclic organic silicon compound (b-4) may include a siloxane unit of a D unit.
- A specific example of such a cyclic organic silicon compound (b-4) can include a compound (PSS-Octa[(3-glycidyloxypropyl)dimethylsiloxy]substituted (593869, manufactured by Sigma-Aldrich Corporation)) represented by Formula (B41) below.
- As the first cross-linking agent (b), a cyclic organic silicon compound (b-3) or (b-4) in which Si—O bonds are aggregated is preferably used.
- The photocationic polymerization initiator (c) is a compound that initiates the cationic polymerization reaction of a curable composition using the cationic species or Lewis acid generated by the absorption of light (for example, ultraviolet light) energy. As the photocationic polymerization initiator, known photocationic polymerization initiators, such as aromatic diazonium salts, aromatic sulfonium salts, aromatic iodonium salts, metallocene compounds, phosphonium salts, and silanol-aluminum complexes, can be used. These compounds may be used alone or in a mixture of two or more.
- A specific example of the photocationic polymerization initiator (c) may include OMPH076 manufactured by Glest Inc., which is an aromatic sulfonium salt.
- Here, in order to increase the reactivity of the photocationic polymerization initiator (c), a photosensitizer that accelerates the reaction of the photocationic polymerization initiator (c) by absorbing light and transferring the absorbed energy to the photocationic polymerization initiator (c) may be added to the curable composition.
- The curable composition of the present embodiment may further include a second cross-linking agent (d) that is an organic compound having two or more cyclic ether groups. When the curable composition further includes the second cross-linking agent, it is possible to add physical properties due to the second cross-linking agent to an insulator, which will be formed, and the degree of freedom of design is enhanced.
- For example, in order to improve insulation properties of the insulator to be formed and additionally improve the dielectric constant, the second cross-linking agent can be a compound having an aromatic ring and is preferably a compound represented by Formula (d1) below.
- (R2 and R3 are each a cyclic ether group. R2 and R3 may be identical to each other or may be different from each other.)
- The cyclic ether group represented as R2 and R3 can be a group formed by substituting a 3 to 4-membered oxa cycloalkyl group for a hydrogen atom included in one selected from the group including: a straight-chain, branched, or cyclic alkyl group of 1 to 20 carbon atoms; an alkoxyalkyl group formed by substituting a straight-chain, branched, or cyclic alkoxy group of 1 to 10 carbon atoms for a hydrogen atom included in a straight-chain, branched, or cyclic alkyl group of 1 to 10 carbon atoms; and an aromatic group.
- The oxa cycloalkyl group included in the group represented as R2 and R3 can be a group having an epoxy ring that is a three-membered ring or a group having an oxetanyl ring that is a four-membered ring. Since the epoxy ring and the oxetanyl ring have strain in the ring structure, the epoxy ring and the oxetanyl ring have a high reactivity, and the ring is easily opened such that a cationic polymerization reaction occurs.
- A specific example of the second cross-linking agent (d) can include a bisphenol A epoxy monomer (RE310S, manufactured by Nippon Kayaku Co., Ltd.) represented by Formula (d2) below.
- In the curable composition of the present embodiment, the ratio of the sum of the mass of the first cross-linking agent (b) and the second cross-linking agent (d) to the total sum of the mass of the organic compound (a) having a hydroxy group, the first cross-linking agent (b), and the second cross-linking agent (d) can be 40 mass % to 90 mass %, and the ratio of the mass of the second cross-linking agent (d) to the total sum of (a), (b) and (d) can be 5 mass % to 30 mass %. Although most of second cross-linking agents (d) are insoluble in an alkaline solution, when such a combination is used, it is possible to add physical properties due to the second cross-linking agent to the insulator in a state where the entire curable composition is soluble in an alkaline solution.
- The curable composition of the present embodiment may be used in combination with various fillers within a range that does not impair the advantages of the present invention. When the curable composition is used in combination with a filler, the curable composition functions as the binder of the filler, and physical properties due to the filler can be further imparted to an insulator, which will be formed.
- Although most of such fillers are insoluble in an alkaline solution, when a coating film of a curable composition including a filler is immersed in an alkaline solution, the curable composition is dissolved in the alkaline solution. Thereby, the support of the filler is lost, and the filler is dispersed in the alkaline solution. Accordingly, it is possible to remove even a composition using a curable composition with a filler by the alkaline solution.
- The curable composition as described above is developable by an alkaline solution and is capable of forming an insulator layer. Therefore, it is possible to reduce a manufacturing load.
- (Manufacturing Method of Laminate, Laminate)
- Hereinafter, a method of manufacturing a laminate according to the present embodiment and a laminate will be described with reference to
FIGS. 1A to 1C . In all the following drawings, for ease of understanding the drawings, dimensions, proportions, and the like of each component are appropriately varied. -
FIGS. 1A to 1C are process views showing a method of manufacturing a laminate according to the present embodiment. - First, as shown in
FIG. 1A , a solution in which the aforementioned curable composition is dissolved in an organic solvent (hereinafter, referred to as “a raw material solution”) is applied over aconductive layer 200 formed on asubstrate 100, and the solvent is removed. Thereby, acoating film 300 is formed. - Examples of the formation material of the
substrate 100 may include: inorganic materials, such as glass, quartz glass, and silicon nitride; and organic materials (resin materials), such as acrylic resins, polycarbonate resins, polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT). - As the
conductive layer 200, wirings and electrodes can be exemplified. Examples of the formation material of theconductive layer 200 may include conductive polymers, metals such as Al, Ag and Au, and alloys. Generally known formation materials can be used in addition to these formation materials. - The
coating film 300 is formed by applying the raw material solution and then removing the solvent. As the method of applying the raw material solution, generally known methods, such as spin coating, dip coating, spray coating, roll coating, brushing, flexographic printing, inkjet printing, and screen printing, may be exemplified. - In addition, as the solvent dissolving the curable composition, various organic solvents can be used. Examples of the organic solvent may include: alcohols, such as methanol, ethanol, 1-propanol, and 2-propanol (isopropyl alcohol (IPA)); ethers, such as propylene glycol monomethyl ether acetate (PGMEA); aromatic hydrocarbons, such as toluene and xylene; nitriles such as acetonitrile; esters such as acetic acid ester; ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. These organic solvents may be used alone or in a mixture of two or more.
- In order to remove a solvent from the applied raw material solution, a method of volatilizing the solvent using generally known operations such as heating, air blow and depressurization can be used. These operations may be used in a combination of two or more. In addition, the film obtained by removing a solvent from the raw material solution is prebaked. Thereby, the
non-patterned coating film 300 is formed. The prebaking is performed, for example, by heating the film obtained by removing a solvent from the raw material solution at 105° C. for 5 minutes. - Next, as shown in
FIG. 1B , thecoating film 300 is irradiated with ultraviolet L (light) through a mask M provided with an opening Ma in a region overlapping theconductive layer 200 in a plan view and having a light shielding portion Mb around the opening Ma, so as to allow thecoating film 300 to be exposed to light. The ultraviolet L is light having an absorption wavelength of the photocationic polymerization initiator included in the curable composition. For example, in the mask exposure of the present embodiment, ultraviolet of i-line ray (365 nm) is irradiated at an irradiation intensity of 500 mJ/cm2. Accordingly, a photocationic polymerization reaction proceeds in thecoating film 300, and the latent image of aninsulator layer 310 is formed on thecoating film 300. - Here, in order to accelerate a curing reaction by photocationic polymerization, a heat treatment may be performed in a temperature range of 100° C. to 120° C. for 10 minutes. This heat treatment may be performed simultaneously with the irradiation of ultraviolet L and may also be performed after the irradiation of ultraviolet L.
- Next, as shown in
FIG. 1C , thecoating film 300 subjected to mask exposure as shown inFIG. 1B is developed using an alkaline solution as a developer S. As the developer S, for example, 2.38 mass % of an aqueous TMAH solution can be used, and the developing time, for example, may be set to 1 minute. - The solubility of the exposed region (insulator layer 310) of the
coating film 300 in the developer S relatively decreases compared to that of the non-exposed region in thecoating film 300, because photocationic polymerization proceeds and the molecular weight increases. Therefore, the non-exposed region of thecoating film 300 is dissolved and developed by the developer S, and thereby it is possible to form a laminate 1000 having theinsulator layer 310 covering theconductive layer 200. - Prior to applying a raw material solution shown in
FIG. 1A , a surface treatment may be applied on at least a region in which theinsulator layer 310 will be formed by using a silane coupling agent (first silane coupling agent) having a cyclic ether group. A specific example of such a silane coupling agent includes 3-glycidoxypropyl triethoxysilane (KBM-403, manufactured by Shin-Etsu Silicone Co., Ltd.). When such a silane coupling agent is applied in advance and a surface treatment is performed, the cyclic ether group included in the silane coupling agent reacts and bonds to an organic compound included in the curable composition during a photocationic polymerization reaction. Therefore, an adhesion power between theinsulator layer 310 to be formed and thesubstrate 100 and an adhesion power between theinsulator layer 310 to be formed and theconductive layer 200 are enhanced, and it is possible to suppress damage to thelaminate 1000. - The method of manufacturing a laminate as described above uses a curable composition that is developable by an alkaline solution and is capable of forming an insulator layer. Therefore, it is possible to provide a manufacturing process in which a manufacturing load is reduced.
- The laminate as described above uses a curable composition that is developable by an alkaline solution and is capable of forming an insulator layer. Therefore, even when a resin substrate is used, it is possible to preventing the substrate from being dissolved or swelled.
- As the laminate 1000 having a laminated structure manufactured in this way, a wiring board, a condenser, and the like, each having a multi-layer interconnect structure, are exemplified.
- Next, a method of manufacturing a transistor according to a second embodiment of the present invention and a transistor will be described with reference to
FIGS. 2 to 4B . -
FIG. 2 is a schematic cross-sectional view showing a transistor manufactured by the method of manufacturing a transistor according to the present embodiment, and a transistor according to the present embodiment. Atransistor 1A is a so-called bottom-contact type transistor. In the following description, there will be described an organic transistor using an organic semiconductor as the formation material of a semiconductor layer, but the present invention is also applicable to an inorganic transistor using an inorganic semiconductor as the formation material of a semiconductor layer. - The
transistor 1A includes asubstrate 2,base films electroless plating catalysts gate electrode 6, aninsulator layer 7, asource electrode 16, adrain electrode 17, and an organic semiconductor layer (semiconductor layer) 20. In thetransistor 1A, the layer of a combination of theinsulator layer 7 and thebase film 13 refers to “a layer containing an insulator layer”. - As the
substrate 2, any of a substrate having optical transparency and a substrate not having optical transparency can be used. For example, thesubstrate 2 can be made of any one of: inorganic materials such as glass, quartz glass, and silicon nitride; and organic polymers (resins), such as acrylic resins, polycarbonate resins, and polyester resins (for example, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and the like). - The formation material of these
substrates 2 does not form a metallic bond together with a metal-made plating film formed as a result of electroless plating. For this reason, in the present embodiment, the formation material of thesesubstrates 2 is treated as a poor plating material on which a plating film is not easily formed directly, and the formed plating film is easily stripped. Due to the similar reason, if the plating film is made of an easily-strippable material, for example, a composite material of the above-mentioned material and the like can also be similarly used as the formation material of thesubstrate 2. - The
base film 3 is a gate base film in the present invention. Thebase film 3 is formed over the entire surface of the main side of thesubstrate 2, and part of the surface of thebase film 3 is selectively provided with a catalyst (electroless plating catalyst) 5. Thecatalyst 5 is a catalyst for reducing metal ions contained in a plating solution for electroless plating. As the catalyst, silver, metal palladium, and the like are exemplified. In the present embodiment, metal palladium is used. - The
base film 3 is a film capable of capturing a metal that is the above-mentionedcatalyst 5, and a silane coupling agent (second silane coupling agent) having a group capable of capturing the metal is used as the formation material of thebase film 3. Thebase film 3 is formed by applying a liquid product containing such a silane coupling agent onto the main side of thesubstrate 2. - The “silane coupling agent”, which is the formational material of the
base film 3, is a compound in which a group capable of capturing the metal (catalyst 5) and a group capable of being bonded to thesubstrate 2 are bonded to a silicon atom. - Here, the “group capable of capturing the metal” refers to a group that can capture the metal (catalyst 5) or ions of this metal, for example, by an ion bond or a coordinate bond. As this group, a group having a nitrogen atom or a sulfur atom is exemplified. Examples of the group having a nitrogen atom or a sulfur atom may include an amino group, a urea group, a thiol group (or a mercapto group), a thiocarbonyl group, a thiourea group, and a group obtained by removing one or more hydrogen atoms bonded to a heterocyclic compound containing a nitrogen atom or a sulfur atom. Examples of the “heterocyclic compound containing a nitrogen atom or a sulfur atom” include: monocyclic aromatic heterocyclic compounds, such as pyrrole, imidazole, pyridine, pyrimidine, and thiophene; polycyclic aromatic heterocyclic compounds, such as indole and benzothiophene; and non-aromatic heterocyclic compounds in which two or more carbon atoms in an aromatic ring of each of these aromatic compounds are hydrogenated.
- As the “group capable of being bonded to the
substrate 2”, a hydroxyl group and an alkoxy group of 1 to 6 carbon atoms are exemplified. - Specific examples of the compound that can be used as the formation material of the
base film 3 may include N-cyclohexyl-aminopropyltrimethoxysilane, bis(3-(trimethoxysilyl)propyl)ethylenediamine, 1-(3-(trimethoxysilylpropyl))urea, bis(3-trimethoxysilylpropyl))urea, 2,2-dimethoxy-1,6-diaza-2-silacyclooctane, N-(3-(trimethoxysilyl propyl))-4,5-dihydroimidazole, bis(3-(trimethoxysilyl)propyl)thiourea, 3-trimethoxysilylpropanethiol, and polyethyleneimine modified with a trimethoxysilylpropyl group. - Among these, as the silane coupling agent, a silane coupling agent having an amino group as the “group capable of capturing metal” is preferable, and a silane coupling agent, which is a primary amine or a secondary amine (“group capable of capturing metal” is a group represented by —NH2 or —NH—), is more preferable. In the following description, as the
base film 3, a base film formed by using a silane coupling agent as a primary amine will be described. - The
gate electrode 6 is a metal electrode formed on the surface of thecatalyst 5, and, as described later, is formed of a metal deposited on the surface of thecatalyst 5 by electroless plating. As the material of thegate electrode 6, nickel phosphorus (NiP) or copper (Cu) is exemplified. - The
insulator layer 7 electrically insulates thegate electrode 6 having insulating properties from thesource electrode 16 and thedrain electrode 17. In theinsulator layer 7 of the present embodiment, the above-mentioned curable composition in the first embodiment is used as a formation material. - The
base film 13 is formed on the entire upper surface of theinsulator layer 7. Thebase film 13 is a source base film and is a drain base film in the present invention, and the source base film and the drain base film are formed as a continuous film. Thebase film 13 is formed over the entire surface of the main side of thesubstrate 2, and part of the surface of thebase film 13 is selectively provided with a catalyst (catalyst for electroless catalyst) 15. The formation material of thecatalyst 15 may be the same as that of the above-mentionedcatalyst 5. - The formation material of the
base film 13 is the same as that of the above-mentionedbase film 3, but the formation materials of thebase film 3 and thebase film 13 may be different from each other. In the following description, a case where thebase film 13 is formed by using a silane coupling agent as a primary amine which is the same as that used for thebase film 3 will be described. - In the drawing, it is shown that the
base film 13 is formed on the entire upper surface of theinsulator layer 7, but thebase film 13 may be selectively formed on only a location where thecatalyst 15 is provided. In this case, a silane coupling agent, which is a formation material of thebase film 13, is selectively applied to the upper surface of theinsulator layer 7 using a generally known method, and thereby it is possible to selectively form thebase film 13. Further, in the upper surface of theinsulator layer 7, first, the silane coupling agent may be applied to a region larger than the region forming thebase film 13, and then a film formed at a portion protruding from the region forming thebase film 13 may be irradiated with ultraviolet to thereby decompose and remove the silane coupling agent to selectively form thebase film 13. - The
source electrode 16 and thedrain electrode 17 are metal electrodes formed on the surface of thecatalyst 15. Thesource electrode 16 has afirst electrode 161 and asecond electrode 162 covering the surface of thefirst electrode 161. Similarly, thedrain electrode 17 has athird electrode 171 and afourth electrode 172 covering the surface of thethird electrode 171. - The
first electrode 161 and thethird electrode 171, similarly to the above-mentionedgate electrode 6, are formed by electroless plating. As the material of each of thefirst electrode 161 and thethird electrode 171, nickel phosphorus (NiP) or copper (Cu) is exemplified. In the present embodiment, it is described that nickel phosphorus (work function: 5.5 eV) is used as the formation material of each of thefirst electrode 161 and thethird electrode 171. Here, thefirst electrode 161 and thethird electrode 171 may each be formed using a different material. - The
second electrode 162 and thefourth electrode 172 are metal plating layers, each being formed over the entire surface of each of thefirst electrode 161 and thethird electrode 171, the surface not being in contact with thecatalyst 15. That is, thesecond electrode 162 is provided to cover alateral side 16 a in thesource electrode 16. Thefourth electrode 172 is provided to cover alateral side 17 a in thedrain electrode 17. The lateral sides 16 a and 17 a (opposing surfaces) face each other. - As the formation material of each of the
second electrode 162 and thefourth electrode 172, a metal material having a work function in which electron transfer (or hole transfer) is easy in relation to the HOMO/LUMO level of the formation material of asemiconductor layer 20 to be described later is used. In the present embodiment, it is described that gold (work function: 5.4 eV) is used as the formation material of each of thesecond electrode 162 and thefourth electrode 172. Here, thesecond electrode 162 and thefourth electrode 172 may each be formed using a different material. - The
semiconductor layer 20 is provided on the surface of thebase film 13 between thesource electrode 16 and thedrain electrode 17, and is formed in contact with thesource electrode 16 and thedrain electrode 17. Specifically, thesemiconductor layer 20 is provided in contact with thelateral side 16 a of thesource electrode 16 and thelateral side 17 a of thedrain electrode 17, and is in contact with thesecond electrode 162 and thefourth electrode 172. - As the formation material of the
semiconductor layer 20, generally known organic semiconductor materials can be used. Examples of the semiconductor materials may include: p-type semiconductors, such as copper phthalocyanine (CuPc), pentacene, rubrene, tetracene, and P3HT (poly(3-hexylthiophene-2,5-diyl)); and n-type semiconductors, such as fullerenes such as C60 and perylene derivatives such as PTCDI-C8H (N,N′-dioctyl-3,4,9,10-perylene tetracarboxylic diimide). Among these, soluble pentacene such as TIPS pentacene (6,13-bis(triisopropylsilylethynyl)pentacene) or an organic semiconductor polymer such as P3HT is soluble in an organic solvent such as toluene and can be used in forming thesemiconductor layer 20 by a wet process, which is preferable. In the present embodiment, it will be described that TIPS pentacene (HOMO level: 5.2 eV), which is a p-type semiconductor, is used as the formation material of thesemiconductor layer 20. - Further, the formation material of the
semiconductor layer 20 is not limited to organic semiconductor materials, and generally known inorganic semiconductor materials can also be used as the formation material of thesemiconductor layer 20. - In this
transistor 1A, thegate electrode 6, thesource electrode 16, and thedrain electrode 17, which are formed by electroless plating, are formed on thebase films 3 and 13 (gate base film, source base film, and drain base film), which are formed by using a silane coupling agent as a formation material. For example, when these electrodes are formed in the region having an uneven shape, an uneven shape is imparted to each of these electrodes in response to unevenness of a base. In this case, the distance between the electrodes laminated through an insulator layer is not constant, and there is a possibility that the insulation is damaged and leak current is generated at the position where the distance between the gate electrode and the source electrode or the distance between the gate electrode and the drain electrode becomes closer to each other. Further, if the base has an uneven shape, there is a possibility that an uneven shape is imparted even to the channel region (represented by AR inFIG. 2 ) of the semiconductor layer overlapping the gate electrode in a plan view, and the migration distance of a carrier in the channel region becomes longer, thereby deteriorating the performance of thetransistor 1A. - However, in the
transistor 1A of the present embodiment, since thebase films base films transistor 1A becomes a high-performance transistor. - Hereinafter, the method of manufacturing the above-mentioned
transistor 1A will be described with reference toFIGS. 3A to 3Q . - First, as shown in
FIG. 3A , a liquid product, which is obtained, if necessary, by diluting the above-mentioned silane coupling agent with an organic solvent, is applied onto the surface of asubstrate 2 to form acoating film 3A. As the method of applying the liquid product, generally known methods, such as spin coating, dip coating, spray coating, roll coating, brushing, flexographic printing, and screen printing, may be exemplified. - Here, it will be described that 3-aminopropyltriethoxysilane, which is a primary amine, is used as the silane coupling agent.
- As the organic solvent, various organic solvents can be used as long as the solvents are capable of dissolving the silane coupling agent. Among these organic solvents, a polar solvent can be preferably used. Examples of the solvent that can be used may include: alcohols, such as methanol, ethanol, 1-propanol, and 2-propanol (isopropyl alcohol (IPA)); ethers, such as propylene glycol monomethyl ether acetate (PGMEA); aromatic hydrocarbons, such as toluene; nitriles such as acetonitrile; esters such as acetic acid ester; and ketones, such as acetone, methyl ethyl ketone, and methyl isobutyl ketone.
- Next, as shown in
FIG. 3B , the organic solvent is volatilized and removed by a heat treatment to form abase film 3. Thebase film 3 formed in this manner is a silane coupling agent layer having an extremely thin film thickness, and therefore becomes a transparent film in which light scattering does not easily occur. Therefore, for example, if the transistor manufactured by the method of the present embodiment is provided on a substrate having optical transparency, it is possible to maintain the optical transparency as a combination of thesubstrate 2 and thebase film 3 even when thebase film 3 is formed on the entire surface of thesubstrate 2, and it is possible to easily form the film. - Next, as shown in
FIG. 3C , a resist material is applied onto thebase film 3, and is then prebaked to thereby form a resistlayer 4A that is not patterned. Here, as the resist material, a positive photoresist is used. - Thereafter, the resist
layer 4A is irradiated with ultraviolet L through a mask M1 including an opening Ma provided at the position corresponding to the region forming a metal electrode and including a light shielding portion Mb provided in the region not forming the metal electrode, so as to expose the resistlayer 4A to light. - Next, as shown in
FIG. 3D , the resist layer irradiated with ultraviolet is developed by a developer that dissolves the resist layer to thereby form a resistlayer 4 provided with anopening 4 a. - Next, as shown in
FIG. 3E , acatalyst 5 used in electroless plating is captured on the surface of thebase film 3 exposed through theopening 4 a formed in the resistlayer 4. Specifically, a metal, which is thecatalyst 5, is captured on thebase film 3 by contacting a colloidal solution of a divalent palladium salt. - A general electroless plating process of a resin proceeds in the order of washing, etching, catalyst imparting, and then electroless plating. Here, the “catalyst imparting” is a process of attaching a metal such as palladium (Pd), serving as an electroless plating reaction initiator (catalyst), to the surface of the region for carrying out plating. Generally, the “catalyst imparting” includes a process of bringing a colloidal solution of a divalent palladium salt and a divalent tin (Sn) salt into contact with a substrate to be attached by palladium and then immersing the substrate coated with the colloidal solution into an acid or alkali solution, called an accelerator. Thereby, the divalent palladium is reduced to zero-valent palladium, and the catalyst is activated.
- In contrast, as described in the present embodiment, it was confirmed by the inventors that, if the silane coupling agent, which is a formation material of a base film, is a primary amine or a secondary amine, the reduction treatment using the above-mentioned accelerator is not required (which will be described later). Therefore, when a primary amine or a secondary amine is used as the silane coupling agent, the operation of electroless plating is simplified.
- In the present embodiment, since 3-aminopropyltriethoxysilane, which is a primary amine, is used as the formation material of the
base film 3, a reduction treatment is not required, and the operation is simplified. - On the other hand, when the silane coupling agent is a tertiary amine or a silicon compound having another “group capable of capturing a metal”, a colloidal solution of a divalent palladium salt is applied, and then a normal treatment (activating process) using the above-mentioned accelerator is performed. Thereby, it is possible to capture a
catalyst 5 for electroless plating on thebase film 3. - Next, as shown in
FIG. 3F , an electroless plating solution is brought into contact with thecatalyst 5. Thereby, metal ions dissolved in the electroless plating solution is reduced and deposited on the surface of thecatalyst 5, and agate electrode 6 containing nickel phosphorus as a formation material is selectively formed in theopening 4 a. When the silane coupling agent is a primary amine or a secondary amine, thecatalyst 5 is immersed in the electroless plating solution without performing the activation using the accelerator, and thereby the surface of thecatalyst 5 is plated. Therefore, it can be indirectly confirmed that metal palladium is captured on the surface of thebase film 3. - Next, as shown in
FIG. 3G , the entire surface of the remaining resist layer is exposed to ultraviolet, and then the resist layer is removed by a generally known developer. In this way, thegate electrode 6 is formed. - Next, as shown in
FIG. 3H , a solution (raw material solution), in which the curable composition of the first embodiment is dissolved in an organic solvent, is applied to the surface of thebase film 3 to cover thegate electrode 6. As the application method, the above-mentioned method can be used. - As the organic solvent, a material which is the same as that described in the first embodiment can be used.
- Further, in the raw material solution, when concentration and the kind of an organic solvent are changed, the viscosity of the entire raw material solution can be adjusted, and the thickness of the
coating film 7A of the raw material solution can be controlled. - In the process shown in
FIG. 3H , in order to control the leak between thegate electrode 6 and the source electrode to be formed above and the leak between thegate electrode 6 and the drain electrode to be formed above, the photoresist is thickly applied such that the thickness of thecoating film 7A is about several hundreds of nanometers. Here, the thickness of thecoating film 7A is not limited thereto. - Next, as shown in
FIG. 3I , thecoating film 7A is irradiated with ultraviolet L through a mask M2 provided with an opening corresponding to the region forming aninsulator layer 7 to cure the curable composition, thereby forming theinsulator layer 7. In this case, in order to accelerate the curing reaction of the curable composition, a heat treatment can be performed simultaneously with the ultraviolet irradiation or after the ultraviolet irradiation. - Next, as shown in
FIG. 3J , thecoating film 7A is developed by an alkaline solution (developer S) that dissolves thecoating film 7A to thereby remove the uncured coating film and form aninsulator layer 7 that is patterned. - Here, in order to improve the adhesiveness between the
insulator layer 7 and thegate electrode 6, the silane coupling agent may be applied to cover the surface including thegate electrode 6 before the application of the raw material solution. - Next, as shown in
FIG. 3K , a liquid product, which is obtained, if necessary, by diluting the above-mentioned silane coupling agent with an organic solvent, is applied onto the entire upper surface of theinsulator layer 7, and then a heat treatment is performed to volatilize and remove the organic solvent, so as to form abase film 13. The silane coupling agent and the organic solvent may be the same as those used in the formation of thebase film 3 described above. - Next, as shown in
FIG. 3L , a resist material is applied over theinsulator layer 7 and thebase film 13 and is then prebaked. Thereby, a resistlayer 14A that is not patterned is formed. Here, as the resist material, a positive photoresist is used. - Thereafter, the resist
layer 14A is irradiated with ultraviolet L through a mask M3 provided with an opening corresponding to the region forming a source electrode and a drain electrode, so as to expose the resistlayer 14A to light. - Next, as shown in
FIG. 3M , the resist layer irradiated with ultraviolet is developed by a developer that dissolves the resist layer to thereby form a resistlayer 14 provided with anopening 14 a. - Next, as shown in
FIG. 3N , a colloidal solution of a divalent palladium salt is made to come into contact with thebase film 13 exposed through the opening 14 a. Thereby, thecatalyst 15 used in electroless plating is captured to the surface of thebase film 13. Thereafter, an electroless plating solution is made to come into contact with thecatalyst 15. Thereby, metal ions dissolved in the electroless plating solution are reduced and deposited on the surface of thecatalyst 15, and afirst electrode 161 and athird electrode 171 made of nickel phosphorus are selectively formed in theopening 14 a. - Next, as shown in
FIG. 3O , the entire surface of the remaining resist layer is exposed to ultraviolet, and then the resist layer is removed by a generally known developer. In this way, thefirst electrode 161 and thethird electrode 171 are formed. - Next, as shown in
FIG. 3P , the entire body is immersed into a gold plating bath for substitution to allow the surface of thefirst electrode 161 and thethird electrode 171 to be substituted and deposited with gold, and is further immersed into a gold plating bath for reduction to thereby form asecond electrode 162 and afourth electrode 172, which are plated with gold, on the surface of thefirst electrode 161 and thethird electrode 171. In this way, asource electrode 16 and adrain electrode 17 are formed. - Next, as shown in
FIG. 3Q , a solution S1, in which an organic semiconductor material soluble in an organic solvent, such as TIPS pentacene, is dissolved in the organic solvent, is applied between thesource electrode 16 and thedrain electrode 17, and is dried to thereby form asemiconductor layer 20. Here, thesemiconductor layer 20 is formed by a wet method, but can also be formed by a sublimation method, a transfer method, or the like. - In this way, it is possible to manufacture the
transistor 1A. - Prior to applying a raw material solution shown in
FIG. 3H , a surface treatment may be applied on at least a region in which theinsulator layer 7 will be formed by using a silane coupling agent having a cyclic ether group. - A specific example of such a silane coupling agent includes 3-glycidoxypropyl triethoxysilane (KBM-403, manufactured by Shin-Etsu Silicone Co., Ltd.). When such a silane coupling agent is applied in advance and a surface treatment is performed, the cyclic ether group included in the silane coupling agent reacts and bonds to an organic compound included in the curable composition during a photocationic polymerization reaction. Therefore, an adhesion power between the
insulator layer 7 to be formed and the substrate 2 (base film 3) and an adhesion power between theinsulator layer 7 to be formed and thegate electrode 6 are enhanced, and it is possible to suppress damage to thetransistor 1A. - In the method of manufacturing a transistor of the configuration as described above, a curable composition that is developable by an alkaline solution and is capable of forming an insulator layer is used. Therefore, it is possible to provide a manufacturing process in which a manufacturing load is reduced.
- In the transistor as described above, the
insulator layer 7 is formed by using a curable composition that is developable by an alkaline solution. Therefore, even when a resin substrate is used, it is possible to prevent the substrate from being dissolved or swelled by a developer, and it is possible to form a transistor with reduced degradation during manufacturing. - Further, since the
base films - Further, since the resist
layer 14 is previously removed before the formation of thesecond electrode 162 and thefourth electrode 172, thesecond electrode 162 and thefourth electrode 172 can be surely formed even on thelateral side 16 a of thesource electrode 16 and thelateral side 17 a of thedrain electrode 17. Therefore, in the manufacturedtransistor 1A, electric current easily flows between thesemiconductor layer 20 and the source electrode 16 (or between thesemiconductor layer 20 and the drain electrode 17) at the time of driving, and thetransistor 1A can be well driven. - Further, the
first electrode 161 is covered with thesecond electrode 162, and thethird electrode 171 is covered with thefourth electrode 172. Thereby, the temporal corrosion of thefirst electrode 161 and thethird electrode 171 is suppressed, and there is also an advantage in that the performance of the transistor can be stably maintained. -
FIGS. 4A and 4B are schematic views showing the drive status of a transistor.FIG. 4A is a view showing atransistor 1 x which has the same configuration as thetransistor 1A except that thetransistor 1 x does not have the second electrode.FIG. 4B is a view showing thetransistor 1A manufactured by the method of the present embodiment. - Here, in the present embodiment, the phrase “energy level of molecular orbital used in electron transfer in the formation material of an organic semiconductor layer” refers to the energy level of HOMO in the case where the organic semiconductor layer is made of a p-type semiconductor, and refers to the energy level of LUMO in the case where the organic semiconductor layer is made of an n-type semiconductor.
- First, as in the
transistor 1 x shown inFIG. 4A , when thetransistor 1 x has a configuration which does not include the second electrode, since the gap (energy level difference) between the energy level of HOMO of thesemiconductor layer 20 and the work function of thefirst electrode 161 becomes large, Schottky barrier occurs, and electric current hardly flows. Therefore, for example, as shown by an arrow A inFIG. 4A , it is easy to form the flow of electric current through the highly-resistant semiconductor layer 20, and it is difficult to secure a good conduction. - In contrast, as shown in
FIG. 4B , in thetransistor 1A, when a voltage is applied to the gate electrode (not shown), a channel region AR having a thickness of several nanometers (nm) is formed in thesemiconductor layer 20 around the interface between thesemiconductor layer 20 and thebase film 13, enabling the conduction between thesource electrode 16 and the drain electrode (not shown). In this case, the surface of thesource electrode 16 is provided with thesecond electrode 162, which is formed using a metal material having a work function (energy level difference with HOMO of thesemiconductor layer 20 is small) at which electron transfer is easier between thesecond electrode 162 and the formation material of thesemiconductor layer 20 compared to between thesecond electrode 162 and thefirst electrode 161, and the Shottky barrier is reduced, so that electric current easily flows into the channel region AR through thefirst electrode 161 and thesecond electrode 162.FIG. 4B shows the flow of electric current using an arrow B. Therefore, it is possible to realize a high-performance transistor 1A. -
FIG. 5 is a schematic cross-sectional view of atransistor 1B, which is manufactured by the manufacturing method of a transistor according to a third embodiment of the present invention. - The
transistor 1B of the present embodiment is partially in common with thetransistor 1A of the second embodiment. The difference between thetransistor 1A and thetransistor 1B is that the transistor of the second embodiment is a bottom contact transistor, and thetransistor 1B of the present embodiment is a top contact transistor. Accordingly, in the present embodiment, the same reference numerals for the components in common with the second embodiment are used, and detailed description of the components will be omitted. - The
transistor 1B includes asemiconductor layer 20 disposed on aninsulator layer 7 and having a surface on which asource electrode 16 and adrain electrode 17 are formed. - That is, a
semiconductor layer 20 is formed on the entire upper surface of aninsulator layer 7, and abase film 13 is formed on the entire upper surface of thesemiconductor layer 20. In thetransistor 1B, the layer of a combination of theinsulator layer 7, thesemiconductor layer 20, and thebase film 13 refers to a “layer containing an insulator layer”. - A
catalyst 15 is selectively provided on the upper surface of thebase film 13, and asource electrode 16 including afirst electrode 161 and asecond electrode 162, and adrain electrode 17 including athird electrode 171 and afourth electrode 172 are formed on the upper surface. In thesemiconductor layer 20, the region located in the vicinity of the upper surface of the semiconductor layer and sandwiched between thesource electrode 16 and thedrain electrode 17 becomes a channel region AR. - Hereinafter, the method of manufacturing the above-mentioned
transistor 1B will be described with reference toFIGS. 6A to 6G - In the manufacture of the
transistor 1B, first, similarly to the second embodiment, abase film 3, acatalyst 5, agate electrode 6, and aninsulator layer 7 are laminated on the upper surface of asubstrate 2. Next, as shown inFIG. 6A , a solution S1 in which an organic semiconductor soluble in an organic solvent is dissolved in the organic solvent is applied onto theinsulator layer 7, and then dried to thereby form thesemiconductor layer 20. - Next, as shown in
FIG. 6B , a liquid product, which is obtained, if necessary, by diluting the above-mentioned silane coupling agent with an organic solvent, is applied onto the entire upper surface of thesemiconductor layer 20, and then is heat-treated to volatilize and remove the organic solvent, thereby forming abase film 13. - Next, as shown in
FIG. 6C , a resist material is applied over theinsulator layer 7, thesemiconductor layer 20, and thebase film 13, and is then prebaked to thereby form a resistlayer 14A that is not patterned. Thereafter, the resistlayer 14A is irradiated with ultraviolet L through a mask M3 provided with an opening corresponding to the region forming a source electrode and a drain electrode, so as to expose the resistlayer 14A to light. - Next, as shown in
FIG. 6D , the resist layer irradiated with ultraviolet is developed by a developer dissolving the resist layer to thereby form a resistlayer 14 provided with anopening 14 a. - Next, as shown in
FIG. 6E , a colloidal solution of a divalent palladium salt is made to come into contact with thebase film 13 exposed through the opening 14 a, thereby capturing thecatalyst 15 used in electroless plating to the surface of thebase film 13. Thereafter, an electroless plating solution is made to come into contact with thecatalyst 15. Thereby, metal ions dissolved in the electroless plating solution is reduced and deposited on the surface of thecatalyst 15, and afirst electrode 161 and athird electrode 171 made of nickel phosphorus are formed selectively in theopening 14 a (first electroless plating). - Next, as shown in
FIG. 6F , the entire surface of the remaining resist layer is exposed to ultraviolet, and then the resist layer is removed by a generally known developer. In this way, thefirst electrode 161 and thethird electrode 171 are formed. - Next, as shown in
FIG. 6G , the entire body is immersed into a gold plating bath for substitution to allow the surface of thefirst electrode 161 and thethird electrode 171 to be substituted and deposited with gold, and is further immersed into a gold plating bath for reduction to thereby form asecond electrode 162 and afourth electrode 172, which are plated with gold, on the surface of thefirst electrode 161 and the third electrode 171 (second electroless plating). In this way, asource electrode 16 and adrain electrode 17 are formed. - In this way, it is possible to manufacture the
transistor 1B. - Also in the
transistor 1B as described above, theinsulator layer 7 is formed by using a curable composition that is developable by an alkaline solution. Therefore, even when a resin substrate is used, it is possible to prevent the substrate from being dissolved or swelled by a developer, and it is possible to form a transistor with reduced degradation during manufacturing. - Further, the
base films - Further, in the
source electrode 16 of thetransistor 1B, thesecond electrode 162 is formed using a metal material having a work function (energy level difference with HOMO of thesemiconductor layer 20 is small) at which electron transfer is easier between the formation material of thesemiconductor layer 20 and thesecond electrode 162 compared to between thefirst electrode 161 and thesecond electrode 162. In thedrain electrode 17 of thetransistor 1B, thefourth electrode 172 is formed using a metal material having a work function (energy level difference with HOMO of thesemiconductor layer 20 is small) at which electron transfer is easier between the formation material of thesemiconductor layer 20 and thefourth electrode 172 compared to between thethird electrode 171 and thefourth electrode 172. In the enclosed position shown by a reference numeral a, electric current easily flows into the channel region AR from thesecond electrode 162 and thefourth electrode 172, and therefore it is possible to realize a high-performance transistor 1B. - Further, since the
first electrode 161 is covered with thesecond electrode 162 and thethird electrode 171 is covered with thefourth electrode 172, the temporal corrosion of thefirst electrode 161 and thethird electrode 171 is suppressed, and there is also an advantage in that the performance of the transistor can be stably maintained. - The transistor of the present embodiment is configured such that the
semiconductor layer 20 is not in contact directly with thesource electrode 16 and thedrain electrode 17 but is in contact with thesource electrode 16 and thedrain electrode 17 through thebase film 13, but thebase film 13 is formed in a very thin layer having a thickness of several nanometers (nm). Therefore, the effect of thebase film 13 influencing transistor characteristics is small, and electric current flows well between thesemiconductor layer 20 and thesource electrode 16 and between thesemiconductor layer 20 and thedrain electrode 17. - Heretofore, examples of embodiments of the present invention have been described with reference to the accompanying drawing, but the present invention is not limited to the examples. The shapes, combination, and the like of the components described in the above-mentioned examples are merely examples, and can be variously modified based on design requirements and the like without departing from the scope of the present invention.
- For example, a substrate can be made of a non-metallic material. A plurality of plating members in each of which a base film is formed on a PET substrate (non-metallic substrate) are prepared. The plating members are conveyed, and simultaneously a transistor is manufactured using the above-mentioned manufacturing method in the conveying process. Thereby, it is possible to form a high-performance transistor on the PET substrate.
- Moreover, in a roll to roll process, in which a plating member in which a base film is formed on a long PET film having flexibility, as a substrate, is rolled, the rolled plating member is conveyed while unrolling, transistors are continuously manufactured using the above-mentioned manufacturing method, and then the manufactured transistors are rolled, it is possible to form a transistor on the PET film.
- Further, in the present embodiment, a base film is formed using a silane coupling agent as a formation material, a catalyst for electroless plating is captured on the base film, and then electroless plating is performed, so as to form a gate electrode, a source electrode and a drain electrode. However, these electrodes may also be formed by forming any one or two electrodes of these electrodes using the above-mentioned method and forming the remaining electrodes using another method. For example, the gate electrode may be formed using a generally known patterning method, and the source electrode and drain electrode, which are formed in the same layer, may be formed using the above-mentioned manufacturing method.
- Hereinafter, the present invention will be described in more detail with reference to the following Examples, but the scope of the present invention is not limited to these Examples.
- In Example 1, a solution of the following combination was used for a raw material solution in which a curable composition is dissolved.
- (Raw Material Solution 1)
- (a) organic compound having a hydroxy group: 4 mass % of polyvinyl phenol (PVP) (436224, manufactured by Sigma-Aldrich Corporation)
- (b) first cross-linking agent: 5 mass % of (Tris(glycidoxypropyldimethylsiloxy)phenylsilane (SIT8715.6, manufactured by Gelest Inc.)
- (c) second cross-linking agent: 1 mass % of bisphenol A epoxy monomer (RE-310s, manufactured by Nippon Kayaku Co., Ltd.)
- (d) photocationic polymerization initiator: 0.5 mass % of (thiophenoxyphenyl)diphenylsulfonium hexafluorophosphate-bis(diphenylsulfonium)diphenylthioether hexafluorophosphate blend, 50% in propylene carbonate (OMPH076, manufactured by Gelest Inc.)
- (e) solvent: 89.5 mass % of cyclohexanone
- (Raw Material Solution 2)
-
Raw material solution 2 was prepared in the same manner asraw material solution 1, except that PSS-Octa[(3-glycidyloxypropyl)dimethylsiloxy]substituted (593869, manufactured by Sigma-Aldrich Corporation) was used as the first cross-linking agent (b). - (Raw Material Solution 3)
Raw material solution 3 was prepared in the same manner asraw material solution 1, except that tetraphenylol ethane glycidyl ether (412961, manufactured by Sigma-Aldrich Corporation) represented by Formula (100) below was used as the first cross-linking agent (b). - (Raw Material Solution 4)
-
Raw material solution 4 was prepared in the same manner asraw material solution 1, except that poly(2-hydroxyethyl methacrylate) (529265, manufactured by Sigma-Aldrich Corporation) was used as the organic compound (a) having a hydroxy group. - The raw material solution was applied on a PET substrate (Model number: A-4100 (no coat), manufactured by Toyobo Co., Ltd.) by spin coating (1500 rpm×30 seconds). Then, the substrate was heated at 105° C. for 5 minutes to volatilize cyclohexanone as a solvent to form a coating film of a curable composition on the PET substrate.
- Next, the coating film was irradiated with i-line ray (365 nm) at an irradiation intensity of 500 mJ/cm2 through a photomask having a pattern of L/S=30 μm/30 μm and was further heated (post-baked) at 105° C. for 10 minutes. Then, the substrate was immersed into 2.38 mass % of an aqueous TMAH solution for 1 minute to be developed.
-
FIG. 7 shows optical microscope images of insulator layers after the development.FIG. 7( a) shows a result whenraw material solution 1 was used.FIG. 7( b) shows a result whenraw material solution 2 was used.FIG. 7( c) shows a result whenraw material solution 3 was used.FIG. 7( d) shows a result whenraw material solution 4 was used. - As shown in
FIG. 7 , in a case whereraw material solution 1 was used, in a case whereraw material solution 2 was used, and in a case whereraw material solution 4 was used, it was possible to obtain a good pattern having a width of 30 μm for all cases. On the other hand, in a case whereraw material solution 3 using tetraphenylol ethane glycidyl ether as the first cross-linking agent, it was impossible to perform the development by the aqueous TMAH solution at all, and it was impossible to obtain a pattern. -
FIGS. 8A to 8C are views showing a process of manufacturing the sandwich cell evaluated in Example 2. - First, an insulator layer and a base film were laminated (refer to
FIG. 8B ) on a silicon substrate (n-type abrasive product, ≦0.003Ω cm, manufactured by Nakayama Semiconductor Co., Ltd.) (refer toFIG. 8A ) by the following method. - Specifically,
raw material solution 2 of Example 1 described above was applied onto the silicon substrate by spin coating (1000 rpm×30 seconds). Then, the substrate was heated at 105° C. for 5 minutes to volatilize cyclohexanone (solvent), and a coating film of a curable composition was formed on the silicon substrate. - Next, the coating film was irradiated with i-line ray (365 nm) at an irradiation intensity of 700 mJ/cm2 through a photomask, was further heated (post-baked) at 120° C. for 10 minutes, and then immersed in 2.38 mass % of an aqueous TMAH solution for 1 minute to be developed, so as to form an insulator layer.
- The surface of the formed insulator layer was cleaned with atmospheric-pressure oxygen plasma, and then a silane coupling agent, which is a formation material of a base film for electroless plating, was formed into a film. In the present Example, as the silane coupling agent, 3-aminopropyltriethoxysilane having a primary amino group (KBE-903, manufactured by Shin-Etsu Silicone Co., Ltd.) was used. The silane coupling agent was dissolved in methyl isobutyl ketone to have a content of 0.2 mass % to obtain a liquid product, and then the liquid product was applied onto the substrate by spin coating (4000 rpm×30 seconds). Thereafter, the substrate coated with the liquid product was heated at 120° C. for 5 minutes to volatilize methyl isobutyl ketone (solvent), so as to form a base film.
- Then, hexamethyldisiloxane (hereinafter, sometimes referred to as “HMDS”) was applied onto the surface of the base film by spin coating (2000 rpm×30 seconds) and was heated at 120° C. for 5 minutes.
- Next, as shown in
FIG. 8C , an upper electrode was formed on the base film, and a sandwich cell was fabricated. - Specifically, a photoresist (SUMIRESIST PFI-34A, manufactured by Sumitomo Chemical Co., Ltd.) was applied to the surface of the base film coated with HMDS by spin coating (1000 rpm×30 seconds), and heated at 90° C. for 5 minutes, so as to form a resist layer.
- Next, the resist layer was irradiated with light emitted from a low-pressure mercury lamp through a quartz photomask for 5 minutes, heated (post-baked) at 110° C. for 5 minutes, and then immersed into 2.38 mass % of an aqueous TMAH solution for 90 seconds to thereby develop the resist layer, so as to form an opening in the resist layer.
- Next, the substrate provided with the resist layer having the opening was washed with water at room temperature for 30 seconds, and then immersed into a catalyst colloid solution for electroless plating (Melplate activator 7331, manufactured by Meltex Corporation) at room temperature for 60 seconds, so as to adhere a catalyst to the base film exposed through the opening of the resist layer.
- Next, the surface of the base film was washed with water, and then immersed into an electroless plating solution (Melplate NI-867, manufactured by Meltex Corporation) at 70° C. for 180 seconds to deposit nickel phosphorus on the catalyst adhered to the opening of the resist layer, so as to perform nickel-phosphorus plating.
- Next, the surface of the nickel-phosphorus plated portion (NiP electrode) was washed with water, and then immersed into a gold plating bath for substitution for 1 minute and further immersed into a plating bath for reduction for 3 minutes to thereby perform electroless gold plating on the upper surface of the NiP electrode and coat the upper surface of the NiP electrode with gold, so as to fabricate an upper electrode.
- Next, the surface of the upper electrode was water-washed and then dried. Then, the entire surface including the remaining resist layer was irradiated with i-line ray at an irradiation intensity of 300 mJ/cm2, and then immersed into 2.38 mass % of an aqueous TMAH solution to remove the resist layer. The resulting product was water-washed and dried to thereby fabricate a sandwich cell.
- The dielectric constant and insulation characteristics of the insulator layer were measured using the fabricated sandwich cell by the following method.
- (Dielectric Constant)
- The measurement of capacitance of the fabricated insulator layer was performed in a frequency range of 100 Hz to 1 MHz using an LCR meter (4284A, manufactured by Agilent Technologies).
-
FIG. 9 is a graph showing the frequency dependency of dielectric constant calculated from capacitance of the insulator layer of the fabricated sandwich cell. In the graph ofFIG. 9 , the horizontal axis indicates the measurement frequency (unit: Hz), and the vertical axis indicates the measured dielectric constant. - It was found that the insulator layer fabricated in Example 2 had a high dielectric constant greater than ∈=3.9, which is a dielectric constant of a SiO2 thermal oxide film (generally known inorganic insulator), with respect to any measurement frequency.
- (Insulating Characteristics)
- In the evaluation of insulating characteristics of the fabricated insulator layer, current density was measured using the Semiconductor Characterization System (4200-SCS, manufactured by KEITHLEY Co., Ltd.) when a voltage of 0 MV/cm to 2 MV/cm was applied.
-
FIG. 10 is a graph showing the evaluation result of insulating characteristics of the insulator layer of the fabricated sandwich cell. In the graph ofFIG. 10 , the horizontal axis indicates the measurement voltage (unit: MV/cm), and the vertical axis indicates the measured current density (A/cm2). - Most of general resin-based insulators have a current density on the order of 1×10−7 A/cm2. On the other hand, it was found that the current density of the insulator layer fabricated in Example 2 was a value on the order of 1×10−8 A/cm2 with respect to any measurement voltage and the insulator layer had improved insulation properties.
- In Example 3, 3-aminopropyltriethoxysilane (KBE903, manufactured by Shin-Etsu Silicone Co., Ltd.), which is an amine-based silane coupling agent, was dissolved in methyl isobutyl ketone (hereinafter, sometimes referred to as MIBK) to have 0.2 mass % to prepare a liquid product, and this liquid product was used in forming a base film.
- The surface of a PET substrate (Model number: A-4100 (no coat), manufactured by Toyobo Co., Ltd.) was cleaned with atmospheric-pressure oxygen plasma, and then the above liquid product was applied onto the PET substrate by spin coating (4000 rpm×30 seconds). Thereafter, the PET substrate coated with the liquid product was heated at 120° C. for 10 minutes, so as to form a base film.
- Next, a resist material (SUMIRESIST PFI-34A6, manufactured by Sumitomo Chemical Co., Ltd.) was applied to the surface of the substrate provided with the base film by spin coating, and then heated (prebaked) at 90° C. for 5 minutes, so as to form a resist layer. The spin coating was performed under a condition of 1000 rpm and 30 seconds, and a resist layer having a thickness of about 1 μm was formed.
- Next, the resist layer was exposed with ultraviolet having an intensity of 25 mW/cm2 through a photomask for 5 seconds, heated (post-baked) at 110° C. for 5 minutes, and then immersed into 2.38 mass % of an aqueous TMAH solution for 2 minutes to thereby develop a mask pattern on the resist layer, so as to form an opening.
- Next, the substrate provided with the resist layer having the opening was ultrasonically water-washed at room temperature for 30 seconds, and then immersed into a catalyst colloid solution for electroless plating (Melplate activator 7331, manufactured by Meltex Corporation) at room temperature for 60 seconds, so as to adhere a catalyst (Pd metal) to the base film exposed through the opening of the resist layer.
- Next, the surface of the base film was washed with water, and then immersed into an electroless plating solution (Melplate NI-867, manufactured by Meltex Corporation) at 73° C. for 60 seconds to deposit nickel phosphorus on the catalyst adhered to the opening of the resist layer, so as to perform nickel-phosphorus plating.
- Next, the surface of the resulting product was water-washed and then dried. Then, the entire surface including the remaining resist layer was exposed to ultraviolet having an intensity of 25 mW/cm2 for 1 minute, and then immersed into ethanol for 1 minute to thereby remove the resist layer, so as to fabricate a gate electrode.
-
FIG. 11 shows photographs of the gate electrode.FIG. 11 (a) is an overall photograph of the substrate provided with the gate electrode.FIG. 11 (b) is an enlarged photograph of the gate electrode using an optical microscope. FromFIG. 11 , it is found that a slightly uneven flat gate electrode is formed. - (Fabrication of Insulator Layer)
- In order to improve the adhesiveness between the gate electrode and the insulator layer to be formed, the substrate provided with the gate electrode was immersed into an aqueous NaOH solution of 50 g/L, and a degreasing process of the surface was performed.
- Next, an aqueous solution of a silane coupling agent (3-glycidoxypropyl triethoxysilane, KBM-403, manufactured by Shin-Etsu Silicone Co., Ltd.) was applied to the whole surface, on which the gate electrode was formed, of the PET substrate by spin coating, and the substrate was heated at 120° C. for 10 minutes. Thereafter, the
raw material solution 2 of Example 1 was applied onto the surface by spin coating (1000 rpm×30 seconds). Then, the resulting product was heated at 105° C. for 5 minutes to volatilize cyclohexanone (solvent), so as to form a coating film of a curable composition. - Next, the coating film was irradiated with ultraviolet for 25 seconds through a mask having an opening in the portion forming an insulator layer. In order to accelerate curing, the ultraviolet-irradiated coating film was heated at 120° C. for 10 minutes, and then immersed into 2.38 mass % of an aqueous TMAH solution for 1 minute to form a patterned film. Then, the patterned film was heat-treated at 120° C. for 30 minutes to form an insulator layer.
-
FIG. 12 is a photograph of the insulator layer.FIG. 12 (a) is an overall photograph of the substrate provided with the insulator layer.FIG. 12 (b) is an enlarged photograph of the insulator layer of the region surrounded by the dash line ofFIG. 12 (a). As a result of the observation, it was confirmed that the insulator layer was formed without unevenness and a slightly uneven flat insulator layer was formed by development with an alkaline solution. - (Fabrication of Source and Drain Electrodes)
- Next, the fabrication and electroless plating of the base film and the resist layer were performed on the entire surface of the side where the insulator layer was formed on the PET substrate in the same manner as the above-mentioned process (fabrication of the gate electrode), so as to form a patterned NiP electrode on the insulator layer. The NiP electrode corresponds to the first electrode and the third electrode described in the embodiment.
- In addition, after stripping the resist, the NiP electrode was immersed into a gold plating bath for substitution for 1 minute and further immersed into a plating bath for reduction for 3 minutes to thereby perform electroless gold plating to coat the surface of the NiP electrode with gold, so as to fabricate a source electrode and a drain electrode. The gold film coating the surface of the NiP electrode corresponds to the second electrode and the fourth electrode described in the embodiment.
-
FIG. 13 shows the photographs of the source electrode and the drain electrode. -
FIG. 13 (a) is an overall photograph of the substrate provided with the source electrode and the drain electrode.FIG. 13 (b) is an enlarged photograph of the source electrode and the drain electrode. As a result of the observation, in the surface of the insulator layer of the present invention, it was confirmed that a good source electrode and a good drain electrode were formed. Further, damage to the insulator layer in the electroless plating process was not confirmed. - (Fabrication of Organic Semiconductor Layer)
- A toluene solution of 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS pentacene) (716006, manufactured by Sigma-Aldrich, Inc.) was dropped between the source electrode and the drain electrode under a nitrogen atmosphere, and naturally dried to thereby form a semiconductor layer, so as to fabricate a transistor. Here, the adjustment of the TIPS pentacene/toluene solution used was also performed under a nitrogen atmosphere.
-
FIG. 14 shows an enlarged photograph of the source electrode and the drain electrode having the surface provided with the organic semiconductor layer. It was observed that crystals of TIPS pentacene were formed between the source electrode and the drain electrode. - (Evaluation of Transistor)
- The transistor characteristics of the fabricated transistor were evaluated using the Semiconductor Characterization System (4200-SCS, manufactured by KEITHLEY Co., Ltd.).
-
FIG. 15 shows a graph showing the transistor characteristics of the transistor fabricated by a wet process using the above-mentioned method. In the graph ofFIG. 15 , the horizontal axis indicates a voltage applied between the source electrode and the drain electrode, and the vertical axis indicates a current value detected by the drain electrode. One of the plurality of results shown inFIG. 15 corresponds to each of the gate voltages applied to a gate electrode. - A gate voltage of 0 V to −40 V was applied to the gate electrode of the obtained organic thin film transistor, and a voltage of 0 V to −50 V was applied between source and drain to flow electric current. As a result, as shown in
FIG. 15 , holes are induced in the channel region (between source and drain) of a semiconductor layer, and the fabricated transistor was operated as a p-type transistor. - From the above results, it was found that, when a composition according to the aspect of the present invention was used to form an insulator layer by development with an alkaline solution, it was possible to fabricate a transistor (organic thin film transistor) in an all wet process. Further, it was found that, when the base film was formed using a silane coupling agent (primary amine), the treatment using an accelerator was not required, and the operation of electroless plating was simplified. Further, it was found that, since the base film formed using a silane coupling agent was a flat film having very small unevenness, at the time of forming a laminated structure, uneven shape was not imparted to the configuration of the upper layer of the base film, and it was possible to fabricate a high-performance transistor. Moreover, it was found that, since it was possible to coat the entire surface of source and drain electrodes with a metal material having a work function that provides a small energy gap with HOMO of the formation material of the organic semiconductor layer by using an electroless plating method, it was possible to provide a transistor having small electrical contact resistance between the organic semiconductor layer and the source and drain electrodes.
- From the above results, the usefulness of the present invention has been confirmed.
Claims (33)
1. A composition comprising:
(a) an organic compound having a hydroxy group;
(b) a first cross-linking agent that is at least one organic silicon compound selected from the group including
(b-1) an organic silicon compound including a siloxane bond in the molecule and having three or more cyclic ether groups in the molecule,
(b-2) a chain organic silicon compound including two or more siloxane bonds in the molecule and having two or more cyclic ether groups in the molecule,
(b-3) a cyclic organic silicon compound including a siloxane unit (D unit) represented by R1R2SiO2/2 in the molecule, any one of or both of R1 and R2 being a cyclic ether group, and having four or more cyclic ether groups bonded to a silicon atom of the D unit in the molecule, and
(b-4) a cyclic organic silicon compound including a siloxane unit (T unit) represented by R3SiO3/2 in the molecule, R3 being a cyclic ether group, and having two or more cyclic ether groups in the molecule; and
(c) a photocationic polymerization initiator.
2. The composition according to claim 1 , wherein
the two or more cyclic ether groups included in the first cross-linking agent are any one of or both of a group including an epoxy ring and a group including an oxetanyl ring.
3. The composition according to claim 1 , further comprising:
(d) a second cross-linking agent that is an organic compound having two or more cyclic ether groups.
4. The composition according to claim 3 , wherein
a ratio of a sum of mass of the first cross-linking agent and the second cross-linking agent to a total sum of mass of the organic compound having a hydroxy group, the first cross-linking agent, and the second cross-linking agent is 40 mass % to 90 mass %, and
a ratio of mass of the second cross-linking agent to the total sum is 5 mass % to 30 mass %.
5. The composition according to claim 3 , wherein
the second cross-linking agent is a compound having an aromatic ring.
7. The composition according to claim 6 , wherein
the cyclic ether group included in the second cross-linking agent is any one of or both of a group including an epoxy ring and a group including an oxetanyl ring.
8. The composition according to claim 1 , wherein
the organic compound having a hydroxy group includes a phenolic hydroxy group.
9. A method of manufacturing a laminate, comprising:
applying a solution containing the composition according to claim 1 over a conductive layer to form a coating film;
selectively irradiating the coating film with light including light having an absorption wavelength of the photocationic polymerization initiator included in the coating film to form a latent image in the light-irradiated region of the coating film; and
developing the coating film with an alkaline solution to form an insulator layer.
10. The method of manufacturing a laminate according to claim 9 , further comprising:
prior to forming the coating film, applying a surface treatment on at least a region to be provided with the coating film by using a silane coupling agent having a cyclic ether group.
11. A laminate, comprising:
a conductive layer; and
an insulator layer formed by cationic-polymerization of the composition according to claim 1 .
12. The laminate according to claim 11 ,
wherein the conductive layer is covered with the insulator layer.
13. A method of manufacturing a transistor, comprising:
forming a gate electrode on a substrate;
applying a solution including the composition according to claim 1 over the gate electrode to form a coating film;
selectively irradiating the coating film with light including light having an absorption wavelength of a photocationic polymerization initiator included in the coating film to form a latent image in the light-irradiated region of the coating film;
developing the coating film with an alkaline solution to form an insulator layer; and
forming a source electrode and a drain electrode on the surface of a layer including the insulator layer.
14. The method of manufacturing a transistor according to claim 13 , further comprising:
prior to forming the coating film, applying a surface treatment on at least a region to be provided with the coating film by using a first silane coupling agent having a cyclic ether group.
15. The method of manufacturing a transistor according to claim 13 ,
wherein at least one of the gate electrode, the source electrode, and the drain electrode is formed by:
applying a formation material containing a second silane coupling agent having a group capable of capturing a metal, which is an electroless plating catalyst, to form a base film; and
capturing the metal on the surface of the base film and then performing electroless plating.
16. The method of manufacturing a transistor according to claim 15 ,
wherein the source electrode and the drain electrode are formed by:
forming a source base film and a drain base film, each being the base film; and
then capturing the metal on the surface of each of the source base film and the drain base film to perform electroless plating.
17. The method of manufacturing a transistor according to claim 16 ,
wherein the source base film and the drain base film are formed as a continuous film.
18. The method of manufacturing a transistor according to claim 15 ,
wherein the gate electrode is formed by:
forming a gate base film, which is the base film; and
then capturing the metal on the surface of the gate base film to perform electroless plating.
19. The method of manufacturing a transistor according to claim 15 ,
wherein the second silane coupling agent has an amino group.
20. The method of manufacturing a transistor according to claim 19 ,
wherein the second silane coupling agent is a primary amine or a secondary amine.
21. The method of manufacturing a transistor according to claim 15 ,
wherein the layer including the insulator layer includes: the insulator layer; and
an organic semiconductor layer disposed on the insulator layer and having a surface on which the source electrode and the drain electrode are formed.
22. The method of manufacturing a transistor according to claim 15 , comprising:
forming the source electrode and the drain electrode; and
then forming an organic semiconductor layer that is in contact with surfaces of the source electrode and the drain electrode that face each other.
23. The method of manufacturing a transistor according to claim 21 , comprising, prior to forming the source electrode and the drain electrode:
forming a resist layer having an opening corresponding to the source electrode and the drain electrode and capturing the metal on the surface of the base film formed on the surface exposed at least in the opening;
performing first electroless plating and then removing the resist layer; and
performing second electroless plating on the surface of an electrode formed by the first electroless plating to form the source electrode and the drain electrode,
wherein the energy level difference between the work function of a metal material used in the second electroless plating and the energy level of a molecular orbital used for electron transfer in a formation material of the organic semiconductor layer is smaller than the energy level difference between the work function of a metal material used in the first electroless plating and the energy level of the molecular orbital.
24. The method of manufacturing a transistor according to claim 13 ,
wherein the substrate is made of a non-metallic material.
25. The method of manufacturing a transistor according to claim 24 ,
wherein the substrate is made of a resin material.
26. The method of manufacturing a transistor according to claim 25 ,
wherein the substrate has flexibility.
27. A transistor, comprising:
a source electrode and a drain electrode;
a gate electrode provided corresponding to a channel between the source electrode and the drain electrode;
a semiconductor layer provided in contact with the source electrode and the drain electrode; and
an insulator layer disposed between the source electrode and the gate electrode and between the drain electrode and the gate electrode,
wherein the insulator layer is formed by cationic polymerization of the composition according to claim 1 .
28. The transistor according to claim 27 ,
wherein at least one of the gate electrode, the source electrode, and the drain electrode is laminated on a base film containing a silane coupling agent having a group capable of capturing a metal, which is an electroless plating catalyst.
29. The transistor according to claim 27 ,
wherein the semiconductor layer is an organic semiconductor layer.
30. The transistor according to claim 29 ,
wherein the source electrode has a first electrode and a second electrode formed to cover the first electrode;
the drain electrode has a third electrode and a fourth electrode formed to cover the third electrode;
the energy level difference between the work function of a formation material of the second electrode and the energy level of a molecular orbital used for electron transfer in a formation material of the organic semiconductor layer is smaller than the energy level difference between the work function of a formation material of the first electrode and the energy level of the molecular orbital; and
the energy level difference between the work function of a formation material of the fourth electrode and the energy level of the molecular orbital used for electron transfer in the formation material of the organic semiconductor layer is smaller than the energy level difference between the work function of a formation material of the third electrode and the energy level of the molecular orbital.
31. The transistor according to claim 27 , which is formed on a substrate made of a non-metallic material.
32. The transistor according to claim 31 ,
wherein the substrate is made of a resin material.
33. The transistor according to claim 32 ,
wherein the substrate has flexibility.
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US10374178B2 (en) * | 2014-06-11 | 2019-08-06 | Eastman Kodak Company | Method for making devices having dielectric layers with thiosulfate-containing polymers |
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JP6701630B2 (en) * | 2015-06-02 | 2020-05-27 | 日立化成株式会社 | Thermosetting resin composition, prepreg, laminated board and printed wiring board |
JP6810410B2 (en) * | 2017-02-27 | 2021-01-06 | 地方独立行政法人大阪産業技術研究所 | Manufacturing method of organic insulating thin film, organic transistor, capacitor and organic insulating thin film |
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