Semiconductor element, manufacturing method of the same, circuit using the same, wireless communication device, thin film transistor array, and sensor

Abstract

To provide a semiconductor element having an insulating layer with a high processing stability and a chemical resistance in addition to a good continuous operation stability.SOLUTION: A semiconductor element comprises: at least a substrate; a first electrode; a second electrode; a semiconductor layer in contact with both the first electrode and the second electrode; an insulating layer in contact with the semiconductor layer; and a third electrode in contact with the insulating layer on a side opposite to the insulating layer with respect to the semiconductor layer. The insulating layer contains the following (a) that is titanium compound particles, and (b) that is a polymer having the following structures (b1) that is an addition reaction structure of an alkenyl group, an acrylic group, or a methacrylic group, (b2) that is a 1,2-dihydroxyethyl group, a 1,2-dihydroxyethylene group, a 1,3-dihydroxypropyl group, a 1,3-dihydroxypropylene group, (b3) that is a carboxyl group, a sulfo group, a thiol group, a phenolic hydroxyl group, and or an organic group containing at least two of derivatives thereof. However, when the derivative is a cyclic condensed structure of two of a carboxyl group, a sulfo group, a thiol group and the phenolic hydroxyl group, the (b3) is an organic group having at least one of the cyclic condensed structures.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a semiconductor element, a manufacturing method thereof, a circuit using the semiconductor element, a wireless communication device, a thin film transistor array, and a sensor. [Background technology]

[0002] In recent years, with the aim of realizing low-cost, large-area, flexible, and bendable electronic devices, field-effect transistors (FETs) using semiconductor materials such as carbon nanotubes (CNTs), graphene, organic semiconductors, and oxide semiconductors, which can be applied using coating techniques such as inkjet technology and screen printing, have been actively investigated. Examples of electronic devices include displays, wireless communication devices using RFID (Radio Frequency IDentification) technology, and sensors, and FETs are used in the logic circuits and sensor sections within these IC chips.

[0003] The insulating layer, one of the components of an FET, is known as an important component related to transistor characteristics such as on-current, off-current, threshold voltage, and subthreshold swing when functioning as a gate insulating layer. Furthermore, when combining FETs to form a circuit, operational stability during continuous operation of the FET is an important factor. If the FET's operation is unstable during continuous operation, incorrect signal processing will occur, preventing the circuit from functioning correctly. The operational stability of an FET is significantly affected by carrier traps within the insulating layer and at the insulating / semiconductor layer interface, so the insulating layer plays an important role.

[0004] On the other hand, when forming a circuit by combining FETs as described above, it is necessary to form contact holes in the insulating layer to electrically connect the electrodes located above and below the insulating layer. A known method for forming such hole patterns is to use a photosensitive resin composition that can be patterned by photolithography as an insulating layer (see, for example, Patent Document 1). Furthermore, when forming a semiconductor layer or an electrode on an insulating layer by coating in the process of forming an FET, the insulating layer must be resistant to solvents used in the semiconductor layer or the electrode, and chemicals used in processing the semiconductor layer or the electrode, and therefore the insulating layer must have high chemical resistance. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2019 / 065561 Summary of the Invention [Problem to be solved by the invention]

[0006] Patent Document 1 discloses that the use of a resin composition containing a polymer to which inorganic particles are bonded as an insulating layer improves the transistor characteristics of semiconductor elements and enables the formation of a patterned insulating layer. However, there is no disclosure regarding the operational stability of semiconductor elements during continuous operation. Furthermore, there is room for further improvement in the processing stability of the insulating layer, such as peeling of the insulating layer on the lower electrode during the process of forming a hole pattern in the insulating layer, and in the chemical resistance of the insulating layer during the process of forming the semiconductor layer and electrodes.

[0007] SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a semiconductor device having an insulating layer that has high processing stability and chemical resistance in addition to good continuous operation stability. [Means for solving the problem]

[0008] That is, the present invention has the following configuration. [1] A semiconductor element including at least a substrate, a first electrode, a second electrode, a semiconductor layer in contact with both the first electrode and the second electrode, an insulating layer in contact with the semiconductor layer, and a third electrode in contact with the insulating layer on the opposite side of the semiconductor layer from the insulating layer, The insulating layer comprises the following (a) and (b); (a) Titanium compound particles (b) Polymers having the following structures (b1), (b2), and (b3): (b1) Addition reaction structure of an alkenyl group, an acrylic group, or a methacrylic group (b2) a 1,2-dihydroxyethyl group, a 1,2-dihydroxyethylene group, a 1,3-dihydroxypropyl group, or a 1,3-dihydroxypropylene group (b3) an organic group containing at least two of a carboxyl group, a sulfo group, a thiol group, a phenolic hydroxyl group, or a derivative thereof; provided that, when the derivative has a cyclic condensation structure formed by two of the carboxyl group, the sulfo group, the thiol group, and the phenolic hydroxyl group, (b3) is an organic group having at least one of the cyclic condensation structures. A semiconductor element comprising: [2] The semiconductor element according to [1], wherein the (b) polymer is polysiloxane. [3] The semiconductor element according to [2], wherein the polysiloxane has at least structural units represented by general formula (1), general formula (2), and general formula (3).

[0009] [ka]

[0010] [ka]

[0011] [ka]

[0012] (In the general formula (1), the general formula (2) and the general formula (3), A 1 represents an organic group containing an addition reaction structure of an alkenyl group, an acrylic group, or a methacrylic group. 2 represents an organic group having at least one structure selected from the group consisting of a 1,2-dihydroxyethyl group, a 1,2-dihydroxyethylene group, a 1,3-dihydroxypropyl group, and a 1,3-dihydroxypropylene group. 3 represents an organic group containing at least two of a carboxyl group, a sulfo group, a thiol group, a phenolic hydroxyl group, or a derivative thereof, provided that when the derivative has a cyclic condensation structure formed by two of the carboxyl group, the sulfo group, the thiol group, and the phenolic hydroxyl group, A 3 R represents an organic group having at least one cyclic condensed structure. 1 , R 3 and R 5 R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a heterocyclic group, an aryl group, a heteroaryl group, or an alkenyl group. 2 , R 4 and R 6 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, or a silyl group. m, n, and o each independently represent 0 or 1. [4] The semiconductor device according to any one of [1] to [3], wherein the (a) titanium compound particles are inorganic titanium compound particles. [5] The semiconductor element according to [4], wherein the inorganic titanium compound particles are titanic acid compound particles. [6] The semiconductor element according to any one of [1] to [5], wherein the content of the (a) titanium compound particles is 60% by weight or more when the total of the (a) titanium compound particles and the (b) polymer is 100% by weight. [7] The semiconductor element according to any one of [1] to [6], wherein the semiconductor layer contains nanocarbon. [8] The semiconductor element according to [7], wherein the nanocarbon is a carbon nanotube. [9] A method for manufacturing a semiconductor device according to any one of [1] to [8], comprising the following (Step 1) to (Step 3):

[0013] (Step 1) A step of forming a conductive pattern on a substrate (Step 2) A step of applying a solution containing at least titanium compound particles and (b) a polymer or its precursor onto the substrate on which the conductive pattern has been formed, drying the solution, obtaining a coating film, and then curing the coating film to form an insulating layer. (Step 3) A step of forming a conductive pattern on the insulating layer.

[10] A method for manufacturing a semiconductor device according to any one of [1] to [8], comprising the following (Step 1') to (Step 3'):

[0014] (Step 1') Step of forming a conductive pattern on a substrate (Step 2') A step of applying a solution containing at least titanium compound particles and (b) a polymer or a precursor thereof to the substrate on which the conductive pattern has been formed, drying the solution to obtain a coating film, and then irradiating the coating film with actinic rays through a photomask and developing the coating film to form a pattern having openings on the conductive pattern or the substrate, thereby forming an insulating layer having openings. (Step 3') A step of forming a conductive pattern on the insulating layer.

[11] A circuit comprising the semiconductor element according to any one of [1] to [8].

[12] A wireless communication device having at least the circuit according to

[11] and an antenna.

[13] A thin film transistor array having the semiconductor element according to any one of [1] to [8].

[14] A sensor having the semiconductor element according to any one of [1] to [8]. [Effects of the Invention]

[0015] According to the present invention, a semiconductor device can be obtained that has an insulating layer that has not only good continuous operation stability but also high processing stability and chemical resistance. [Brief explanation of the drawings]

[0016] [Figure 1]Schematic cross-sectional view showing an example of the configuration of a semiconductor element [Figure 2] Schematic cross-sectional view showing an example of the configuration of a semiconductor element [Figure 3] Schematic cross-sectional view showing an example of the configuration of a semiconductor element [Figure 4] A schematic cross-sectional view showing an example of a circuit configuration combining semiconductor elements. [Figure 5] Schematic diagram showing an example of the configuration of a thin-film transistor array DETAILED DESCRIPTION OF THE INVENTION

[0017] Hereinafter, preferred embodiments of the semiconductor element, its manufacturing method, a circuit using the semiconductor element, a wireless communication device, a thin film transistor array, and a sensor according to the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and can be modified in various ways depending on the purpose and application.

[0018] (semiconductor element) A semiconductor element according to an embodiment of the present invention is a semiconductor element comprising at least a substrate, a first electrode, a second electrode, a semiconductor layer in contact with both the first electrode and the second electrode, an insulating layer in contact with the semiconductor layer, and a third electrode in contact with the insulating layer on the opposite side of the semiconductor layer from the insulating layer, wherein the insulating layer contains (a) titanium compound particles and (b) a polymer having the structures of (b1), (b2), and (b3) described below.

[0019] 1 is a schematic cross-sectional view showing a semiconductor device according to a first embodiment of the present invention. The semiconductor device 10 according to the first embodiment has a gate electrode 2 formed on an insulating substrate 1, a gate insulating layer 3 covering the gate electrode 2, a source electrode 5 and a drain electrode 6 provided thereon, and a semiconductor layer 4 provided between the electrodes.

[0020] 1, the semiconductor element 10 can function as a field-effect transistor. That is, the first electrode corresponds to the source electrode 5, the second electrode corresponds to the drain electrode 6, and the third electrode corresponds to the gate electrode 2. This structure is a so-called bottom-gate / top-contact structure, in which the gate electrode is disposed below the semiconductor layer and the source electrode and drain electrode are disposed on the top surface of the semiconductor layer.

[0021] 2 is a schematic cross-sectional view showing a semiconductor device according to a second embodiment of the present invention. The semiconductor device 20 according to the second embodiment has a source electrode 15 and a drain electrode 16 formed on an insulating substrate 11, a semiconductor layer 14 provided between the electrodes, a gate insulating layer 13 covering the electrodes, and a gate electrode 12 provided on the semiconductor layer.

[0022] 2, the semiconductor element 20 can function as a field-effect transistor. That is, the first electrode corresponds to the source electrode 15, the second electrode corresponds to the drain electrode 16, and the third electrode corresponds to the gate electrode 12. This structure is a so-called top-gate bottom-contact structure in which the gate electrode is disposed above the semiconductor layer, and the source electrode and drain electrode are disposed below the semiconductor layer.

[0023] When a semiconductor element is made to function as a field effect transistor, the structure of the semiconductor element may be a bottom gate / bottom contact structure, a top gate / top contact structure, or the like, in addition to those shown in FIGS.

[0024] 3 is a schematic cross-sectional view showing a semiconductor device according to a third embodiment of the present invention. The semiconductor device 30 according to the third embodiment has a third electrode 22 formed on an insulating base material 21, an insulating layer 23 covering the third electrode 22, a cathode 25 and an anode 26 provided thereon, a semiconductor layer 24 provided between these electrodes, and a fourth electrode 29 electrically connecting the third electrode 22 and the first electrode 25.

[0025] 3, the semiconductor element 30 can function as a diode. That is, the first electrode corresponds to the cathode 25, and the second electrode corresponds to the anode 26. This structure is a diode-connected transistor.

[0026] The structure of the semiconductor element according to the embodiment of the present invention is not limited to these, and the following description is common regardless of the structure of the semiconductor element unless otherwise specified.

[0027] (insulating layer) The insulating layer of the present invention contains (a) titanium compound particles and (b) a polymer having the following structures (b1), (b2) and (b3) (hereinafter sometimes simply referred to as (b) polymer).

[0028] (b1) Addition reaction structure of an alkenyl group, an acrylic group, or a methacrylic group (b2) a 1,2-dihydroxyethyl group, a 1,2-dihydroxyethylene group, a 1,3-dihydroxypropyl group, or a 1,3-dihydroxypropylene group (b3) An organic group containing at least two of a carboxyl group, a sulfo group, a thiol group, a phenolic hydroxyl group, or a derivative thereof, provided that when the derivative has a cyclic condensation structure formed by two of the carboxyl group, the sulfo group, the thiol group, and the phenolic hydroxyl group, (b3) is an organic group having at least one of the cyclic condensation structures.

[0029] The addition reaction structure of an alkenyl group, an acrylic group, or a methacrylic group is one in which an alkenyl group, an acrylic group, or a methacrylic group undergoes an addition reaction with itself and / or with an alkenyl group, an acrylic group, or a methacrylic group contained in another radically polymerizable compound. The addition reaction is a crosslinking reaction accompanying radical polymerization caused by light or heat.

[0030] By including (a) titanium compound particles and (b) a polymer in the insulating layer, it is possible to obtain a semiconductor device having an insulating layer with high processing stability and chemical resistance, in addition to good continuous operation stability. Processing stability here refers to the ability to obtain a uniformly processed film with few defects caused by peeling of the insulating layer on the electrode, and chemical resistance refers to the resistance of the insulating layer to solvents used in the semiconductor layer and electrodes and to chemical solutions used in processing the semiconductor layer and electrodes.

[0031] The insulating layer of the present invention can achieve the above-mentioned effects because it achieves the following three points: (i) there are few locations inside the insulating layer or at the interface between the insulating layer and the semiconductor layer where carrier traps can occur, which has the effect of improving the continuous operation stability of the element; (ii) the insulating layer has high adhesion to the electrode, which has the effect of improving processing stability; and (iii) there is strong interaction between (a) the titanium compound particles and (b) the polymer, which has the effect of improving resistance to chemical solutions.

[0032] Regarding (i), it is thought that the (b2) structure easily interacts with (a) titanium compound particles, particularly at highly active sites on the particle surface where carrier trapping is likely to occur, thereby suppressing carrier trapping, and furthermore, that there are few sites inside the (a) titanium compound particles where carrier trapping is likely to occur. Regarding (ii), it is thought that the (b2) structure easily interacts with the electrode. Regarding (iii), it is thought that the (b1) structure makes the (b) polymer structure stronger, and furthermore, the (b2) structure easily interacts with (a) titanium compound particles, resulting in a high ability to immobilize the (a) titanium compound particles to the (b) polymer.

[0033] ((b) Polymer) The (b) polymer is not particularly limited as long as it exhibits sufficient insulating properties to allow the semiconductor device to function normally, and the polymer skeleton may be linear, cyclic, or branched. Furthermore, the (b) polymer preferably has structures (b1), (b2), and (b3) in its side chains. This can further enhance the effects of (i), (ii), and (iii) described above.

[0034] Furthermore, the (b) polymer may have a crosslinkable functional group other than the structures of (b1), (b2), and (b3), a polar functional group, or a functional group that controls various properties of the (b) polymer introduced into its side chain.

[0035] Examples of the (b) polymer that can be used include polysiloxane, polyamide, polyamideimide, polyimide, polybenzimidazole, polyvinyl alcohol, polyvinylphenol, polyacetal, polycarbonate, polyarylate, polyphenylene sulfide, polyethersulfone, polyetherketone, polyphthalamide, polyethernitrile, polymethyl methacrylate, polymethacrylamide, fluorine-based resin, polystyrene, polyester, aromatic polyether, novolac resin, phenolic resin, acrylic resin, olefin resin, alicyclic olefin resin, vinyl chloride resin, epoxy resin, melamine resin, and urea resin. These polymers can also be copolymerized or mixed with other polymers.

[0036] From the viewpoints of (a) interaction with the titanium compound particles and chemical resistance, (b) the polymer is preferably polysiloxane, acrylic resin, or polyimide, and more preferably polysiloxane.

[0037] It is more preferable that the polysiloxane has at least structural units represented by general formula (1), general formula (2) and general formula (3). By using polysiloxanes having these structures, the effects of (i), (ii) and (iii) described above can be further enhanced. The reasons for this are considered as follows: In the insulating layer of the semiconductor element according to the embodiment of the present invention, the structures of general formula (1), general formula (2) and general formula (3) can form a large number of cross-linking points within the (b) polymer and between the (b) polymers. Furthermore, A in the structure of general formula (2) 2 The interaction between the (a) titanium compound particles and the (b) polymer creates numerous cross-linked structures within and between the (b) polymers. As a result, the density of the insulating layer can be increased. This reduces the number of areas where carrier traps can occur within the insulating layer, further improving its resistance to chemical solutions. In addition, the increased density of the insulating layer suppresses peeling of the insulating layer on the electrode, thereby improving the processing stability of the insulating layer.

[0038] [ka]

[0039] [ka]

[0040] [ka]

[0041] In the general formula (1), the general formula (2) and the general formula (3), A 1 represents an organic group containing an addition reaction structure of an alkenyl group, an acrylic group, or a methacrylic group. 2 represents an organic group having at least one structure selected from the group consisting of a 1,2-dihydroxyethyl group, a 1,2-dihydroxyethylene group, a 1,3-dihydroxypropyl group, and a 1,3-dihydroxypropylene group. 3represents an organic group containing at least two of a carboxyl group, a sulfo group, a thiol group, a phenolic hydroxyl group, or a derivative thereof, provided that when the derivative has a cyclic condensation structure formed by two of the carboxyl group, the sulfo group, the thiol group, and the phenolic hydroxyl group, A 3 R represents an organic group having at least one cyclic condensed structure. 1 , R 3 and R 5 R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a heterocyclic group, an aryl group, a heteroaryl group, or an alkenyl group. 2 , R 4 and R 6 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, or a silyl group. m, n, and o each independently represent 0 or 1.

[0042] Among the derivatives of carboxyl groups, sulfo groups, thiol groups, or phenolic hydroxyl groups, examples of acyclic condensed structures include carboxylic acid esters, sulfonate esters, thioesters, thioethers, and phenyl ethers with hydrocarbon groups or silyl groups, as well as carboxylic acid anhydrides and amide compounds or imide compounds formed by the reaction of carboxylic acid anhydrides with amine compounds.

[0043] Examples of the cyclic condensation structure formed by two of a carboxyl group, a sulfo group, a thiol group, and a phenolic hydroxyl group include a cyclic acid anhydride structure, a cyclic ester structure, a cyclic thioester structure, a cyclic ether structure, and a cyclic thioether structure. The condensation includes both intramolecular condensation and intermolecular condensation.

[0044] The alkyl group refers to a saturated aliphatic hydrocarbon group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group. The alkyl group may or may not have a substituent, and the substituent may further have a substituent. The explanation regarding these substituents is common to the following descriptions unless otherwise specified. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 20, more preferably 1 to 8, from the viewpoints of availability and cost.

[0045] The alkenyl group refers to an unsaturated aliphatic hydrocarbon group containing a double bond, such as a vinyl group or a butadienyl group. The alkenyl group may or may not have a substituent. The number of carbon atoms in the alkenyl group is not particularly limited, but is preferably in the range of 2 to 20.

[0046] The cycloalkyl group refers to a saturated alicyclic hydrocarbon group such as a cyclopropyl group, a cyclohexyl group, a norbornyl group, or an adamantyl group. The cycloalkyl group may or may not have a substituent. The number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably in the range of 3 to 20.

[0047] The heterocyclic group refers to a group derived from an aliphatic ring having atoms other than carbon atoms in the ring, such as a pyran ring, a piperidine ring, or an amide ring, and may or may not have a substituent. The number of carbon atoms in the heterocyclic group is not particularly limited, but is preferably in the range of 2 to 20.

[0048] The aryl group refers to an aromatic hydrocarbon group such as a phenyl group, a naphthyl group, a biphenyl group, an anthracenyl group, a phenanthryl group, a terphenyl group, or a pyrenyl group. The aryl group may or may not have a substituent. The number of carbon atoms in the aryl group is not particularly limited, but is preferably in the range of 6 to 40.

[0049] The heteroaryl group refers to an aromatic group having one or more atoms other than carbon in the ring, such as a furanyl group, a thiophenyl group, a benzofuranyl group, a dibenzofuranyl group, a pyridyl group, or a quinolinyl group. The heteroaryl group may or may not have a substituent. The number of carbon atoms in the heteroaryl group is not particularly limited, but is preferably in the range of 2 to 30.

[0050] The silyl group is not particularly limited as long as it is a functional group with a silicon atom as the bonding point, and may have a hydrogen atom, an organic group, and a silyl group, or may be bonded via an oxygen atom. Polysiloxanes are also possible.

[0051] In the present invention, the organic group includes the alkyl group, cycloalkyl group, heterocyclic group, It represents an aryl group, a heteroaryl group, or an alkenyl group. Among these, from the viewpoint of availability, an alkyl group, a cycloalkyl group, an aryl group, and an alkenyl group are preferred, an alkyl group and an aryl group are more preferred, and an alkyl group is even more preferred.

[0052] Examples of the structural unit represented by general formula (1) include 3-acryloxypropyldimethoxymethylsilane, 3-methacryloxypropyldimethoxymethylsilane, styryldimethoxymethylsilane, styreneethyldimethoxymethylsilane, 3-acryloxypropyldiethoxymethylsilane, 3-methacryloxypropyldiethoxymethylsilane, styryldiethoxymethylsilane, styreneethyldiethoxymethylsilane, 3-acryloxypropyldimethoxyphenylsilane, 3-methacryloxypropyldimethoxyphenylsilane, styryldimethoxyphenylsilane, styreneethyldimethoxyphenylsilane, 3-acryloxypropyldiethoxyphenylsilane, 3-methacryloxypropyldiethoxyphenylsilane, styryldiethoxyphenylsilane, styreneethyldiethoxyphenylsilane, Structural units obtained by addition reaction of a structure derived from styrene-ethyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, styryltrimethoxysilane, styreneethyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltriethoxysilane, styryltriethoxysilane, or styreneethyltriethoxysilane are preferred from the viewpoint of the reactivity of the addition reaction, and structural units obtained by addition reaction of a structure derived from 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, styryltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltriethoxysilane, or styryltriethoxysilane are more preferred examples, but other known materials can also be used.

[0053] Examples of the structural unit represented by general formula (2) include 3-glycidoxypropyldimethoxymethylsilane, 2-(3,4-epoxycyclohexyl)ethyldimethoxymethylsilane, 5,6-epoxyhexyldimethoxymethylsilane, 3-(3-ethyl-3-oxetanylmethoxy)propyldimethoxymethylsilane, 3-glycidoxypropyldiethoxymethylsilane, 2-(3,4-epoxycyclohexyl)ethyldiethoxymethylsilane, 5,6-epoxyhexyldiethoxymethylsilane, and 3-(3-ethyl-3-oxetanylmethoxy)propyldimethoxymethylsilane. Propyldiethoxymethylsilane, 3-glycidoxypropyldimethoxyphenylsilane, 2-(3,4-epoxycyclohexyl)ethyldimethoxyphenylsilane, 5,6-epoxyhexyldimethoxyphenylsilane, 3-(3-ethyl-3-oxetanylmethoxy)propyldimethoxyphenylsilane, 3-glycidoxypropyldiethoxyphenylsilane, 2-(3,4-epoxycyclohexyl)ethyldiethoxyphenylsilane, 5,6-epoxyhexyldiethoxyphenylsilane, 3-(3-ethyl-3-oxetanylmethoxy)propyldimethoxyphenylsilane Derived from propyl diethoxyphenylsilane, 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 5,6-epoxyhexyltrimethoxysilane, 3-(3-ethyl-3-oxetanylmethoxy)propyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 5,6-epoxyhexyltriethoxysilane, 3-(3-ethyl-3-oxetanylmethoxy)propyltriethoxysilane Structural units obtained by hydrolysis of an epoxy group or an oxetanyl group are preferred, and more preferred examples include structural units obtained by hydrolysis of an epoxy group or an oxetanyl group derived from 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 5,6-epoxyhexyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, and 5,6-epoxyhexyltriethoxysilane; however, other known materials can also be used.

[0054] Examples of the structural unit represented by general formula (3) include structural units derived from the following silane compounds.

[0055] Those having a carboxyl group or a derivative thereof include dimethoxymethylsilylmethylsuccinic acid, diethoxymethylsilylmethylsuccinic acid, dimethoxyphenylsilylmethylsuccinic acid, diethoxyphenylsilylmethylsuccinic acid, trimethoxysilylmethylsuccinic acid, triethoxysilylmethylsuccinic acid, 2-dimethoxymethylsilylethylsuccinic acid, 2-diethoxymethylsilylethylsuccinic acid, 2-dimethoxyphenylsilylethylsuccinic acid, 2-diethoxyphenylsilylethylsuccinic acid, Diphenylsilylethyl succinate, 2-trimethoxysilylethyl succinate, 2-triethoxysilylethyl succinate, 3-dimethoxymethylsilylpropyl succinate, 3-diethoxymethylsilylpropyl succinate, 3-dimethoxyphenylsilylpropyl succinate, 3-diethoxyphenylsilylpropyl succinate, 3-trimethoxysilylpropyl succinate, 3-triethoxysilylpropyl succinate, 4-dimethoxymethylsilylbutyl succinate, 4-diethoxymethylsilylpropyl succinate 4-Dimethoxyphenylsilylbutylsuccinic acid, 4-Diethoxyphenylsilylbutylsuccinic acid, 4-Trimethoxysilylbutylsuccinic acid, 4-Triethoxysilylbutylsuccinic acid, 5-Dimethoxymethylsilylpentylsuccinic acid, 5-Diethoxymethylsilylpentylsuccinic acid, 5-Dimethoxyphenylsilylpentylsuccinic acid, 5-Diethoxyphenylsilylpentylsuccinic acid, 5-Diethoxyphenylsilylpentylsuccinic acid, 5-Trimethoxysilylpentylsuccinic acid, Examples include 5-triethoxysilylpentylsuccinic acid, 6-dimethoxymethylsilylhexylsuccinic acid, 6-diethoxymethylsilylhexylsuccinic acid, 6-dimethoxyphenylsilylhexylsuccinic acid, 6-diethoxyphenylsilylhexylsuccinic acid, 6-trimethoxysilylhexylsuccinic acid, 6-triethoxysilylhexylsuccinic acid, anhydrides of these compounds having a succinic acid structure, and structural units derived from compounds in which these succinic acids have become glutaric acid.

[0056] Examples of those having a sulfo group or a derivative thereof include 5-dimethoxymethylsilylpentane-1,2-disulfonic acid, 5-diethoxymethylsilylpentane-1,2-disulfonic acid, 5-dimethoxyphenylsilylpentane-1,2-disulfonic acid, 5-diethoxyphenylsilylpentane-1,2-disulfonic acid, 5-trimethoxysilylpentane-1,2-disulfonic acid, 5-triethoxysilylpentane-1,2-disulfonic acid, and structural units derived from their methyl esters, ethyl esters, n-propyl esters, isopropyl esters, n-butyl esters, sec-butyl esters, and t-butyl esters.

[0057] Examples of those having a thiol group or a derivative thereof include 3-(3-dimethoxymethylsilylpropyloxy)propane-1,2-dithiol, 3-(3-diethoxymethylsilylpropyloxy)propane-1,2-dithiol, 3-(3-dimethoxyphenylsilylpropyloxy)propane-1,2-dithiol, 3-(3-diethoxyphenylsilylpropyloxy)propane-1,2-dithiol, 3-(3-diethoxyphenylsilylpropyloxy)propane-1,2-dithiol, 3-(3-trimethoxysilylpropyloxy)propane-1,2-dithiol, 3-(3-triethoxysilylpropyloxy)propane-1,2-dithiol, and structural units derived from these methyl thioethers, ethyl thioethers, n-propyl thioethers, isopropyl thioethers, n-butyl thioethers, sec-butyl thioethers, and t-butyl thioethers.

[0058] Examples of compounds having a phenolic hydroxyl group or a derivative thereof include structural units derived from catechol, resorcinol, hydroquinone, or phloroglucinol having a 3-dimethoxymethylsilylpropyl group, a 3-diethoxymethylsilylpropyl group, a 3-dimethoxyphenylsilylpropyl group, a 3-diethoxyphenylsilylpropyl group, a 3-trimethoxysilylpropyl group, or a 3-triethoxysilylpropyl group, as well as the methyl ether, ethyl ether, n-propyl ether, isopropyl ether, n-butyl ether, sec-butyl ether, and t-butyl ether of these compounds.

[0059] Examples of compounds containing one each of different types of carboxyl group, sulfo group, thiol group, phenolic hydroxyl group or derivatives thereof include 1-carboxyl-2-sulfo-5-trimethoxysilylpentane, 1-carboxyl-2-mercapto-5-trimethoxysilylpentane, 1-sulfo-2-mercapto-5-trimethoxysilylpentane, 1-carboxyl-2-hydroxy-4-trimethoxysilylbenzene, 1-sulfo-2-hydroxy-4-trimethoxysilylbenzene, 1-mercapto-2-hydroxy-4-trimethoxysilylbenzene, and derivatives thereof. These include positional isomers having different positions of the substituents, as well as structural units derived from methyl(thio)ester, ethyl(thio)ester, n-propyl(thio)ester, isopropyl(thio)ester, n-butyl(thio)ester, sec-butyl(thio)ester, t-butyl(thio)ester, methyl(thio)ether, ethyl(thio)ether, n-propyl(thio)ether, isopropyl(thio)ether, n-butyl(thio)ether, sec-butyl(thio)ether, t-butyl(thio)ether, cyclic(thio)ester, and cyclic(thio)ether.

[0060] Among them, structural units derived from silane compounds having at least two carboxyl groups or derivatives thereof, or at least one cyclic acid anhydride group are preferred, structural units derived from silane compounds having succinic acid, succinic anhydride structures, or derivatives thereof are more preferred, and structural units derived from silane compounds having succinic acid or succinic anhydride structures are even more preferred.Specifically, structural units derived from 3-dimethoxymethylsilylpropylsuccinic acid, 3-diethoxymethylsilylpropylsuccinic acid, 3-dimethoxyphenylsilylpropylsuccinic acid, 3-diethoxyphenylsilylpropylsuccinic acid, 3-trimethoxysilylpropylsuccinic acid, 3-triethoxysilylpropylsuccinic acid, and anhydrides thereof are more preferred, and structural units derived from 3-trimethoxysilylpropylsuccinic acid, 3-triethoxysilylpropylsuccinic acid, and anhydrides thereof are particularly preferred.

[0061] Among the silane compounds exemplified above, silane compounds in which some or all of the methoxy groups are replaced with other alkoxy groups such as ethoxy groups are also preferably used.

[0062] The polysiloxane can be obtained, for example, by the following method. All silane compounds are dissolved in a solvent, and an acid or base catalyst and water are added thereto over a period of 1 to 180 minutes. The hydrolysis reaction is then carried out at 15 to 80°C for 1 to 180 minutes. The temperature during the hydrolysis reaction is preferably 15 to 55°C. The reaction solution is heated at a temperature above 50°C and below the boiling point of the solvent for 1 to 100 hours to carry out a condensation reaction, thereby obtaining the polysiloxane. Various conditions for the hydrolysis, such as catalyst concentration, reaction temperature, and reaction time, can be appropriately set taking into account the reaction scale, size, and shape of the reaction vessel, etc.

[0063] Furthermore, when the (b) polymer is a polysiloxane having at least the structures represented by general formula (1), general formula (2), and general formula (3), the content of the structural unit represented by general formula (2) in all structural units of the polysiloxane is preferably 1 to 10 mol %. By keeping it in this range, the processing stability and chemical resistance of the insulating layer can be further improved.

[0064] (a) Titanium compound particles The (a) titanium compound particles are particles made of a compound having a titanium atom, such as an inorganic titanium compound or an organic titanium compound. In the insulating layer using the resin composition according to the embodiment of the present invention, the (a) titanium compound particles are preferably used for the purpose of reducing the number of locations where carrier traps may occur, as described above.

[0065] The (a) titanium compound particles are not particularly limited as long as they contain titanium atoms, but inorganic titanium compound particles are preferred. Inorganic titanium compound particles more easily interact with the (b2) group of the (b) polymer, and can further enhance the effects of (i) and (iii) above.

[0066] Examples of inorganic titanium compound particles include titanium oxide particles and titanic acid compound particles, with titanic acid compound particles being more preferred. This is because titanic acid compound particles have fewer potential carrier trap sites within the particle. Additionally, the surface of titanic acid compound particles is particularly susceptible to interaction with the (b2) group of the (b) polymer, resulting in fewer highly active sites on the particle surface that could potentially cause carrier traps, thereby reducing the number of potential carrier trap sites in the insulating layer. Furthermore, the particularly susceptible interaction between the surface of titanic acid compound particles and the (b2) group of the (b) polymer results in a denser insulating layer, thereby improving chemical resistance and processing stability of the insulating layer. Examples of titanic acid compound particles include potassium titanate particles, barium titanate particles, strontium titanate particles, calcium titanate particles, magnesium titanate particles, lead titanate particles, or composite particles thereof. Barium titanate particles, strontium titanate particles, and calcium titanate particles are more preferred, with barium titanate particles being particularly preferred.

[0067] The shape of the (a) titanium compound particles is not particularly limited. However, to maintain a smooth surface of the insulating layer, a shape with a low aspect ratio is preferred, and spherical shapes are more preferred. Furthermore, from the viewpoint of the interaction between the (a) titanium compound particles and the (b) polymer, the number-average particle diameter of the (a) titanium compound particles is preferably 1 nm or more, more preferably 5 nm or more, even more preferably 15 nm or more, and particularly preferably 20 nm or more. On the other hand, from the viewpoint of improving the surface flatness and pattern processability of the insulating layer, the number-average particle diameter of the (a) titanium compound particles is preferably 100 nm or less, more preferably 70 nm or less, even more preferably 60 nm or less, and particularly preferably 50 nm or less. The number-average particle diameter of the (a) titanium compound particles can be determined by the following measurement using a scanning electron microscope (SEM) or a transmission electron microscope (TEM). The cross section of the insulating layer is observed at a magnification of 50,000 to 200,000 times. If the (a) titanium compound particles are spherical, the diameter of the sphere is measured and used as the particle diameter. (a) If the titanium compound particles are not perfectly spherical, measure the longest diameter (hereinafter referred to as the "major axis diameter") and the longest diameter in the direction perpendicular to the major axis diameter (hereinafter referred to as the "minor axis diameter"), and average the major axis diameter and minor axis diameter to obtain the biaxial mean diameter, which is the particle diameter of the particles. This particle diameter measurement is performed on 20 or more randomly selected particles, and the arithmetic mean of the measurements is the number average particle diameter.

[0068] The content of the (a) titanium compound particles is preferably 60% by weight or more, and more preferably 75% by weight or more, when the total of the (a) titanium compound particles and the (b) polymer is 100% by weight. This reduces the number of areas in the insulating layer where carrier trapping can occur. In addition, by using the (b) polymer in the present invention, high processing stability and chemical resistance of the insulating layer can be achieved even when the weight ratio of the (a) titanium compound particles is high as described above.

[0069] (Other ingredients) The insulating layer may further contain, as a photosensitive organic component, a compound that undergoes bond cleavage and / or reaction upon irradiation with UV light to generate radicals (photopolymerization initiator), a compound that generates an acid upon exposure to light (photoacid generator), a compound that generates a base upon exposure to light (photobase generator), a sensitizer, a chain transfer agent or its addition reactant, and a polymerization inhibitor.

[0070] The thickness of the insulating layer is preferably 0.05 μm to 5 μm, more preferably 0.1 μm to 1 μm. By setting the thickness within this range, it becomes easy to form a uniform thin film. The thickness can be measured by an atomic force microscope, ellipsometry, or the like.

[0071] (semiconductor layer) The semiconductor layer can be made of inorganic semiconductor materials such as oxide semiconductors, organic semiconductor materials, nanocarbons, etc. Among these, it is preferable that the semiconductor layer contains nanocarbons, which have excellent carrier mobility and can be applied to a low-cost and simple coating process. Note that, since the insulating layer of the semiconductor element of the present invention has high chemical resistance as described above, it can also be suitably used when the semiconductor layer is formed by a coating process using an organic solvent, etc.

[0072] Nanocarbons are substances made of carbon and have a nanometer-sized structure, and examples include carbon nanotubes (CNTs), graphene, fullerenes, carbon nanohorns, graphene nanoribbons, and encapsulated CNTs. From the viewpoint of semiconductor properties, nanocarbons are preferably CNTs and graphene, and more preferably CNTs. Furthermore, CNTs are preferably used as CNT composites in which a conjugated polymer is attached to at least a portion of the surface. The semiconductor layer may further contain an organic semiconductor or insulating material, as long as the electrical properties are not impaired.

[0073] The thickness of the semiconductor layer is preferably 1 nm or more and 100 nm or less. Within this range, it becomes easier to form a uniform thin film. The thickness of the semiconductor layer is more preferably 1 nm or more and 50 nm or less, and even more preferably 1 nm or more and 20 nm or less. The thickness can be measured using an atomic force microscope, ellipsometry, an electron microscope, or the like.

[0074] CNTs can be single-walled CNTs, which are made up of a single carbon film (graphene sheet) wound into a cylindrical shape; double-walled CNTs, which are made up of two concentrically wound graphene sheets; or multi-walled CNTs, which are made up of multiple concentrically wound graphene sheets. To obtain high semiconducting properties, single-walled CNTs are preferred. CNTs can be obtained by arc discharge, chemical vapor deposition (CVD), laser ablation, and other methods.

[0075] The CNTs are preferably CNTs having a conjugated polymer attached to at least a portion of the surface of the CNTs (hereinafter referred to as "CNT composites"). Here, the conjugated polymer refers to a compound whose repeating unit has a conjugated structure and whose degree of polymerization is 2 or more.

[0076] By attaching a conjugated polymer to at least a portion of the CNT surface, it becomes possible to uniformly disperse the CNT in a solution without impairing the high electrical properties of the CNT. If a solution in which CNTs are uniformly dispersed is used, it becomes possible to form a film containing uniformly dispersed CNTs by a coating method. This makes it possible to achieve high semiconducting properties. The state in which a conjugated polymer is attached to at least a portion of the CNT surface means that the CNT surface is partially or entirely covered with a conjugated polymer.

[0077] Examples of conjugated polymers include, but are not limited to, polythiophene-based polymers, polypyrrole-based polymers, polyaniline-based polymers, polyacetylene-based polymers, poly-p-phenylene-based polymers, and poly-p-phenylenevinylene-based polymers. As the above-mentioned polymers, those in which a single monomer unit is arranged are preferably used, but those in which different monomer units are block copolymerized, random copolymerized, or graft polymerized are also preferably used. Among these, polythiophene-based polymers are preferred from the viewpoint of easy attachment to CNTs and easy formation of CNT composites. Furthermore, among polythiophene-based polymers, those containing a fused heteroaryl unit having a nitrogen-containing double bond in the ring and a thiophene unit in the repeating unit are more preferred.

[0078] Specific examples of the above CNTs and CNT composites include those described in WO 2009 / 139339, WO 2020 / 066741, and WO 2020 / 261891.

[0079] (base material) The substrate may be made of any material as long as at least the surface on which the electrode system is disposed is insulating. Preferred substrates include inorganic materials such as silicon wafers, glass, sapphire, and sintered alumina, and organic materials such as polyimide, polyvinyl alcohol, polyvinyl chloride, polyethylene terephthalate, polyvinylidene fluoride, polysiloxane, polyvinylphenol (PVP), polyester, polycarbonate, polysulfone, polyethersulfone, polyethylene, polyphenylene sulfide, and polyparaxylene.

[0080] The substrate may also be a laminate of multiple materials, such as a PVP film formed on a silicon wafer or a polysiloxane film formed on polyethylene terephthalate.

[0081] (electrode) The materials used for the first, second, and third electrodes may be any conductive material commonly used for electrodes. Examples of conductive materials include, but are not limited to, conductive metal oxides such as tin oxide, indium oxide, and indium tin oxide (ITO); metals such as platinum, gold, silver, copper, iron, tin, zinc, aluminum, indium, chromium, lithium, sodium, potassium, cesium, calcium, magnesium, palladium, molybdenum, amorphous silicon, and polysilicon, as well as alloys thereof; inorganic conductive materials such as copper iodide and copper sulfide; polythiophene, polypyrrole, polyaniline; complexes of polyethylenedioxythiophene and polystyrenesulfonic acid; conductive polymers whose conductivity is improved by doping with iodine or the like; carbon materials; and materials containing an organic component and a conductor.

[0082] In particular, it is preferable that the electrode contains an organic component and a conductor, since this increases the flexibility of the electrode, provides good adhesion to the substrate and the insulating layer even when bent, and provides good electrical connection with the wiring and the semiconductor layer.

[0083] The organic component is not particularly limited, and examples thereof include monomers, oligomers, polymers, photopolymerization initiators, plasticizers, leveling agents, surfactants, silane coupling agents, antifoaming agents, and pigments. From the viewpoint of improving the bending resistance of the electrode, the organic component is preferably an oligomer or a polymer. Furthermore, from the viewpoint of improving productivity, the organic component preferably contains a photosensitive organic component. This enables patterning of the electrode by photolithography without using a resist.

[0084] The oligomer or polymer is not particularly limited, and examples thereof include acrylic resin, epoxy resin, novolac resin, phenolic resin, polyimide precursor, and polyimide. Among these, acrylic resin is preferred from the viewpoint of crack resistance when the electrode is bent. This is presumably because acrylic resin has a glass transition temperature of 100°C or less, and softens during thermal curing of the conductive film, enhancing the bonding between the conductive particles.

[0085] An acrylic resin is a resin containing a repeating unit derived from at least an acrylic monomer. Specific examples of the acrylic monomer include all compounds having a carbon-carbon double bond. These acrylic monomers may be used alone or in combination of two or more.

[0086] The conductor may be any conductive material that can be generally used as an electrode, but is preferably a conductive particle that is composed entirely or partially of a conductive material and the particles themselves are conductive. By using conductive particles as the conductor, irregularities are formed on the surface of the electrode containing them. When the insulating layer penetrates into these irregularities, an anchor effect occurs, further improving the adhesion between the electrode and the insulating layer. Improved adhesion between the electrode and the insulating layer has the effect of improving the bending resistance of the electrode and the effect of suppressing fluctuations in electrical characteristics when voltage is repeatedly applied to the semiconductor element. These effects further improve the reliability of the semiconductor element.

[0087] Suitable conductive materials for the conductive particles include gold, silver, copper, nickel, tin, bismuth, lead, zinc, palladium, platinum, aluminum, tungsten, molybdenum, and carbon. More preferred conductive particles are conductive particles containing at least one element selected from the group consisting of gold, silver, copper, nickel, tin, bismuth, lead, zinc, palladium, platinum, aluminum, and carbon. These conductive particles may be used alone, as an alloy, or as a mixed particle.

[0088] Among these, gold, silver, copper, or platinum particles are preferred from the viewpoint of conductivity, with silver being more preferred from the viewpoint of cost and stability.

[0089] The width and thickness of each of the first, second, and third electrodes, as well as the distance between the first and second electrodes, can be designed to any value. For example, the electrode width is preferably 10 μm to 10 mm, the electrode thickness is preferably 0.01 μm to 100 μm, and the distance between the first and second electrodes is preferably 1 μm to 1 mm, but is not limited to these.

[0090] These materials for producing the electrodes may be used alone, or the electrodes may be formed by laminating a plurality of materials, or by mixing a plurality of materials.

[0091] Furthermore, in the semiconductor device according to the third embodiment of the present invention, the material used for the fourth electrode 29 is not particularly limited, and a commonly used conductive material can be used, similar to the materials used for the first, second, and third electrodes. The third electrode 22 and the first electrode 25 can be electrically connected by any method that can ensure electrical continuity. The width and thickness of the connection portion are also optional.

[0092] The electrodes may be formed in a pattern by patterning the prepared electrode thin film into the desired shape using a known photolithography method, or by forming the pattern through a mask of the desired shape during vapor deposition or sputtering of the electrode, wiring, and connection material. Alternatively, the pattern may be formed directly using an inkjet or printing method. Since the insulating layer of the semiconductor element of the present invention has high chemical resistance as described above, it can also be suitably used when patterning the electrodes using chemical solutions.

[0093] The electrode patterns may be formed by processing each separately, or at least two of them may be processed together to form them. From the viewpoint of reducing the processing steps and connecting the patterns, it is preferable to process the electrode patterns together.

[0094] (Second insulating layer) The semiconductor element may have a second insulating layer. The second insulating layer is formed on the side of the semiconductor layer opposite to the side on which the insulating layer is formed. For example, when the insulating layer is formed below the semiconductor layer, the side opposite to the side on which the insulating layer is formed refers to the upper side of the semiconductor layer.

[0095] Forming the second insulating layer can protect the p-type semiconductor element and the n-type semiconductor element from physical damage, humidity, and the like, and can improve the characteristics of the n-type semiconductor element. Examples of p-type semiconductor elements include the p-type semiconductor element described in JP 2013-62391 A. Examples of n-type semiconductor elements include the n-type semiconductor elements described in WO 2018 / 180146, WO 2019 / 097978, WO 2020 / 195707, and WO 2020 / 195708.

[0096] The thickness of the second insulating layer is preferably 500 nm or more, more preferably 1.0 μm or more, even more preferably 3.0 μm or more, and particularly preferably 10 μm or more. The upper limit of the thickness is not particularly limited, but is preferably 500 μm or less. The thickness of the second insulating layer is determined by measuring the cross section of the second insulating layer using a scanning electron microscope, calculating the thickness at 10 randomly selected locations in the image of the second insulating layer located on the semiconductor layer, and taking the arithmetic average of the calculated thicknesses.

[0097] (protective layer) The semiconductor element may further have a protective layer on the semiconductor layer, the second insulating layer, etc. The role of the protective layer is to protect the semiconductor element from physical damage such as rubbing and from moisture and oxygen in the atmosphere.

[0098] Examples of materials for the protective layer include inorganic materials such as silicon wafer, glass, sapphire, and sintered alumina, and organic materials such as polyimide, polyvinyl alcohol, polyvinyl chloride, polyethylene terephthalate, polyvinylidene fluoride, polysiloxane, polyvinyl phenol, polyester, polycarbonate, polysulfone, polyether sulfone, polyethylene, polyphenylene sulfide, polyparaxylene, polyacrylonitrile, and cycloolefin polymer. Furthermore, the protective layer may be a laminate of multiple materials, such as a polyvinyl phenol film formed on a silicon wafer or an aluminum oxide film formed on polyethylene terephthalate.

[0099] In the semiconductor device according to the embodiment of the present invention, when it is operated as a field-effect transistor, the current flowing between the source electrode and the drain electrode (source-drain current) can be controlled by changing the gate voltage. A semiconductor device that shows small changes in on-current and off-current when continuously operated is a semiconductor device with excellent continuous operational stability.

[0100] (Method of manufacturing semiconductor devices) A method for manufacturing a semiconductor device according to an embodiment of the present invention will be described below, taking as an example a method for manufacturing a semiconductor device shown in the configuration of Fig. 1. Note that the manufacturing method is not limited to the following. The manufacturing method described below includes the following (Step 1) to (Step 3).

[0101] (Step 1) A step of forming a conductive pattern on a substrate First, a conductive pattern that will become the gate electrode 2 is formed on the substrate 1. Examples of the formation method include known methods such as metal vapor deposition, spin coating, blade coating, slit die coating, screen printing, bar coating, molding, print transfer, immersion and lift-up, and inkjet printing. The conductive pattern may be formed directly using a mask or the like, or the gate electrode may be patterned by applying a resist to the formed gate electrode, exposing and developing the resist film to a desired pattern, and then etching it. Furthermore, when a conductive paste containing a photosensitive organic component is used, the gate electrode can be patterned by photolithography without using a resist.

[0102] (Step 2) A step of applying a solution containing at least titanium compound particles and (b) a polymer or its precursor to the substrate on which the conductive pattern has been formed, drying the solution, obtaining a coating film, and then curing the coating film to form an insulating layer. Next, a gate insulating layer 3 is formed on the substrate on which the conductive pattern is formed. The gate insulating layer 3 can be formed by applying a solution containing at least titanium compound particles and a (b) polymer or its precursor to the substrate on which the conductive pattern is formed, drying the solution, obtaining a coating film, and then curing the coating film. The (b) polymer precursor is a compound that becomes a (b) polymer through a process such as heat treatment or irradiation with activated actinic rays, which will be described later. Examples of the (b) polymer precursor include polymers having the structures (b1'), (b2), and (b3) below.

[0103] (b1') an alkenyl group, an acrylic group, or a methacrylic group (b2) a 1,2-dihydroxyethyl group, a 1,2-dihydroxyethylene group, a 1,3-dihydroxypropyl group, or a 1,3-dihydroxypropylene group (b3) an organic group containing at least two of a carboxyl group, a sulfo group, a thiol group, a phenolic hydroxyl group, or a derivative thereof; provided that, when the derivative has a cyclic condensation structure formed by two of the carboxyl group, the sulfo group, the thiol group, and the phenolic hydroxyl group, (b3) is an organic group having at least one of the cyclic condensation structures. The above polymer can be converted into polymer (b) by addition reaction between structures of (b1') and / or with an alkenyl group, an acrylic group, or a methacrylic group contained in another radically polymerizable compound.

[0104] When using a solution containing at least titanium compound particles and a precursor of the (b) polymer, the precursor of the (b) polymer is preferably a polymer having the structures (b1'), (b2), and (b3), which allows for the formation of an insulating layer with superior processing stability and chemical resistance.

[0105] Examples of methods for applying the solution include known coating methods such as spin coating, blade coating, slit die coating, screen printing, bar coating, casting, print transfer, immersion and lifting, and ink jet printing.

[0106] The solution may contain a solvent for the coating process. While the solvent is not particularly limited, specific examples include ethers such as propylene glycol monomethyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-t-butyl ether, ethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether; acetates such as propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, and ethyl lactate; ketones such as acetylacetone, methyl isobutyl ketone, and cyclopentanone; alcohols such as 3-methyl-3-methoxybutanol and diacetone alcohol; and aromatic hydrocarbons such as toluene and xylene. These solvents may be used alone or in combination.

[0107] The drying temperature when obtaining a coating film is preferably 50 to 150°C, more preferably 60 to 140°C, even more preferably 70 to 130°C, and particularly preferably 80 to 120°C. A drying temperature in this range is preferred from the viewpoints of facilitating the removal of the solvent from the coating film and the processing into a desired shape during patterning, which will be described later. The drying time is preferably 0.5 to 5 minutes, more preferably 1 to 3 minutes. A drying time in this range is preferred from the viewpoints of facilitating the removal of the solvent from the coating film and the processing into a desired shape during patterning, which will be described later.

[0108] Furthermore, the temperature for heat treatment of the coating film to harden the coating film to obtain a gate insulating layer is preferably in the range of 100 to 300° C., more preferably 120 to 250° C. When the heat treatment temperature is in this range, a sufficiently hardened gate insulating layer can be obtained.

[0109] Furthermore, when a semiconductor element is formed on a plastic substrate, the temperature is preferably 120 to 200° C., and particularly preferably 120 to 150° C. When the temperature is in this range, shrinkage of the plastic substrate during heat treatment can be suppressed.

[0110] The heat treatment time for the coating film is preferably 0.5 to 60 minutes, more preferably 5 to 30 minutes. By keeping the heat treatment time within this range, a sufficiently hardened gate insulating layer can be obtained.

[0111] Furthermore, when the solution is a composition containing a photoradical generator and a radical polymerizable compound, curing of the coating film can also be preferably carried out by irradiating (exposing) it to actinic rays. This is particularly preferred when forming semiconductor elements on plastic substrates, as it allows heat treatment to be performed without heat treatment or under milder conditions, thereby suppressing shrinkage of the plastic substrate. When a precursor of the (b) polymer is used, the addition reaction structure (b1) in the (b) polymer may be formed by this curing process.

[0112] After forming the insulating layer, the insulating layer may be patterned by applying a resist onto the insulating layer, exposing and developing the resist film into a desired pattern, and then treating it with an etching solution such as hydrofluoric acid. From the viewpoint of productivity, it is preferable to perform patterning using an insulating layer material having a photosensitive organic component, as described later in (Step 2').

[0113] Next, the semiconductor layer 4 is formed on the gate insulating layer. Although dry methods such as resistance heating evaporation, electron beam deposition, sputtering, and CVD can be used to form the semiconductor layer 4, a coating method is preferred from the perspective of manufacturing costs and suitability for large areas. Examples of coating methods include known methods such as spin coating, blade coating, slit die coating, screen printing, bar coating, casting, print transfer, dipping and lifting, and inkjet coating. The coating method can be selected depending on the desired coating film characteristics, such as coating film thickness and orientation control. In particular, when forming a semiconductor layer containing CNTs, it is preferable to coat the gate insulating layer with a solution containing CNTs. In this case, although there are no particular limitations on the coating method, the inkjet method is advantageous in that it reduces the amount of solution used and increases productivity. When forming the semiconductor layer by coating, the formed coating film is dried in air, under reduced pressure, or in an inert gas (nitrogen or argon) atmosphere. The drying temperature is preferably 50 to 150°C.

[0114] (Step 3) forming a conductive pattern on the insulating layer Next, a conductive pattern that will become the source electrode 5 and the drain electrode 6 is formed on the gate insulating layer. This results in a semiconductor device having the configuration shown in FIG. 1 . Similar to the gate electrode 1, methods for forming the source electrode 5 and the drain electrode 6 include known methods such as metal vapor deposition, spin coating, blade coating, slit die coating, screen printing, bar coating, molding, print transfer, immersion and lift-up, and inkjet printing. The conductive pattern can be formed directly using a mask or the like, or the source electrode and the drain electrode can be patterned by applying a resist to the formed electrode, exposing and developing the resist film to the desired pattern, and then etching it. Furthermore, when a conductive paste containing a photosensitive organic component is used, it is also possible to pattern the gate electrode using photolithography from the conductive paste alone without using a resist.

[0115] The above (Step 1) to (Step 3) can be replaced with the following (Step 1') to (Step 3').

[0116] (Step 1') Step of forming a conductive pattern on a substrate This step (Step 1') can be carried out in the same manner as the above step (Step 1).

[0117] (Step 2') A step of applying a solution containing at least titanium compound particles and (b) a polymer or a precursor thereof onto the substrate on which the conductive pattern has been formed, drying the solution to obtain a coating film, and then irradiating the coating film with actinic rays through a photomask and developing the coating film to form a pattern having openings on the conductive pattern or the substrate, thereby forming an insulating layer having openings. When forming a circuit by combining a plurality of semiconductor elements according to the embodiment of the present invention, it is preferable to perform this step (step 2'). This is because, in the circuit, it is necessary to form an opening pattern (contact hole) in the gate insulating layer to establish electrical connection between the first electrode or second electrode of one semiconductor element and the third electrode of another semiconductor element. FIG. 4 is a schematic cross-sectional view showing an example of this. A contact hole 43 is formed in the gate insulating layer 3, and electrical connection can be established between the source electrode 5 (first electrode) of the semiconductor element 40 and the gate electrode 2 (third electrode) of the semiconductor element 50.

[0118] A negative pattern formation of an insulating layer using a composition containing a photoradical generator and a radical polymerizable compound in a photosensitive organic component will be described.

[0119] First, a coating film is formed in the same manner as in (Step 2). Then, the coating film is irradiated (exposed) with activated actinic rays from above through a negative mask having a desired pattern. Activated actinic rays used for exposure include ultraviolet light, visible light, electron beams, and X-rays. In the present invention, it is preferable to use i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) from a mercury lamp.

[0120] The exposed coating film is then developed. In negative pattern formation, the exposed areas are insoluble and the unexposed areas are soluble. The developer is preferably an aqueous solution of an alkaline compound such as tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, triethylamine, sodium hydroxide, potassium hydroxide, sodium carbonate, or potassium carbonate, and may contain one or more of these compounds. These alkaline aqueous solutions can also be mixed with polar solvents such as N-methyl-2-pyrrolidone and γ-butyrolactone, alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, or ketones such as cyclopentanone and methyl isobutyl ketone.

[0121] After development, the film is usually rinsed with water, but it may also be rinsed with water containing alcohols such as ethanol and isopropyl alcohol, or esters such as ethyl lactate and propylene glycol monomethyl ether acetate.

[0122] In forming a positive pattern on a gate insulating layer using a composition containing a diazoketone compound as a photoacid generator in a photosensitive organic component, the gate insulating layer is irradiated with actinic radiation from above through a positive mask having a desired pattern. The preferred actinic radiation species and the development and rinsing treatment of the gate insulating layer are the same as in the case where a photoradical generator and a radical polymerizable compound are used in the photosensitive organic component. In forming a positive pattern, the exposed areas are patterned as soluble areas, and the unexposed areas are patterned as insoluble areas.

[0123] (Step 3') A step of forming a conductive pattern on the insulating layer This step (Step 3') can be carried out in the same manner as the above step (Step 3).

[0124] (Applicability of semiconductor elements) The semiconductor device according to the embodiment of the present invention is applicable to circuits and ICs of various electronic devices, wireless communication devices such as RFID tags, wireless power supply devices, TFT arrays for displays, sensors, tamper detection systems, and the like.

[0125] (circuit) The semiconductor element according to the embodiment of the present invention can be applied to various circuits. Examples include analog circuits such as rectifier circuits, logic circuits such as NOT circuits, NAND circuits, NOR circuits, AND circuits, and OR circuits, combinational circuits and sequential circuits using these circuits, and integrated circuits such as memories, microprocessors, and logic ICs. These circuits can also be used in various electronic devices. The semiconductor element according to the present invention has excellent continuous operational stability, as well as an insulating layer with high processing stability and chemical resistance, making it suitable for use in the above-mentioned circuits. Furthermore, the inclusion of the (b) polymer in the insulating layer provides resistance to bending and stretching, making it suitable for use in flexible and bendable electronic devices.

[0126] (wireless communication device) A wireless communication device according to an embodiment of the present invention, which includes a circuit according to an embodiment of the present invention, will be described. This wireless communication device is a device that communicates information using radio waves, such as a product tag, an anti-shoplifting tag, various tickets, or a smart card.

[0127] An example of the configuration of the wireless communication device is the wireless communication device described in JP 2022-108261 A. Various circuits are included, and the circuit of the present invention can be suitably used in these circuits or in part thereof.

[0128] (Product tag) The wireless communication device can be used for any purpose, but can be applied to, for example, a product tag. Known product tags can be used, including, for example, those having a base and the wireless communication device covered by the base. When applied to product tags with an identification information return function, it becomes possible to simultaneously identify multiple products without contact at a checkout register. Therefore, payment processing can be facilitated and accelerated compared to identification using barcodes.

[0129] Furthermore, for example, when paying for a product, the reader / writer can transmit the product information read from the product tag to a POS (Point of Sale System) terminal. This function also allows the POS terminal to register the sale of a product identified by the product information, making inventory management easier and faster.

[0130] (Thin-film transistor array) A thin film transistor (hereinafter, referred to as TFT) array can be obtained using a semiconductor device according to an embodiment of the present invention. FIG. 5 is a schematic diagram showing an example of a TFT array. As shown in FIG. 5, a TFT array 200 includes two gate lines 250 and 260, two source lines 270 and 280, and four TFTs 210, 220, 230, and 240. The gate line 250 is electrically coupled to the gate electrodes of the TFTs 210 and 230, and the gate line 260 is electrically coupled to the gate electrodes of the TFTs 220 and 240. The source line 270 is electrically coupled to the source electrodes of the TFTs 210 and 220, and the source line 280 is electrically coupled to the source electrodes of the TFTs 230 and 240. Note that, for the sake of simplicity, FIG. 5 illustrates a TFT array 200 including four TFTs; however, the number of gate lines, source lines, and TFTs may be changed as desired.

[0131] The material for electrically connecting the gate lines, source lines, and TFTs is not particularly limited, and may be, for example, a commonly used conductive material. The connection method may be any method that provides electrical continuity. The width and thickness of the connection portion may be any desired value.

[0132] The TFT array according to the embodiment of the present invention can be used, for example, in an active matrix driven liquid crystal display, electronic paper, and the like.

[0133] (sensor) The semiconductor device according to the embodiment of the present invention may be used in various sensors, for example, sensors for detecting temperature, moisture, gas, light, electromagnetic waves, radiation, pressure, etc. [Example]

[0134] The present invention will be described in more detail below based on examples. However, the present invention is not limited to the following examples. The evaluation methods used in the examples are described in the following (1) to (3).

[0135] (1) Processing stability of the insulating layer In the processing stability evaluation area of ​​the insulating layer of a semiconductor element manufactured by the method described below, the number of peeled insulating layers on the copper electrodes was counted, and the number was judged as follows, with A to D being considered to have good processing stability. A: 0 or more and 10 or less B: 11 or more and 20 or less C: 21 to 30 pieces D: 31 or more and 50 or less E: 51 to 100 pieces F: 101 or more.

[0136] (2) Chemical resistance of the insulating layer Chemical resistance was evaluated in the chemical resistance evaluation area of ​​the insulating layer of a semiconductor element fabricated by the method described below using the following method. 400 pL of o-dichlorobenzene (solvent for the semiconductor layer) was applied to the chemical resistance evaluation area using an inkjet device (Cluster Technology Co., Ltd.), followed by heat treatment at 150°C for 30 minutes. The chemical resistance evaluation area was then observed using a laser microscope (Keyence Corporation, VK-9700). The number of cracks in the chemical resistance evaluation area was counted and color unevenness was observed (color differences between the inside and outside of the chemical resistance evaluation area were considered to be color unevenness, and no color differences were considered to be color unevenness). The results were evaluated as follows, with A to D being considered to have good chemical resistance. A: 0 cracks. No color unevenness. B: 0 cracks. Color unevenness. C+: 1 to 10 cracks. No color unevenness. C: 1 to 10 cracks. Color unevenness. D+: 11 to 30 cracks. No color unevenness. D: 11 to 30 cracks. Color unevenness. E+: 31 to 100. No color unevenness. E: 31 to 100 pieces. Color unevenness. F+: 101 or more. No color unevenness. F: 101 or more pieces. Color unevenness.

[0137] (3) Continuous operation stability of semiconductor elements A semiconductor device sample fabricated using the method described below was evaluated in air using a semiconductor device parameter analyzer (Keysight Technologies, B1500A). First, the source-drain voltage (Vsd) was set to -5 V, and the gate voltage (Vg) was swept from +2 V to -7 V in 0.1 V increments. Note that the voltage is referenced to the source electrode, and so on. This is the initial characteristic. Next, Vsd was set to 0 V, and Vg = 0 V and Vg = -5 V were applied alternately at 1 kHz for 1 minute. Finally, Vsd was set to -5 V, and Vg was swept from +2 V to -7 V in 0.1 V increments. This is the characteristic after continuous operation. The on-current or off-current of the characteristic after continuous operation divided by the on-current or off-current of the initial characteristic is multiplied by 100 to obtain the characteristic variation ratio (%). The on-current is the source-drain current (Isd) at Vg = -5 V, and the off-current is the Isd at Vg = 0 V. The larger of the on-current or off-current characteristic fluctuation rates was determined as follows, and A to D were determined to indicate good continuous operational stability of the device. A: 150% or less B: More than 150% and less than 200% C: Greater than 200% and less than 250% D: More than 250% and less than 300% E: Greater than 300%.

[0138] (Example of composition preparation) (1) Preparation example 1 of insulating layer material: Insulating layer material solution A Polysiloxane was synthesized using the following procedure. A three-neck flask was charged with 35.70 g of methyltrimethoxysilane (MeSi), 68.59 g of p-styryltrimethoxysilane (StSi), 30.71 g of 3-acryloxypropyltrimethoxysilane (AcrSi), 34.38 g of 3-trimethoxysilylpropylsuccinic anhydride (SucSi), 0.50 g of dibutylhydroxytoluene, and 181.28 g of propylene glycol monomethyl ether (PGME). The flask was immersed in a 40°C oil bath and stirred for 60 minutes. Then, an aqueous solution of phosphoric acid (0.88 g of phosphoric acid dissolved in 47.18 g of water) was added over 10 minutes. After 50 minutes, the oil bath temperature was set to 70°C, and the mixture was stirred for 60 minutes. The oil bath temperature was then set to 110°C, and the solution was allowed to reach a temperature of 90°C, after which it was stirred for 2 hours. The resulting solution was cooled in an ice bath, and then 2% by weight of anion exchange resin and cation exchange resin were added to the resin solution, followed by stirring for 12 hours. After stirring, the anion exchange resin and cation exchange resin were removed by filtration, yielding polysiloxane solution A. During stirring, nitrogen was passed through at 0.1 L / min to distill off the reaction by-products, methanol and water. The solids concentration of the resulting polysiloxane solution A was 42.4% by mass.

[0139] Next, 100.10 g of "Optlake (registered trademark)" TR-550 (manufactured by JGC Catalysts and Chemicals Co., Ltd.), which is a methanol dispersion of titanium oxide-silicon oxide composite particles, and 79.68 g of diacetone alcohol (DAA) were mixed, and the methanol was then distilled off under reduced pressure using a rotary evaporator to obtain titanium oxide particle dispersion A. The solids concentration of the obtained titanium oxide particle dispersion A was 21.1 mass %.

[0140] 4.5 g of polysiloxane solution A, 23.1 g of titanium oxide particle dispersion A, 0.1 g of 2,3-dihydroxypropyl acrylate, 0.098 g of OXE-04 (trade name "Irgacure", BASF Ltd.), 0.007 g of 4-tert-butylcatechol, 21.1 g of PGME, and 100 ppm of DFX-18 (fluorine-based surfactant, manufactured by Neos Corporation) were mixed, stirred at room temperature for 2 hours, and filtered through a 0.22 μm pore filter to obtain insulating layer material solution A. In insulating layer material solution A, the polysiloxane and 2,3-dihydroxypropyl acrylate in polysiloxane solution A correspond to precursors of the (b) polymer. These react to form the (b) polymer in a later step in the example.

[0141] (2) Preparation example 2 of insulating layer material: Insulating layer material solution B Polysiloxane was synthesized according to the following procedure. 35.70 g of MeSi, 68.59 g of StSi, 30.71 g of AcrSi, 34.38 g of SucSi, 10.76 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (EpoSi), 0.50 g of dibutylhydroxytoluene, and 183.33 g of PGME were placed in a three-neck flask and stirred for 60 minutes in a 40°C oil bath. An aqueous solution of phosphoric acid (0.90 g of phosphoric acid dissolved in 49.54 g of water) was then added over 10 minutes. After 50 minutes, the oil bath temperature was set to 70°C and the mixture was stirred for 60 minutes. The oil bath temperature was then set to 110°C. After the solution reached 90°C, the mixture was stirred for 2 hours. The resulting solution was cooled in an ice bath, and then 2% by weight of anion exchange resin and cation exchange resin were added to the resin solution, followed by stirring for 12 hours. After stirring, the anion exchange resin and cation exchange resin were removed by filtration, yielding polysiloxane solution B. During stirring, nitrogen was passed through at a rate of 0.1 L / min, and the reaction by-products, methanol and water, were distilled off. The solids concentration of the resulting polysiloxane solution B was 42.0% by mass.

[0142] 4.7 g of polysiloxane solution B, 23.1 g of titanium oxide particle dispersion A, 0.098 g of OXE-04, 0.007 g of 4-tert-butylcatechol, 21.00 g of PGME, and 100 ppm of DFX-18 were mixed, stirred at room temperature for 2 hours, and filtered through a filter with a 0.22 μm pore size to obtain insulating layer material solution B. In insulating layer material solution B, the polysiloxane in polysiloxane solution B corresponds to the precursor of (b) polymer.

[0143] (3) Preparation example 3 of insulating layer material: Insulating layer material solution C 5.0 g of barium titanate particles (particle size 50 nm, manufactured by Aldrich) and 45.0 g of PGME were mixed and ultrasonically stirred in an ice bath using an ultrasonic homogenizer (Tokyo Rikakikai Co., Ltd., VCX-500). Next, 4.9 g of polysiloxane solution B was added, and the mixture was ultrasonically treated using an ultrasonic disperser (Thinky Corporation, PR-1) to obtain barium titanate particle dispersion A. The solids concentration of the obtained barium titanate particle dispersion A was 13.0 mass%.

[0144] 45.6 g of barium titanate particle dispersion A, 0.090 g of OXE-04, 0.006 g of 4-tert-butylcatechol, 3.6 g of PGME, and 100 ppm of DFX-18 were mixed, stirred at room temperature for 2 hours, and filtered through a filter with a 0.22 μm pore size to obtain insulating layer material solution C. In insulating layer material solution C, the polysiloxane in polysiloxane solution B corresponds to the (b) polymer precursor.

[0145] (4) Preparation Example 4 of Insulating Layer Material: Insulating Layer Material Solution D Barium titanate particle dispersion B was obtained in the same manner as in the preparation of barium titanate particle dispersion A, except that 2.8 g of polysiloxane solution B was used. The solids concentration of the obtained barium titanate particle dispersion B was 11.8 mass %.

[0146] 49.3 g of barium titanate particle dispersion B, 0.083 g of OXE-04, 0.006 g of 4-tert-butylcatechol, and 100 ppm of DFX-18 were mixed, stirred at room temperature for 2 hours, and filtered through a filter with a 0.22 μm pore size to obtain insulating layer material solution D. In insulating layer material solution D, the polysiloxane in polysiloxane solution B corresponds to the (b) polymer precursor.

[0147] (5) Preparation example 5 of insulating layer material: insulating layer material solution E Except for using 41.06 g of MeSi, 1.08 g of EpoSi, and 176.83 g of PGME, polysiloxane solution C was obtained in the same manner as in the preparation of polysiloxane solution B. The solids concentration of the obtained polysiloxane solution C was 42.2 mass%.

[0148] Barium titanate particle dispersion liquid C was obtained in the same manner as in the preparation of barium titanate particle dispersion liquid A, except that polysiloxane solution C was used instead of polysiloxane solution B. The solids concentration of the obtained barium titanate particle dispersion liquid C was 13.0 mass %.

[0149] Insulating layer material solution E was obtained in the same manner as in preparing insulating layer material solution C, except that barium titanate particle dispersion solution C was used instead of barium titanate particle dispersion solution A. In insulating layer material solution E, the polysiloxane in polysiloxane solution C corresponds to the (b) polymer precursor.

[0150] (6) Preparation Example 6 of Insulating Layer Material: Insulating Layer Material Solution F Polysiloxane solution D was obtained in the same manner as in the preparation of polysiloxane solution B, except that 23.80 g of MeSi, 32.29 g of EpoSi, and 197.77 g of PGME were used. The solids concentration of the obtained polysiloxane solution D was 42.0 mass%.

[0151] Barium titanate particle dispersion D was obtained in the same manner as in the preparation of barium titanate particle dispersion A, except that polysiloxane solution D was used instead of polysiloxane solution B. The solids concentration of the obtained barium titanate particle dispersion D was 13.0 mass %.

[0152] Insulating layer material solution F was obtained in the same manner as in preparing insulating layer material solution C, except that barium titanate particle dispersion solution D was used instead of barium titanate particle dispersion solution A. In insulating layer material solution F, the polysiloxane in polysiloxane solution D corresponds to the precursor of the (b) polymer.

[0153] (7) Preparation example 7 of insulating layer material: Insulating layer material solution G Except for using 95.20 g of MeSi and 123.63 g of PGME, and not using StSi or AcrSi, polysiloxane solution E was obtained in the same manner as in the preparation of polysiloxane solution B. The solids concentration of the obtained polysiloxane solution E was 41.5 mass%.

[0154] Barium titanate particle dispersion liquid E was obtained in the same manner as in the preparation of barium titanate particle dispersion liquid A, except that polysiloxane solution E was used instead of polysiloxane solution B. The solids concentration of the obtained barium titanate particle dispersion liquid E was 13.0 mass %.

[0155] Insulating layer material solution G was obtained in the same manner as in preparing insulating layer material solution C, except that barium titanate particle dispersion solution E was used instead of barium titanate particle dispersion solution A. In insulating layer material solution G, the polysiloxane in polysiloxane solution E corresponds to the precursor of the polymer for the insulating layer.

[0156] (8) Preparation example 8 of insulating layer material: Insulating layer material solution H Except for using 41.65 g of MeSi and 176.11 g of PGME and not using EpoSi, polysiloxane solution F was obtained in the same manner as in the preparation of polysiloxane solution B. The solids concentration of the obtained polysiloxane solution F was 42.0 mass%.

[0157] Barium titanate particle dispersion liquid F was obtained in the same manner as in the preparation of barium titanate particle dispersion liquid A, except that polysiloxane solution F was used instead of polysiloxane solution B. The solids concentration of the obtained barium titanate particle dispersion liquid F was 13.0 mass %.

[0158] Insulating layer material solution H was obtained in the same manner as in preparing insulating layer material solution C, except that barium titanate particle dispersion solution F was used instead of barium titanate particle dispersion solution A. In insulating layer material solution H, the polysiloxane in polysiloxane solution F corresponds to the precursor of the polymer for the insulating layer.

[0159] (9) Preparation example of insulating layer material 9: Insulating layer material solution I Insulating layer material solution I was obtained in the same manner as in preparing insulating layer material solution C, except that strontium titanate particles (particle size <100 nm, manufactured by Aldrich) were used instead of barium titanate particles. In insulating layer material solution I, the polysiloxane in polysiloxane solution B corresponds to the (b) polymer precursor.

[0160] (10) Preparation Example 10 of Insulating Layer Material: Insulating Layer Material Solution J 4.1 g of polysiloxane solution F, 19.8 g of titanium oxide particle dispersion A, 0.084 g of OXE-04, 0.006 g of 4-tert-butylcatechol, 22.0 g of PGME, and 100 ppm of DFX-18 were mixed, stirred at room temperature for 2 hours, and filtered through a filter with a 0.22 μm pore size to obtain insulating layer material solution J. In insulating layer material solution J, the polysiloxane in polysiloxane solution F corresponds to the precursor of the insulating layer polymer.

[0161] (11) Preparation Example 11 of Insulating Layer Material: Insulating Layer Material Solution K 4.1 g of polysiloxane solution B, 8.4 g of zirconium oxide particle dispersion (manufactured by Aldrich), 0.084 g of OXE-04, 0.006 g of 4-tert-butylcatechol, 36.7 g of propylene glycol monomethyl ether acetate, and 100 ppm of DFX-18 were mixed, stirred at room temperature for 2 hours, and filtered through a filter with a 0.22 μm pore size to obtain insulating layer material solution K. In insulating layer material solution K, the polysiloxane in polysiloxane solution B corresponds to the precursor of the (b) polymer of the insulating layer.

[0162] (12) Preparation Example 1 of Semiconductor Layer Material: Semiconductor Layer Solution A First, the semiconducting CNTs and metallic CNTs were separated as follows.

[0163] CNT-A (Meijo Nanocarbon Co., Ltd., MEIJO eDIPS EC1.5) and sodium cholate (SC) were mixed in water (purified water purified by distillation) measured to give an SC concentration of 0.5% by mass and a CNT concentration of 0.1% by mass. 100 g of this mixture was irradiated with ultrasound (50% output, 3 hours) using an ultrasonic homogenizer (Branson: Digital Sonifier Models 250). The resulting CNT dispersion was placed in an ultracentrifuge (Hitachi, himac CS100GXII) and processed at 50,000 G for 30 minutes to settle and remove impurities that had been mixed in during CNT synthesis. This was used as the raw CNT dispersion.

[0164] Sodium dodecyl sulfonate (SDS) was added to the obtained raw CNT dispersion to adjust the SDS concentration to 0.5% by mass, thereby obtaining raw CNT dispersion 2 with an SC concentration and an SDS concentration of 0.5% by mass. This raw CNT dispersion 2 was then loaded into a gel-filled column, and an aqueous solution with an SC concentration and an SDS concentration of 0.5% by mass was used as the developer. After the metallic CNTs had flowed out, the developer was switched to an aqueous solution with an SC concentration of 0.5% by mass, thereby obtaining a CNT dispersion with a high semiconducting CNT ratio. SDS was added to the obtained CNT dispersion, and the CNT dispersion was adjusted to a CNT dispersion with an SC concentration and an SDS concentration of 0.5% by mass, and this was again loaded into the gel-filled column. Again, an aqueous solution with an SC concentration and an SDS concentration of 0.5% by mass was used as the developer. After the metallic CNTs had flowed out, the developer was switched to an aqueous solution with an SC concentration of 0.5% by mass, thereby obtaining CNT dispersion 3 with an even higher semiconducting CNT ratio. The absorption spectrum of the obtained CNT dispersion 3 was measured using a spectrophotometer (JASCO V-770) in the wavelength range of 300 nm to 1100 nm, and the content of semiconducting CNTs in the CNTs was evaluated, and the content was found to be 96.4% by weight.

[0165] The obtained CNT dispersion 3 was pressure filtered using a 0.1 μm diameter membrane filter paper manufactured by Millipore Corp. The filtered CNT composition was washed twice with about 50 mL of methanol, twice with about 50 mL of water, twice with about 50 mL of methanol, and finally with about 50 mL of chloroform to obtain semiconducting CNT-A in the form of a chloroform wet cake.

[0166] Next, 1.0 mg of semiconducting CNT-A was added to a 10 mL solution of 5.0 mg of poly[3-(ethyl-6-hexanoate)thiophene-2,5-diyl] in chloroform. The mixture was then cooled on ice and ultrasonically stirred for 2 hours at 40% output using an ultrasonic homogenizer (Tokyo Rikakikai Co., Ltd., VCX-500) to obtain CNT dispersion 4. Next, the CNT dispersion 4 was filtered using a membrane filter (pore size 10 μm, diameter 25 mm, Millipore Omnipore Membrane). After adding 8 mL of 1,2-dichlorobenzene to the filtrate, the low-boiling point solvent, chloroform, was removed using a rotary evaporator to obtain CNT dispersion 5. 1,2-dichlorobenzene was added to CNT dispersion 5 to adjust the concentration, yielding CNT dispersion A (CNT concentration relative to the solvent: 0.04 g / L).

[0167] (13) Example of electrode material preparation: Conductive paste A Conductive paste A was obtained in the same manner as in Example 13 of WO 2019 / 065561.

[0168] Example 1 The semiconductor device shown in Figure 1 was fabricated as follows. Copper was vacuum-deposited to a thickness of 100 nm on a substrate 1 made of a 50 μm-thick PET film (product name "U48", Toray Industries, Inc.) by resistance heating, and then a photoresist (Rohm and Haas Co., Ltd., LC140-10cP) was spin-coated (1000 rpm x 20 seconds) and dried by heating at 100°C for 10 minutes. The fabricated photoresist film was subjected to pattern exposure through a mask using an exposure device (Orc Manufacturing Co., Ltd., EXF-2828-A-01) (exposure dose 40 mJ / cm). 2). In addition to the semiconductor element area, this mask pattern also contained a pattern of 100 copper electrode lines (20 μm wide, 1 cm long) spaced 200 μm apart, allowing for the creation of an area for evaluating the processing stability of the insulating layer. In a separate location, a pattern of copper electrode cross marks (20 μm wide, 500 μm square) was also included, allowing for the creation of an area for evaluating the chemical resistance of the insulating layer. The mask was then shower-developed for 60 seconds using an automatic developing system (Takizawa Sangyo Co., Ltd., AD-2000) with a 2.38 wt% aqueous solution of tetramethylammonium hydroxide (Mitsubishi Gas Chemical Co., Inc., ELM-D), followed by a 30-second rinse with water. The mask was then etched for 2 minutes with an etching solution (Kanto Chemical Co., Inc., Cu-03), followed by a 30-second rinse with water. The resist was removed by immersion in a resist remover (Kanto Chemical Co., Ltd., JELK-101) for 2 minutes, and then washed with water for 30 seconds and dried by heating at 100° C. for 3 minutes to form a gate electrode 2.

[0169] Next, the insulating layer material solution A was spin-coated (300 rpm x 10 seconds, then 1000 rpm x 2 seconds), heated at 80°C for 3 minutes, and then exposed using an exposure device (exposure amount 120 mJ / cm 2 Next, using an automatic developing device, the film was shower-developed with a 2.38 wt % aqueous solution of tetramethylammonium hydroxide for 30 seconds, and then washed with water for 30 seconds. A heat treatment was performed in a drying oven at 150°C for 3 minutes to form a gate insulating layer 3 with a film thickness of 400 nm.

[0170] Next, using an inkjet device (Cluster Technology Co., Ltd.), the semiconductor layer solution A was inkjet coated onto the gate insulating layer 3 in the semiconductor element portion and the chemical-resistant processing area. After that, a heat treatment was performed at 150°C for 30 minutes in a nitrogen atmosphere to form the semiconductor layer 4.

[0171] Next, conductive paste A was screen-printed, and after heat treatment at 100°C for 10 minutes using a drying oven, it was subjected to pattern exposure through a mask using an exposure device (exposure dose 70 mJ / cm 2). Next, using an automatic developing device, the film was shower-developed with a 0.5 wt % aqueous sodium carbonate solution for 60 seconds, washed with water, and then cured in a drying oven at 140°C for 30 minutes to form a source electrode 5 and a drain electrode 6. The channel width was 200 μm and the channel length was 20 μm. The semiconductor device thus obtained was evaluated according to the above evaluation methods (1) to (3). The results are summarized in Table 1.

[0172] Examples 2 to 7, Comparative Examples 1 to 4 Semiconductor devices were fabricated and evaluated in the same manner as in Example 1, except that insulating layer material solutions B to K were used instead of insulating layer material solution A. The results are summarized in Table 1. The semiconductor device fabricated using insulating layer material solution G had a large current between the source electrode and gate electrode and did not function as a semiconductor device. This is thought to be due to the low chemical resistance of the insulating layer, which caused a short circuit between the source electrode and gate electrode.

[0173] [Table 1] [Explanation of symbols]

[0174] 1, 11, 21 Base material 2, 12 Gate electrode 3, 13 Gate insulating layer 4, 14, 24 semiconductor layers 5, 15 Source electrode 6, 16 Drain electrode 10, 20, 30 Semiconductor elements 22 3rd electrode 23 Insulating layer 25 cathode 26 anode 29 4th electrode 200 TFT array 210 TFT 220 TFT 230 TFT 240 TFT 250 gate lines 260 gate lines 270 source lines 280 source lines

Claims

1. A semiconductor element including at least a substrate, a first electrode, a second electrode, a semiconductor layer in contact with both the first electrode and the second electrode, an insulating layer in contact with the semiconductor layer, and a third electrode in contact with the insulating layer on a side of the semiconductor layer opposite to the insulating layer, The insulating layer comprises the following (a) and (b): (a) Titanium compound particles (b) Polymers having the following structures (b1), (b2), and (b3): (b1) Addition reaction structure of an alkenyl group, an acrylic group, or a methacrylic group (b2) a 1,2-dihydroxyethyl group, a 1,2-dihydroxyethylene group, a 1,3-dihydroxypropyl group, or a 1,3-dihydroxypropylene group (b3) an organic group containing at least two of a carboxyl group, a sulfo group, a thiol group, a phenolic hydroxyl group, or a derivative thereof; provided that, when the derivative has a cyclic condensation structure formed by two of the carboxyl group, the sulfo group, the thiol group, and the phenolic hydroxyl group, (b3) is an organic group having at least one of the cyclic condensation structures. A semiconductor element comprising:

2. The semiconductor device according to claim 1 , wherein the polymer (b) is polysiloxane.

3. 3. The semiconductor device according to claim 2, wherein the polysiloxane has at least structural units represented by general formula (1), general formula (2), and general formula (3). 【Chemical 1】 【Chemistry 2】 【Chemistry 3】 (In the general formula (1), the general formula (2) and the general formula (3), A １ represents an organic group containing an addition reaction structure of an alkenyl group, an acryl group, or a methacryl group. ２ represents an organic group having at least one structure selected from the group consisting of a 1,2-dihydroxyethyl group, a 1,2-dihydroxyethylene group, a 1,3-dihydroxypropyl group, and a 1,3-dihydroxypropylene group. ３ represents an organic group containing at least two of a carboxyl group, a sulfo group, a thiol group, a phenolic hydroxyl group, or a derivative thereof, provided that when the derivative has a cyclic condensation structure formed by two of the carboxyl group, the sulfo group, the thiol group, and the phenolic hydroxyl group, A ３ represents an organic group having at least one cyclic condensed structure. １ , R ３ and R ５ R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a heterocyclic group, an aryl group, a heteroaryl group, or an alkenyl group. ２ , R ４ and R ６ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, or a silyl group; m, n, and o each independently represent 0 or 1.

4. 2. The semiconductor device according to claim 1, wherein the (a) titanium compound particles are inorganic titanium compound particles.

5. The semiconductor device according to claim 4 , wherein the inorganic titanium compound particles are titanic acid compound particles.

6. 2. The semiconductor device according to claim 1, wherein the content of said (a) titanium compound particles is 60% by weight or more when the total of said (a) titanium compound particles and said (b) polymer is 100% by weight.

7. The semiconductor device of claim 1 , wherein the semiconductor layer comprises nanocarbon.

8. The semiconductor device according to claim 7 , wherein the nanocarbon is a carbon nanotube.

9. The method for manufacturing a semiconductor device according to any one of claims 1 to 8, comprising the following (Step 1) to (Step 3): (Step 1) Step of forming a conductive pattern on a substrate (Step 2) A step of applying a solution containing at least titanium compound particles and (b) a polymer or a precursor thereof to the substrate on which the conductive pattern has been formed, drying the solution, obtaining a coating film, and then curing the coating film to form an insulating layer. (Step 3) forming a conductive pattern on the insulating layer.

10. The method for manufacturing a semiconductor device according to any one of claims 1 to 8, comprising the following (Step 1') to (Step 3'): (Step 1') Step of forming a conductive pattern on a substrate (Step 2') A step of applying a solution containing at least titanium compound particles and (b) a polymer or a precursor thereof onto the substrate on which the conductive pattern has been formed, drying the solution to obtain a coating film, and then irradiating the coating film with actinic rays through a photomask and developing the coating film to form a pattern having openings on the conductive pattern or the substrate, thereby forming an insulating layer having openings. (Step 3') A step of forming a conductive pattern on the insulating layer.

11. A circuit comprising the semiconductor element according to any one of claims 1 to 8.

12. A wireless communication device comprising at least the circuit according to claim 11 and an antenna.

13. A thin film transistor array comprising the semiconductor element according to any one of claims 1 to 8.

14. A sensor comprising the semiconductor element according to any one of claims 1 to 8.

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