JP6399989B2 - Organic thin film transistor, material for organic thin film transistor, material set for organic thin film transistor, method of manufacturing organic thin film transistor - Google Patents

Description

  The present invention relates to an organic thin film transistor, a material for an organic thin film transistor, a material set for an organic thin film transistor, and a method for manufacturing an organic thin film transistor.

Logics such as FET (field effect transistor), RFID (radio frequency identifier: RF tag) and memory used for liquid crystal display and organic EL (electro luminescence) display because weight reduction, cost reduction and flexibility are possible. 2. Description of the Related Art Organic thin film transistors (organic TFTs) having organic semiconductor films are used for devices using circuits.
As such an organic semiconductor film, for example, Patent Document 1 discloses an organic semiconductor film formed by crystallizing a low molecular weight organic semiconductor compound.

Japanese Patent Publication No. 2013-516054 gazette

The inventor of the present invention examined an organic thin film transistor having an organic semiconductor film formed by crystallizing a low molecular weight organic semiconductor compound described in Patent Document 1, but in the heating process when mounting the organic thin film transistor on an integrated circuit or the like. It has been found that a crack is generated in the organic semiconductor film due to the difference in thermal expansion coefficient between the organic semiconductor film and the substrate and the gate insulating layer adjacent to the organic semiconductor film. The same tendency was also confirmed for an organic thin film transistor having an organic semiconductor film formed by crystallizing an organic semiconductor polymer compound.
Generally, it is considered that when the organic semiconductor film is cracked, the carrier mobility is also reduced, and in view of the recent demand for improvement of the carrier mobility, it is desirable to suppress the occurrence of the crack.

Accordingly, an object of the present invention is to provide an organic thin film transistor in which a crack is not easily generated in an organic semiconductor film even when subjected to a heating process.
In addition, another object of the present invention is an organic thin film transistor material and an organic thin film transistor material set which can be used for forming an organic thin film transistor and can provide an organic semiconductor film in which cracking in a heating process is suppressed. A method of manufacturing a thin film transistor is provided.

As a result of intensive studies to achieve the above object, the present inventor contains a negative expansion material at a position adjacent to an organic semiconductor film (hereinafter also referred to as "organic semiconductor layer") which is a crystal layer in an organic thin film transistor It has been found that by providing a buffer layer (hereinafter also referred to as “intermediate layer”), the occurrence of cracks in the organic semiconductor layer due to the thermal expansion of the substrate and the gate insulating layer can be suppressed. Further, it has been found that the same effect can be obtained by blending this negative expansion material in the gate insulating layer, and the present invention has been completed.
That is, it discovered that the above-mentioned subject could be achieved by the following composition.

(1) A gate electrode, an organic semiconductor layer, a gate insulating layer provided between the gate electrode and the organic semiconductor layer, and the organic semiconductor layer are provided in contact with each other, and are connected via the organic semiconductor layer An organic thin film transistor having a source electrode and a drain electrode,
An organic thin film transistor comprising a negative expansion material in at least one of the gate insulating layer and an intermediate layer disposed adjacent to the organic semiconductor layer.
(2) The organic thin film transistor according to (1), wherein the average particle diameter of the negative expansion material is 10 to 1000 nm.
(3) The organic thin film transistor according to (1) or (2), wherein the aspect ratio of the negative expansion material is 2 to 50.
(4) The organic thin film transistor according to any one of (1) to (3), wherein the negative expansion material is zirconium tungstate.
(5) The organic thin film transistor according to any one of (1) to (4), wherein the gate insulating layer is formed of an organic material.
(6) The organic thin film transistor according to any one of (1) to (5), wherein the negative expansion material is contained in the gate insulating layer.
(7) The organic thin film transistor according to any one of (1) to (6), wherein the negative expansion material is contained in an intermediate layer disposed adjacent to the organic semiconductor layer.
(8) The organic thin film transistor according to any one of (1) to (7), wherein the organic semiconductor layer contains a surfactant having a glass transition temperature of 50 ° C. or higher.
(9) A material for an organic thin film transistor, containing at least an organic semiconductor compound, a binder and a negative expansion material.
(10) A material set for an organic thin film transistor, comprising a composition containing at least an organic semiconductor compound, and a composition containing at least a binder and a negative expansion material.
(11) A gate electrode, an organic semiconductor layer, a gate insulating layer provided between the gate electrode and the organic semiconductor layer, and the organic semiconductor layer are provided in contact with each other, and are connected via the organic semiconductor layer A method of manufacturing an organic thin film transistor having a source electrode and a drain electrode,
It is formed adjacent to the said organic-semiconductor layer and the said organic-semiconductor layer using the organic thin-film transistor material as described in (9) or the organic thin-film transistor material set as described in (10), and contains a binder and a negative expansion material And an intermediate layer to form an organic thin film transistor.

  In the present specification, the expression of a compound is used to include the salt itself and the ion as well as the compound itself.

In the present specification, when there are a plurality of substituents, linking groups and the like (hereinafter referred to as substituents and the like) represented by specific symbols, or when a plurality of substituents and the like are simultaneously defined, the respective substituents are mutually It means that it may be the same or different. The same applies to the definition of the number of substituents and the like.
In addition, unless a plurality of substituents or the like are adjacent (particularly, adjacent), it means that they may be linked to each other or condensed to form a ring.
Furthermore, in the present specification, a substituent or the like which does not specify substitution or non-substitution in the specification means that the group may further have a substituent as long as the target effect is not impaired. This is also the same as for compounds in which no substitution or substitution is specified.

  The numerical range represented using "-" in this specification means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.

According to the present invention, it is possible to provide an organic thin film transistor in which a crack does not easily occur in an organic semiconductor film even if a heating process is performed.
Further, according to the present invention, an organic thin film transistor material and an organic thin film transistor material set that can be used to form an organic thin film transistor and can provide an organic semiconductor film in which cracking in a heating process is suppressed, and an organic thin film transistor using these A manufacturing method can be provided.

(A)-(C) are figures which show typically the preferable structure of the organic thin-film transistor of this invention. (A)-(C) are figures which show the other structure of an organic thin-film transistor typically.

Hereinafter, the present invention will be described in detail.
Although the description of the configuration requirements described below may be made based on the representative embodiments of the present invention, the present invention is not limited to such embodiments.

[Organic thin film transistor]
The structure of the organic thin film transistor of the present invention (hereinafter simply referred to as "the OTFT of the present invention") will be described below.

  The OTFT of the present invention is provided in contact with an organic semiconductor layer and connected via an organic semiconductor, to a gate electrode, an organic semiconductor layer, and a gate insulating layer provided between the gate electrode and the organic semiconductor layer. It has a source electrode and a drain electrode. When a voltage is applied to the gate electrode, a current flow channel (channel) is formed at the interface between the organic semiconductor layer between the source electrode and the drain electrode and the layer adjacent thereto. That is, in accordance with the input voltage applied to the gate electrode, the current flowing between the source electrode and the drain electrode is controlled.

The preferred structure of the OTFT of the present invention will be described based on the drawings. The OTFT shown in each drawing is a schematic diagram for facilitating the understanding of the present invention, and the size or relative magnitude relationship of each member may be different in magnitude for convenience of explanation. Does not indicate that. Moreover, it is not limited to the external shape and shape shown by these figures except the matter prescribed | regulated by this invention. For example, in FIGS. 1 (A) and 1 (B), the gate electrode 5 does not necessarily have to cover the whole of the substrate 6, and the form provided in the central part of the substrate 6 is also preferable as the form of OTFT of the present invention .
1A to 1B show an OTFT having a bottom gate / bottom contact structure.
In the OTFT shown in FIG. 1A, a gate electrode 5, a gate insulating layer 2, a source electrode 3 and a drain electrode 4, an intermediate layer 7, and an organic semiconductor layer 1 are disposed in this order on a substrate 6. It is. As described later, the intermediate layer 7 contains a negative expansion material and is disposed adjacent to the organic semiconductor layer 1.
Further, the OTFT shown in FIG. 1B is one in which the gate electrode 5, the gate insulating layer 12, the source electrode 3 and the drain electrode 4 and the organic semiconductor layer 1 are disposed in this order on the substrate 6. . As described later, the gate insulating layer 12 contains a negative expansion material.

The OTFT of the present invention comprises (1) a point at which an intermediate layer 7 containing a negative expansion material is provided adjacent to the organic semiconductor layer 1 and / or (2) a gate insulating layer 12 containing a negative expansion material. It is characterized by the point used. According to the above configuration, in the organic thin film transistor of the present invention, the occurrence of cracks in the organic semiconductor layer 1 in the heating process is suppressed, and the decrease in carrier mobility is suppressed. Specifically, in the embodiment of the above (1) in which the intermediate layer 7 containing a negative expansion material is provided at a position adjacent to the organic semiconductor layer 1, the thermal stress due to the thermal expansion of the substrate 6 or the gate insulating layer 2 is negative expansion. By being relieved by the intermediate layer 7 having a material, cracks in the organic semiconductor layer 1 are suppressed. Further, when the negative expansion material is directly introduced into the gate insulating layer 2 as in the embodiment (2), the thermal expansion of the gate insulating layer 2 itself is suppressed, whereby the cracks in the organic semiconductor layer 1 are suppressed. Be done.
Generally, the material expands when heated, but it is known that the linear expansion coefficient of an organic material, such as an organic polymer, is large, and thus the organic thin film transistor of the present invention comprises When the substrate 6 is formed of an organic material such as an organic polymer as described later, the crack suppressing effect of the organic semiconductor layer 1 is most effectively exhibited.

In addition, although the intermediate | middle layer 7 is arrange | positioned between the gate insulating layer 2 and the organic-semiconductor layer 1 in FIG. 1 (A), if it is arrange | positioned in the position adjacent to the organic-semiconductor layer 1, this aspect For example, as shown to FIG. 1C, you may arrange | position on the surface on the opposite side to the gate insulating layer 2 side of the organic-semiconductor layer 1, for example.
Further, in FIG. 1A, the intermediate layer 7 is disposed on the gate insulating layer 2 between the source electrode 3 and the drain electrode 4, but is not limited to this embodiment, for example, the source electrode 3 and the drain An intermediate layer may be disposed to cover the electrode 4 and the gate insulating layer 2.

Furthermore, in FIGS. 1A and 1B, although the bottom gate bottom contact OTFT has been described, the present invention is not limited to this embodiment, and a bottom gate top contact OTFT having a top gate bottom contact structure is described. Even in the case of an OTFT, an OTFT having a top gate top contact structure, an intermediate layer adjacent to the organic semiconductor layer as described above is disposed, and / or a negative expansion material is contained in the gate insulating layer. It is sufficient if either one is satisfied.
For example, FIGS. 2A to 2C show an OTFT having a top gate structure, and as shown in FIG. 2A, an intermediate containing a negative expansion material between the organic semiconductor layer 1 and the gate insulating layer 2. 2B, an embodiment in which the intermediate layer 7 containing a negative expansion material is disposed between the organic semiconductor layer 1 and the substrate 6 as shown in FIG. As shown in 2.), the aspect using the gate insulating layer 12 containing a negative expansion material may be sufficient.
In the case of the top gate structure, in addition to the above configuration, an aspect in which the intermediate layer 7 is provided on both sides of the organic semiconductor layer 1 (in other words, the interface of the organic semiconductor layer 1 on the substrate 6 side, the gate insulating electric layer 2 The aspect which provided the intermediate | middle layer in any of the side may be sufficient.
The intermediate layer is preferably disposed on the surface between the organic semiconductor layer and the gate insulating layer or on the surface of the organic semiconductor layer opposite to the gate insulating layer, and the organic semiconductor layer and the gate are preferably disposed. Preferably, it is disposed between the insulating layer.

  Hereinafter, the OTFT shown in FIG. 1A (first embodiment) and the OTFT shown in FIG. 1B (second embodiment) will be described in detail as a representative example.

<< first aspect >>
First, each configuration of the first aspect and a method of manufacturing the same will be described in detail. First, the middle layer which is each feature point will be described in detail.

<Middle class>
The intermediate layer is a layer containing a negative expansion material and formed adjacent to the organic semiconductor layer.
The negative expansion material is a material that shrinks with temperature rise, and preferably has negative expansion property in the range of 0 to 200 ° C., for example, HfW ₂ O ₈ , (ZrO) ₂ P ₂ O ₃ And particles such as ZrW ₂ O ₈ , Nb ₂ O ₅ , and SiO ₂ (faujasite structure). It is excellent in dispersion stability, has an appropriate thermal expansion coefficient, is excellent in coating property, and can form an intermediate layer of appropriate surface free energy (that is, to the wettability of the organic semiconductor layer formed adjacently) ZrW ₂ O ₈ (zirconium tungstate) is preferred in that it is less affected by the reaction, which results in excellent mobility.
ZrW ₂ O ₈ is preferably produced by a wet method from the viewpoint of particle aspect ratio and average particle diameter.
The aspect ratio of the negative expansion material is preferably 1 to 50, and more preferably 2 to 50. The aspect ratio is represented by the ratio of the major axis to the minor axis of the particles (major axis / minor axis), and when it is in the above range, the coating film surface becomes smooth and the crack preventing effect becomes better. The aspect ratio of the negative expansion material is more preferably 2 to 30, and further preferably 5 to 15.
The average particle diameter of the negative expansion material is preferably 10 to 1000 nm, more preferably 50 to 800 nm, and still more preferably 100 to 600 nm. By setting it as the said range, while being excellent by coating property and dispersion stability, it becomes possible to introduce | transduce a predetermined amount of negative expansion materials, without enlarging the thickness of the intermediate | middle layer 7. FIG. Further, since the intermediate layer 7 having a small thickness can be formed, the contact between the organic semiconductor layer 1 and the gate electrode 6 or the drain electrode 4 is not inhibited, and the carrier mobility is more excellent.
As a method of measuring the major axis of the negative expansion material, when observing the negative expansion material by TEM (Transmission Electron Microscope) observation or SEM (Scanning Electron Microscope) observation, among parallel parallel planes circumscribed to the negative expansion material, The distance between two parallel planes selected so as to maximize the distance between the two planes is taken as the “major axis”. In addition, of the two parallel planes perpendicular to the two parallel planes giving the major axis and circumscribed to the negative expansion material, the distance between the two parallel planes selected so as to minimize the distance between the two parallel planes is taken as the “minor axis”.
In addition, as a measuring method of an aspect ratio, the major axis and the minor axis of at least 50 negative expansion materials are measured, the respective aspect ratios are calculated, and they are determined by arithmetic averaging.
As a method of measuring the above average particle diameter, the major axis and minor axis of at least 50 negative expansion materials are measured, and the average value of the major axis and minor axis of each negative expansion material is determined Ask.

  The content of the negative expansion material in the intermediate layer is preferably 0.01 to 70% by mass, more preferably 0.1 to 40% by mass, based on the total solid content, and 5 It is further more preferable to contain by -30 mass%. By being contained in the said range, the thermal stress to an organic-semiconductor layer can be suppressed, and the crack generation of an organic-semiconductor layer is suppressed more effectively.

The intermediate layer may contain components other than the above-mentioned negative expansion material, and may contain, for example, a binder that carries (disperses) the negative expansion material.
Although the kind in particular of the binder used is not restrict | limited, The organic material (organic polymer) or inorganic material which may be contained in the gate insulating layer mentioned later is mentioned.
Among them, a polymer compound having a benzene ring (polymer having a repeating unit having a benzene ring group) is preferable. The content of the repeating unit having a benzene ring group is not particularly limited, but is preferably 50 mol% or more, more preferably 70 mol% or more, and still more preferably 90 mol% or more in all the repeating units. Although the upper limit in particular is not restrict | limited, 100 mol% is mentioned.
Examples of the polymer compound include polystyrene, poly (α-methylstyrene), polyvinylcinnamate, poly (4-vinylphenyl) or poly (4-methylstyrene).
The weight average molecular weight of the polymer compound is not particularly limited, but is preferably 10,000 to 2,000,000, more preferably 20,000 to 1,000,000, and still more preferably 100,000 to 600,000.

  The content of the binder in the intermediate layer is preferably 15 to 95% by mass, and more preferably 20 to 85% by mass, based on the total solid content.

  The intermediate layer may contain components other than the negative expansion material and the binder described above. For example, a surfactant (particularly, a surfactant having a glass transition temperature of 50 ° C. or higher), an organic semiconductor compound, and the like described later can be mentioned.

  In the organic thin film transistor, the thickness of the intermediate layer is preferably 1 to 500 nm, more preferably 10 to 300 nm, and particularly preferably 20 to 150 nm. By setting it in the above-mentioned range, a predetermined amount of negative expansion material can be introduced, and a crack can be effectively suppressed, and at the same time, the carrier mobility is more excellent without blocking the contact between the organic semiconductor layer and the gate electrode or drain electrode. An organic thin film transistor can be used.

  The method of forming the intermediate layer will be described in detail later, but using a material for an organic thin film transistor containing at least an organic semiconductor compound, a binder and a negative expansion material, the intermediate layer and the organic semiconductor layer are simultaneously made using phase separation phenomenon. Method of forming an intermediate layer separately from an organic semiconductor layer using a material set for an organic thin film transistor having a composition containing at least an organic semiconductor compound and a composition containing at least a binder and a negative expansion material Etc.

<Board>
The substrate may be any one that can support the OTFT and the display panel and the like fabricated thereon. The substrate is not particularly limited as long as it has insulating properties on the surface, is sheet-like, and has a flat surface.

An inorganic material may be used as the material of the substrate. As a substrate made of an inorganic material, for example, various glass substrates such as soda lime glass and quartz glass, various glass substrates having an insulating film formed on the surface, a quartz substrate having an insulating film formed on the surface, and an insulating film on the surface The silicon substrate formed, a sapphire substrate, a metal substrate consisting of various alloys such as stainless steel, aluminum, nickel and the like, metal foil, paper and the like can be mentioned.
When the substrate is formed of a conductive or semiconductive material such as stainless steel sheet, aluminum foil, copper foil or silicon wafer, usually, an insulating polymer material or metal oxide is applied or laminated on the surface. Used.

Alternatively, an organic material such as an organic polymer may be used as the material of the substrate. For example, polymethyl methacrylate (polymethyl methacrylate, PMMA), polyvinyl alcohol (PVA), polyvinyl phenol (PVP), polyether sulfone (PES), polyimide, polyamide, polyacetal, polycarbonate (PC), polyethylene terephthalate (PET), Examples thereof include flexible plastic substrates (also referred to as plastic films and plastic sheets) composed of organic polymers exemplified by polyethylene naphthalate (PEN), polyethyl ether ketone, polyolefin, and polycycloolefin. Moreover, what was formed with mica can also be mentioned.
If such a flexible plastic substrate or the like is used, for example, it becomes possible to incorporate or integrate the OTFT into a display device or electronic device having a curved surface shape.

It is preferable that the organic material forming the substrate has a high glass transition point, and it is preferable that the glass transition point is 40 ° C. or higher, because the organic material forming the substrate is difficult to soften when laminating other layers or heating. In addition, it is preferable that the coefficient of linear expansion be small from the viewpoint that the dimensional change is not easily caused by the heat treatment at the time of manufacture and the stability of the transistor performance is excellent. For example, a material having a linear expansion coefficient of 25 × 10 ⁻⁵ cm / cm · C or less is preferable, and a material having 10 × 10 ⁻⁵ cm / cm · C or less is more preferable.
In addition, the organic material forming the substrate is preferably a material having resistance to a solvent used at the time of producing the OTFT, and is preferably a material excellent in adhesion to the gate insulating layer and the electrode.
Furthermore, it is also preferable to use a plastic substrate made of an organic polymer having high gas barrier properties.
It is also preferable to provide a dense silicon oxide film or the like on at least one side of the substrate, or vapor-deposit or laminate an inorganic material.

  As the substrate, in addition to the above, a conductive substrate (a substrate made of a metal such as gold or aluminum, a substrate made of highly oriented graphite, a stainless steel substrate, etc.) can also be mentioned.

  The substrate may be provided with a buffer layer for improving adhesion and flatness, a functional film such as a barrier film for improving gas barrier properties, and a surface treatment layer such as an easy adhesion layer on the surface. Surface treatment such as corona treatment, plasma treatment, UV (ultraviolet light) / ozone treatment may be applied.

  The thickness of the substrate is preferably 10 mm or less, more preferably 2 mm or less, and particularly preferably 1 mm or less. Moreover, on the other hand, it is preferable that it is 0.01 mm or more, and it is more preferable that it is 0.05 mm or more. In particular, in the case of a plastic substrate, the thickness is preferably about 0.05 to 0.1 mm. In the case of a substrate made of an inorganic material, the thickness is preferably about 0.1 to 10 mm.

<Gate electrode>
As the gate electrode, a conventionally known electrode used as a gate electrode of OTFT can be used. It does not specifically limit as a conductive material (it is also called electrode material) which comprises a gate electrode. For example, metals such as platinum, gold, silver, aluminum, chromium, nickel, copper, molybdenum, titanium, magnesium, calcium, barium, sodium, palladium, iron, manganese, etc .; InO ₂ , SnO ₂ , indium-tin oxide (ITO Conductive metals such as tin-doped indium oxide), fluorine-doped tin oxide (FTO, F-doped tin oxide), aluminum-doped zinc oxide (AZO, Al-doped ZnO), gallium-doped zinc oxide (GZO, Ga-doped ZnO) Oxides; conductive polymers such as polyaniline, polypyrrole, polythiophene, polyacetylene, poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid (PEDOT / PSS); acids such as hydrochloric acid, sulfuric acid, sulfonic acid, PF ₆ , _AsF 5, FeCl _3, etc. Lewis acids, halogen atom such as iodine, sodium, Ca The conductive polymer which is added a dopant such as a metal atom such as um, as well as carbon black, graphite powder, a composite material of the conductive dispersed metal fine particles and the like. These materials may be used alone or in any combination of two or more in any proportion.
In addition, the gate electrode may be a single layer made of the above conductive material, or two or more layers may be stacked.

There is no limitation on the method of forming the gate electrode. For example, films formed by physical vapor deposition (PVD) such as vacuum deposition, chemical vapor deposition (CVD), sputtering, printing (coating), transfer, sol-gel, plating, etc. Accordingly, a method of patterning into a desired shape can be mentioned.
In the application method, a solution, paste or dispersion of the above-mentioned material can be prepared, applied, dried, fired, photocured or aged to form a film or directly form an electrode.
In addition, inkjet printing, screen printing, (reversal) offset printing, letterpress printing, intaglio printing, lithographic printing, thermal transfer printing, microcontact printing, etc. can perform desired patterning, and simplify the process, reduce costs, and achieve high speed. From the point of view of
Even in the case of employing a spin coating method, a die coating method, a microgravure coating method, or a dip coating method, patterning can be performed in combination with the following photolithography method or the like.

Examples of the photolithography method include a method of combining patterning of a photoresist with etching such as wet etching with an etching solution or dry etching with reactive plasma, a lift-off method, or the like.
As another patterning method, there is also a method of irradiating the above material with energy rays such as a laser and an electron beam to polish or change the conductivity of the material.
Furthermore, there is also a method of transferring the composition for gate electrode printed on a support other than the substrate onto an underlayer such as the substrate.

  The thickness of the gate electrode is optional, but is preferably 1 nm or more, and particularly preferably 10 nm or more. Moreover, 500 nm or less is preferable and 200 nm or less is especially preferable.

<Gate insulating layer>
The gate insulating layer is not particularly limited as long as it is provided between the gate electrode and the organic semiconductor layer and is a layer having an insulating property, and may be a single layer or a multilayer.
The gate insulating layer is preferably formed of an insulating material, and as the insulating material, for example, an organic material such as an organic polymer, an inorganic material such as an inorganic oxide, and the like are preferably mentioned. From the point of view, it is preferable to use an organic material.
The organic polymer, the inorganic oxide and the like are not particularly limited as long as they have insulating properties, and a thin film, for example, one capable of forming a thin film having a thickness of 1 μm or less is preferable.
The organic polymer and the inorganic oxide may be used alone or in combination of two or more. Further, the gate insulating layer may be a hybrid layer in which an organic polymer and an inorganic oxide which will be described later are mixed.

The organic polymer is not particularly limited. For example, polyvinylphenol, polystyrene (PS), poly (meth) acrylate typified by polymethyl methacrylate, polyvinyl alcohol, polyvinyl chloride (PVC), polyfluoride Vinylidene (PVDF), polytetrafluoroethylene (PTFE), cyclic fluoroalkyl polymers represented by CYTOP, polycycloolefin, polyester, polyether sulfone, polyether ketone, polyimide, poly (meth) acrylic acid, polybenzoxazole, Epoxy resins, polyorganosiloxanes represented by polydimethylsiloxane (PDMS), polysilsesquioxane, butadiene rubber and the like can be mentioned. In addition to the above, thermosetting resins such as phenol resins, novolak resins, cinnamate resins, acrylic resins and polyparaxylylene resins can also be mentioned.
The organic polymer can also be used in combination with a compound having a reactive substituent such as an alkoxysilyl group, a vinyl group, an acryloyloxy group, an epoxy group or a methylol group.

  When the gate insulating layer is formed of an organic polymer, it is also preferable to crosslink and cure the organic polymer for the purpose of increasing the solvent resistance and insulation resistance of the gate insulating layer. Crosslinking is preferably carried out by generating an acid or a radical using light, heat or both.

When it crosslinks by a radical, as a radical generating agent which generate | occur | produces a radical by light or heat, the thermal-polymerization initiator (H1) and photopolymerization start as described in [0182]-[0186] of Unexamined-Japanese-Patent No. 2013-214649, for example Agent (H2), photo radical generator described in [0046] to [0051] of JP-A-2011-186069, photo radical polymerization initiation described in [0042]-[0056] of JP-A-2010-285518 An agent etc. can be used suitably, Preferably these contents are included in this-application specification.
Moreover, as described in [0167] to [0177] of JP 2013-214649 A, "the number average molecular weight (Mn) is 140 to 5,000, has a crosslinkable functional group, and does not have a fluorine atom It is also preferred to use the compounds (G), the content of which is preferably incorporated herein.

When it bridge | crosslinks with an acid, as a photo-acid generator which generate | occur | produces an acid with light, the photocationic-polymerization initiator as described in-of Unexamined-Japanese-Patent No. 2010-285518, for example-, 0034 The acid generators described in [0120] to [0136] of the gazette, particularly sulfonium salts, iodonium salts and the like can be preferably used, and their contents are preferably incorporated into the present specification.
As a thermal acid generator (catalyst) that generates an acid by heat, for example, a thermal cationic polymerization initiator described in JP-A-2010-285518, [0035] to [0038], particularly an onium salt, etc. The catalysts described in paragraphs [0034] to [0035] of JP-35-34012, particularly sulfonic acids and sulfonic acid amine salts can be preferably used, and the contents thereof are preferably incorporated in the present specification.
In addition, crosslinking agents described in paragraphs [0032] to [0033] of JP-A-2005-354012, particularly epoxy compounds having a functionality of two or more, oxetane compounds, [0046] to [0062] of JP-A-2006-303465. A compound described in JP-A-2012-163946, particularly a compound having two or more crosslinking groups, and at least one of the crosslinking groups being a methylol group or an NH group; It is also preferable to use a compound having two or more hydroxymethyl groups or alkoxymethyl groups in the molecule, as described in [0145], and the contents thereof are preferably incorporated in the present specification.

  As a method of forming a gate insulating layer by organic polymer, the method of coating and hardening organic polymer is mentioned, for example. The coating method is not particularly limited, and the respective printing methods described above may be mentioned. Among them, wet coating methods such as microgravure coating method, dip coating method, screen coat printing, die coating method or spin coating method are preferable.

The inorganic oxide is not particularly limited, but, for example, silicon oxide, silicon nitride (SiN _Y ), hafnium oxide, titanium oxide, tantalum oxide, aluminum oxide, niobium oxide, zirconium oxide, copper oxide, oxide oxides such as nickel, _{also, SrTiO 3, CaTiO 3, BaTiO} 3, MgTiO 3, SrNb perovskite such as ₂ O ₆ or a composite oxide thereof, or a mixture thereof. Here, as silicon oxide, in addition to silicon oxide (SiO _x ), BPSG (Boron Phosphorus Silicon Glass), PSG (Phosphorus Silicon Glass), BSG (borosilicate glass), AsSG (arsenic silicate glass), PbSG (lead silicate) Glass), silicon oxynitride (SiON), SOG (spin-on glass), low dielectric constant SiO ₂ -based materials (eg, polyarylethers, cycloperfluorocarbon polymers and benzocyclobutenes, cyclic fluorocarbon resins, polytetrafluoroethylene, fluorocarbons) Arylethers, fluorinated polyimides, amorphous carbon, organic SOG).

As a method of forming the gate insulating layer with an inorganic oxide, for example, a vacuum deposition method such as a vacuum deposition method, a sputtering method, an ion plating, or a CVD (chemical vapor deposition) method can be used. Assisting may be performed by plasma, ion gun, radical gun or the like using any gas.
In addition, precursors corresponding to the respective metal oxides, specifically, metal halides such as chlorides and bromides, metal alkoxides, metal hydroxides, etc., alcohols, such as hydrochloric acid, sulfuric acid, nitric acid, etc. You may form by making it react with bases, such as sodium hydroxide and potassium hydroxide, and hydrolyzing. When using such a solution-based process, the above-mentioned wet coating method can be used.

  The gate insulating layer can also be provided by a method in which any of lift-off method, sol-gel method, electrodeposition method and shadow mask method is combined with the patterning method according to need, other than the above method.

The gate insulating layer may be subjected to surface treatment such as corona treatment, plasma treatment, UV (ultraviolet light) / ozone treatment, but in this case, it is preferable that the surface roughness due to the treatment is not roughened. Preferably, arithmetic mean roughness Ra or root mean square roughness R _MS of the gate insulating layer surface is 0.5 nm or less.

<Organic semiconductor layer>
The organic semiconductor layer is a layer containing an organic semiconductor compound and is a layer capable of accumulating carriers.
The organic semiconductor compound is not particularly limited, and any of a low molecular weight organic semiconductor compound and a high molecular weight organic semiconductor compound may be used. From the viewpoint of further achieving the crack suppressing effect of the present invention, it is preferable to use a low molecular weight organic semiconductor compound having a larger difference in thermal expansion coefficient with the substrate or the gate insulating layer.

(Low-molecular-weight organic semiconductor compounds)
Hereinafter, low molecular weight organic semiconductor compounds that can be used in the present invention will be described.

As low molecular weight organic semiconductor compounds, for example, pentacenes such as 6,13-bis (triisopropylsilylethynyl) pentacene (TIPS pentacene), tetramethylpentacene, perfluoropentacene and the like, 5,11-bis (triethylsilylethynyl) Anthradithiophenes (TES-ADT), anthradithiophenes such as 2,8-difluoro-5,11-bis (triethylsilylethynyl) anthradithiophene (diF-TES-ADT), diphenylbenzothienobenzothiophene (DPh- (BTBT), benzothienobenzothiophenes such as alkylbenzothienobenzothiophene (Cn-BTBT), dinaphthothienothiophenes such as alkyldinaphthothenothiophene (Cn-DNTT), diazo such as perxanthenoxanthene Kisa en tanto alkylene ethers, rubrene compounds, C60, fullerenes such as phenyl _{C 61} butyric acid methyl ester (PCBM), copper phthalocyanine, phthalocyanines such as fluorinated copper phthalocyanine, poly (3-hexylthiophene) (P3RT), Porikuateru Polythiophenes such as thiophene (PQT) and poly (3-hexylthiophene) (P3HT), poly [2,5-bis (3-dodecylthiophen-2-yl) thieno [3,2-b] thiophene] (PBTTT) Etc., and an organic semiconductor compound (T) described later.
Among these, it is preferable to use the following organic semiconductor compounds (T) from the viewpoint of further improving the performance such as carrier mobility of the organic semiconductor layer to be produced.
In the present invention, the organic semiconductor compound (T) has a fused polycyclic aromatic group, and the number of rings in the fused polycyclic aromatic group is four or more, and in the fused polycyclic aromatic group At least two rings each contain at least one atom selected from the group consisting of sulfur atom, nitrogen atom, selenium atom and oxygen atom, and as a partial structure in the fused polycyclic aromatic group, benzene ring, naphthalene ring, And an organic semiconductor compound containing at least one structure selected from the group consisting of phenanthrene rings.
However, it is preferable that the anthracene ring is not contained in the partial structure in the fused polycyclic aromatic group in the organic semiconductor compound (T).
The fused polycyclic aromatic group is a group obtained by condensing a plurality of aromatic rings.
The aromatic ring includes an aromatic hydrocarbon ring (for example, a benzene ring) and an aromatic heterocycle (for example, a thiophene ring, a furan ring, a pyrrole ring, a selenophen ring, and an imidazole ring).

The organic semiconductor compound (T) contains a condensed polycyclic aromatic group (condensed polycyclic aromatic structure), and it is preferable that this group is contained as a main component. Here, the main component means that the content of the molecular weight of the fused polycyclic aromatic group is 30% or more with respect to the total molecular weight of the organic semiconductor compound (T), and is 40% or more preferable. The upper limit is not particularly limited but is preferably 80% or less from the viewpoint of solubility.
The fused polycyclic aromatic group is a ring structure formed by condensation of a plurality of rings, and exhibits aromaticity.
The number of rings in the fused polycyclic aromatic group in the organic semiconductor compound (T) is 4 or more, and from the viewpoint of carrier mobility of the organic thin film transistor, 4 to 9 is preferable, 4 to 7 is more preferable, and 4 to 6 is More preferable.
In the above-mentioned fused polycyclic aromatic group, at least two rings contain at least one atom selected from the group consisting of a sulfur atom, a nitrogen atom, a selenium atom and an oxygen atom, and the carrier mobility of the organic thin film transistor From the viewpoint, it is preferable that 2 to 6 rings contain the above-mentioned atoms, and it is more preferable that 2 to 4 rings contain the above-mentioned atoms.
Further, from the viewpoint of carrier mobility of the organic thin film transistor, it is preferable that the fused polycyclic aromatic group contains at least two heterocycles, and each of the heterocycles has one hetero atom. The type of hetero atom is not particularly limited, and examples thereof include O atom (oxygen atom), S atom (sulfur atom), N atom (nitrogen atom), Se atom (selenium atom) and the like.
The fused polycyclic aromatic group in the organic semiconductor compound (T) contains, as a partial structure, at least one structure selected from the group consisting of a benzene ring, a naphthalene ring and a phenanthrene ring. In addition, as said partial structure, it is preferable that an anthracene ring is not contained.
The organic semiconductor compound (T) preferably has at least a thiophene ring structure and / or a selenophene ring structure, more preferably at least a thiophene ring structure, from the viewpoint of carrier mobility of the organic thin film transistor, and an organic semiconductor compound It is more preferable that all the heterocyclic structures that (T) have are thiophene ring structures.

The fused polycyclic aromatic group includes at least one structure selected from the group consisting of a benzene ring, a naphthalene ring and a phenanthrene ring as a partial structure from the viewpoint of carrier mobility of the organic thin film transistor, and two A fused polycyclic aromatic group containing the above thiophene ring and having 4 or more rings is preferable. Among them, as a partial structure, a fused polycyclic aromatic group containing a benzene ring, containing two or more thiophene rings, and having four or more rings is more preferable.
In addition, as the fused polycyclic aromatic group, the number of thiophene rings in the fused polycyclic aromatic group is preferably 3 or more, more preferably 3 to 5, from the viewpoint of carrier mobility of the organic thin film transistor. Three to four are more preferable, and three are particularly preferable.
Further, from the viewpoint of carrier mobility of the organic thin film transistor, the number of rings in the fused polycyclic aromatic group is preferably 4 to 6, more preferably 5 to 6, and still more preferably 5. The fused polycyclic aromatic group is particularly preferably a fused polycyclic aromatic group containing two benzene rings and three thiophene rings and having five rings.

  Furthermore, as the fused polycyclic aromatic group, a ring (heterocycle, preferably thiophene ring) containing at least one atom selected from the group consisting of sulfur atom, nitrogen atom, selenium atom and oxygen atom, and benzene A group in which rings and a ring are alternately fused (condensed ring) (a group formed by condensation) is preferably mentioned.

From the viewpoint of carrier mobility of the organic thin film transistor, the organic semiconductor compound (T) preferably contains at least one compound represented by any one of the formulas (1) to (16), It is more preferable that it is one or more types of compounds represented by any one of Formula (16).
The organic semiconductor layer may contain only one type of organic semiconductor compound (T) or may contain two or more types of organic semiconductor compounds (T).

In formula (1), A ^1a and A ^1b each independently represent an S atom, an O atom or a Se atom, R ^{1a to} R ^1f each independently represent a hydrogen atom or a substituent, and R ^{1a to} R ^1f And at least one of the groups is a group represented by the following formula (W).
-L ^W -R ^W (W)
In the formula (W), L ^W is a divalent linking group represented by any one of the following formulas (L-1) to (L-25) or two or more of the following formulas (L-1) to (L-) 25) a bivalent linking group to which a bivalent linking group represented by any of 25) is bonded, and R ^W is a repeating number of an alkyl group, a cyano group, a vinyl group, an ethynyl group, an oxyethylene group or an oxyethylene unit v represents an oligooxyethylene group having 2 or more, a siloxane group, an oligosiloxane group having 2 or more silicon atoms, or a trialkylsilyl group.

In formulas (L-1) to (L-25), * represents the bonding position with R ^W , the dashed line portion represents the other bonding position, and formula (L-1), formula (L-2) And R ′ in Formula (L-6) and Formula (L-13) to Formula (L-24) each independently represents a hydrogen atom or a substituent, R ^N represents a hydrogen atom or a substituent, and R ^si Each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group.
In formula (2), X ^2a and X ^2b each independently represent NR ²ⁱ , O atom or S atom, A ^2a represents CR ^2g or N atom, A ^2b represents CR ^2h or N atom, R ²ⁱ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an acyl group, R ^{2a to} R ^2h each independently represent a hydrogen atom or a substituent, and at least one of R ^{2a to} R ^2h has the above formula ( W) is a group represented by W).
In the formula ^(3), each independently ^{X 3a} and ^{X 3b,} represents a S atom, O atom or ^{NR 3 g, A 3a} and ^{A 3b} each independently represent a ^{CR 3h} or N atoms. Each of R ^{3a to} R ^3h independently represents a hydrogen atom or a substituent, and at least one of R ^{3a to} R ^3h is a group represented by the above formula (W).
In formula (4), X ^4a and X ^4b each independently represent an O atom, an S atom or a Se atom, 4p and 4q each independently represent an integer of 0 to 2, R ^{4a to} R ^4j , R ^4k and R ^4m each independently represent a hydrogen atom, a halogen atom or a group represented by the above formula (W), and at least one of R ^{4a to} R ^4j , R ^4k and R ^4m has the above formula ( a group represented by W), ^however, the above formula when at least one of ^{R 4e} and ^{R 4f} is a group represented by the formula (W) represented by ^{R 4e} and ^{R 4f} in (W) L ^W is a divalent linking group represented by Formula (L-2) or Formula (L-3) above.

In formula (5), X ^5a and X ^5b each independently represent NR ⁵ⁱ , O atom or S atom, A ^5a represents CR ^5g or N atom, A ^5b represents CR ^5h or N atom, R ⁵ⁱ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, an aryl group or a heteroaryl group, and R ^{5a to} R ^5h each independently represent a hydrogen atom or a substituent, and R ^{5a to} R ^5h At least one of them is a group represented by the above formula (W).
In formula (6), X ^{6a to} X ^6d each independently represent NR ^6g , O atom or S atom, and R ^6g is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, an aryl group or a heteroaryl group R ^{6a to} R ^6f each independently represent a hydrogen atom or a substituent, and at least one of R ^{6a to} R ^6f is a group represented by the above formula (W).
In formula (7), X ^7a and X ^7c each independently represent S atom, O atom, Se atom or NR ⁷ⁱ , and X ^7b and X ^7d each independently represent S atom, O atom or Se atom. And R ^{7a to} R ⁷ⁱ each independently represent a hydrogen atom or a substituent, and at least one of R ^{7a to} R ⁷ⁱ is a group represented by the above formula (W).
In formula (8), X ^8a and X ^8c each independently represent S atom, O atom, Se atom or NR ⁸ⁱ , and X ^8b and X ^8d each independently represent S atom, O atom or Se atom. And R ^{8a to} R ⁸ⁱ each independently represent a hydrogen atom or a substituent, and at least one of R ^{8a to} R ⁸ⁱ is a group represented by the above formula (W).

In formula (9), X ^9a and X ^9b each independently represent an O atom, an S atom or a Se atom, and R ^9c , R ^9d and R ^{9g to} R ^9j each independently represent a hydrogen atom, a halogen atom or the above R ^9a , R ^9b , R ^9e and R ^9f each independently represent a hydrogen atom or a substituent.
In formula (10), R ^{10a to} R ^10h each independently represent a hydrogen atom or a substituent, and at least one of R ^{10a to} R ^10h represents a substituent represented by the above formula (W), and X ^10a and X ^10b each independently represent S atom, O atom, Se atom or NR ¹⁰ⁱ , and R ¹⁰ⁱ independently represents a hydrogen atom or a group represented by the above formula (W).
In formula (11), X ^11a and X ^11b each independently represent an S atom, an O atom, a Se atom or NR ¹¹ⁿ , and R ^{11a to} R ^11k and R ^11m and R ¹¹ⁿ each independently represent a hydrogen atom or a substituent And at least one of R ^{11a to} R ^11k , R ^11m and R ¹¹ⁿ is a group represented by the above formula (W).
In formula (12), X ^12a and X ^12b each independently represent an S atom, an O atom, a Se atom or NR ¹²ⁿ , and R ^{12a to} R ^12k and R ^12m and R ¹²ⁿ each independently represent a hydrogen atom or a substituent And at least one of R ^{12a to} R ^12k , R ^12m and R ¹²ⁿ is a group represented by the above formula (W).

In formula (13), X ^13a and X ^13b each independently represent an S atom, an O atom, a Se atom or NR ¹³ⁿ , and R ^{13a to} R ^13k and R ^13m and R ¹³ⁿ each independently represent a hydrogen atom or a substituent And at least one of R ^{13a to} R ^13k , R ^13m and R ¹³ⁿ is a group represented by the above formula (W).
In the formula ^(14), the X 14a ^{to X 14c} each independently, S atom, O atom, a Se atom or a ^{NR 14i, R} 14a ^{~R 14i} each independently represent a hydrogen atom or a ^{substituent, R 14a} And at least one of R ¹⁴ⁱ is a group represented by the above formula (W).
In the formula ^(15), the X 15a ^{to X 15d} are each independently, S atom, O atom, a Se atom or a ^{NR 15g, R} 15a ^{~R 15g} each independently represent a hydrogen atom or a ^{substituent, R 15a} at least one of to R ^{15 g} is a group represented by the formula (W).
In the formula (16), X ^{16a to} X ^16d each independently represent an S atom, an O atom, a Se atom or NR ^16g , R ^{16a to} R ^16g each independently represent a hydrogen atom or a substituent, and R ^16a And at least one of R ^16g is a group represented by the above formula (W).

-Compound represented by Formula (1)-

In Formula (1), ^A1a and ^A1b respectively independently represent S atom (sulfur atom), O atom (oxygen atom), or Se atom (selenium atom). A ^1a and A ^1b are preferably S atoms or O atoms. Also, A ^1a and A ^1b may be the same as or different from each other, but are preferably the same as each other.
In Formula (1), R ^{1a to} R ^1f each independently represent a hydrogen atom or a substituent. However, at least one of R ^{1a to} R ^1f is a group represented by Formula (W) described later.

The compound represented by Formula (1) may have other substituents other than the group represented by Formula (W) mentioned later.
The type of the substituents R ^1a to R ^1f may take is not particularly limited in the formula (1), there are substituents X described below. As the substituent X, a group represented by the formula (W) described later, a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group and a tricycloalkyl group), an alkenyl group (cycloalkenyl group and bicycloalkenyl) Group), alkynyl group, aryl group, heterocyclic group (may be referred to as heterocyclic group), cyano group, hydroxy group, nitro group, carboxy group, alkoxy group, aryloxy group, silyloxy group, hetero group Ring oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxy Carbonylamino group, sulfamoylamino group Alkyl and aryl sulfonylamino groups, mercapto groups, alkylthio groups, arylthio groups, heterocyclic thio groups, sulfamoyl groups, sulfo groups, alkyl and arylsulfinyl groups, alkyl and arylsulfonyl groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups , Carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyl oxy group, phosphinyl amino group, phosphono group, silyl group, hydrazino group, ureido group, boronic acid group (-B (OH) ₂ ), phosphato group (-OPO (OH) ₂ ), sulfato group (-OSO ₃ H), and other known substituents. In the formulas (1) to (16) of the present specification, the above-mentioned substituent X is preferably mentioned as the “substituent”.
Among these, as a group other than the group represented by the formula (W) described later, a halogen atom, an alkyl group, an alkynyl group, an alkenyl group, an alkoxy group, an alkylthio group and an aryl group are preferable, and a fluorine atom and carbon number 1 -3 substituted or unsubstituted alkyl group, substituted or unsubstituted alkynyl group having 2 to 3 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 3 carbon atoms, substituted or unsubstituted group having 1 to 2 carbon atoms An alkoxy group, a substituted or unsubstituted methylthio group, a phenyl group is more preferable, a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 3 carbon atoms, a carbon number Two to three substituted or unsubstituted alkenyl groups, substituted or unsubstituted alkoxy groups having 1 to 2 carbon atoms, and substituted or unsubstituted methylthio groups are particularly preferable.

In the compound represented by the formula (1), the number of substituents other than the group represented by the formula (W) among R ^{1a to} R ^1f is preferably 0 to 4, and 0 to 2 Is more preferable, and 0 is particularly preferable.
Moreover, these substituents may further have the above-mentioned substituent X.
Among ^them, are each R 1c ^{to R 1f} independently represent a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkynyl group having 2 to 3 carbon atoms having 1 to 3 carbon atoms, 2 carbon atoms It is preferable that it is 3 substituted or unsubstituted alkenyl groups, a C1-C2 substituted or unsubstituted alkoxy group, or a substituted or unsubstituted methylthio group.

Next, the group represented by Formula (W) will be described.
-L ^W -R ^W (W)
In the formula (W), L is a divalent linking group represented by any one of the following formulas (L-1) to (L-25), or two or more of the following formulas (L-1) to (L) -25 represents a divalent linking group to which a divalent linking group represented by any of -25) is bonded.

In formulas (L-1) to (L-25), * represents the bonding position with R ^W, and the dashed line portion represents the other bonding position. More specifically, for example, in the compound represented by the formula (1), the wavy line part is bonded to a ring forming the skeleton represented by the formula (1). In addition, when Formula (W) is contained in another compound so that it may mention later, a wavy line part couple | bonds with the ring which forms frame | skeleton of each compound.
When L ^W represents a divalent linking group in which two or more divalent linking groups represented by any one of formulas (L-1) to (L-25) are bonded, one of the linking groups * Is bonded to the wavy part of the other linking group.
The bonding position of R ′ in formula (L-13) to formula (L-24) and the bonding position * with R ^W can be taken at any position on the aromatic ring or heteroaromatic ring.
R ′ in Formula (L-1), Formula (L-2), Formula (L-6) and Formula (L-13) to Formula (L-24) each independently represents a hydrogen atom or a substituent. ^RN represents a hydrogen atom or a substituent. Each R ^si independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group.
R ′ in Formula (L-1) and Formula (L-2) may be combined with R ^W adjacent to L ^W to form a fused ring.

  Among these, the divalent linking group represented by any of Formula (L-17) to Formula (L-21), Formula (L-23) and Formula (L-24) is a compound represented by the following Formula (L- It is more preferable that it is a bivalent coupling group represented by 17A)-Formula (L-21A), Formula (L-23A), and Formula (L-24A).

Here, a substituted or unsubstituted alkyl group, an oxyethylene group, an oligooxyethylene group having a repeating number v of 2 or more of an oxyethylene unit, a siloxane group, an oligosiloxane group having a silicon atom number of 2 or more, or a substituted or no group. If a trialkylsilyl group substitutions present at the end of the substituent, can also be interpreted as -R ^W alone in the formula (W), it can also be interpreted as -L ^W -R ^W in the formula (W) .
In the present invention, when a substituted or unsubstituted alkyl group having a carbon number of N in the main chain is present at the end of the substituent, the linking group as much as possible from the end of the substituent is included and then the formula (W) ^-L W -R ^W and the interpreting, R represents in particular the "one group represented by the formula (L-1) corresponding to the ^{L W} in formula (W)" in "formula (W) in ^The main chain corresponding to ^W is interpreted as a substituent in which a substituted or unsubstituted alkyl group having 1 or more carbon atoms is bonded. For example, when an n-octyl group which is an alkyl group having 8 carbon atoms is present at the end of a substituent, one group represented by the formula (L-1) in which two R's are hydrogen atoms, and carbon It interprets as a substituent which n-heptyl group of number 7 couple | bonded.
On the other hand, in the present invention, an oxyethylene group, an oligoethylene group having a repeating number v of 2 or more of oxyethylene units of 2 or more, a siloxane group, an oligosiloxane group having 2 or more silicon atoms, or a substituted or unsubstituted trialkylsilyl When a group is present at the end of a substituent, it is interpreted as R ^W in Formula (W) alone, including the linking group as far as possible from the end of the substituent. For example, when a-(OCH ₂ CH ₂ )-(OCH ₂ CH ₂ )-(OCH ₂ CH ₂ ) -OCH ₃ group is present at the end of a substituent, an oligoethylene having a repetition number v of oxyethylene units of 3 is 3 It is interpreted as a single substituent.

When L ^W forms a linking group in which a divalent linking group represented by any one of Formula (L-1) to Formula (L-25) is bonded, Formula (L-1) to Formula (L-25) It is preferable that it is 2-4, and, as for the number of coupling | bondings of the bivalent coupling group represented by either of, it is more preferable that it is 2 or 3.

As the substituent R ′ in the formula (L-1), the formula (L-2), the formula (L-6) and the formula (L-13) to the formula (L-24), What was illustrated as a substituent which R ^{< 1a} > -R < ^1f can take can be mentioned. Among them, the substituent R ′ in formula (L-6) is preferably an alkyl group, and when R ′ in formula (L-6) is an alkyl group, the carbon number of the alkyl group is 1 to 6 It is preferably 9 and more preferably 4 to 9 in view of chemical stability and carrier transportability, and still more preferably 5 to 9. When R ′ in the formula (L-6) is an alkyl group, the alkyl group is preferably a linear alkyl group from the viewpoint of being able to enhance the carrier mobility.
R ^N represents a hydrogen atom or a substituent, examples of ^{R N,} may be mentioned those exemplified as the substituents ^{of R} 1a ^{to R 1f} may take the above formula (1). Among them, as R ^N , a hydrogen atom or a methyl group is preferable.
Each R ^si independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group, and is preferably an alkyl group. The alkyl group that R ^si can take is not particularly limited, but the preferred range of the alkyl group that R ^si can take is the preferred range of the alkyl group that a trialkylsilyl group can take when R is a trialkylsilyl group Is the same as The alkenyl group that R ^si can adopt is not particularly limited, but is preferably a substituted or unsubstituted alkenyl group, more preferably a branched alkenyl group, and the alkenyl group having a carbon number of 2 to 3 preferable. The alkynyl group that R ^si can adopt is not particularly limited, but a substituted or unsubstituted alkynyl group is preferable, a branched alkynyl group is more preferable, and the number of carbon atoms of the alkynyl group is 2 to 3 preferable.

L ^W is a divalent linking group represented by any of Formula (L-1) to Formula (L-5), Formula (L-13), Formula (L-17) or Formula (L-18) Or a divalent linking group represented by any of Formula (L-1) to Formula (L-5), Formula (L-13), Formula (L-17) or Formula (L-18) It is preferable that it is a divalent linking group bound to two or more, and it is preferable that Or two or more divalent linking groups represented by formula (L-1), formula (L-3), formula (L-13) or formula (L-18) Is more preferably a divalent linking group, and a divalent linking group represented by any of Formula (L-1), Formula (L-3), Formula (L-13) or Formula (L-18). Linking group, or Formula (L-3), Formula (L A divalent linking group in which a divalent linking group represented by any one of L-13) and formula (L-18) and a divalent linking group represented by formula (L-1) are bonded Is particularly preferred.
A divalent linking group represented by any one of Formula (L-3), Formula (L-13) or Formula (L-18) and a divalent linking group represented by Formula (L-1) In the divalent linking group to which is attached, it is preferable that the divalent linking group represented by the formula (L-1) be bound to the R ^W side.
L ^W is particularly preferably a divalent linking group containing a divalent linking group represented by Formula (L-1) from the viewpoint of chemical stability and carrier transportability, and More preferably, it is a divalent linking group represented by 1), and L ^W is a divalent linking group represented by the formula (L-1), and R ^W is a substituted or unsubstituted alkyl group. It is most preferable that

In the formula (W), R ^W is a substituted or unsubstituted alkyl group, cyano group, vinyl group, ethynyl group, oxyethylene group, oligooxyethylene group having a repeating number v of 2 or more of oxyethylene units, siloxane group, silicon It represents an oligosiloxane group having 2 or more atoms, or a substituted or unsubstituted trialkylsilyl group.
In the formula (W), when L ^W adjacent to R ^W is a divalent linking group represented by the formula (L-1), R ^W is a substituted or unsubstituted alkyl group, oxyethylene group, oxy It is preferably an oligooxyethylene group having a repeating number of ethylene units of 2 or more, a siloxane group, or an oligosiloxane group having 2 or more silicon atoms, and more preferably a substituted or unsubstituted alkyl group.
When L ^W adjacent to R ^W in Formula (W) is a divalent linking group represented by any of Formula (L-2) or Formula (L-4) to Formula (L-25): More preferably, R ^W is a substituted or unsubstituted alkyl group.
In the case where L ^W adjacent to R ^W in Formula (W) is a divalent linking group represented by Formula (L-3), R ^W is a substituted or unsubstituted alkyl group, or a substituted or non-substituted alkyl group. It is preferably a substituted trialkylsilyl group.

When R ^W is a substituted or unsubstituted alkyl group, it preferably has 4 to 17 carbon atoms, and more preferably 6 to 14 from the viewpoint of chemical stability and carrier transportability. It is further preferred that It is preferable that R is a long chain alkyl group within the above range, in particular, a long chain linear alkyl group, from the viewpoint of enhancing the linearity of the molecule and increasing the carrier mobility.
When R ^W represents an alkyl group, it may be a linear alkyl group, a branched alkyl group or a cyclic alkyl group, but being a linear alkyl group enhances the linearity of the molecule and enhances the carrier mobility. From the viewpoint of being able to
Among these, as a combination of R ^W and L ^W in the formula (W), in the formula (1), L ^W is a divalent linking group represented by the formula (L-1), and R ^W Is a linear alkyl group having 7 to 17 carbon atoms, or L ^W is represented by any one of formula (L-3), formula (L-13) or formula (L-18) Carrier mobility, which is a divalent linking group in which a divalent linking group and a divalent linking group represented by Formula (L-1) are bonded, and R ^W is a linear alkyl group From the viewpoint of enhancing the
When L ^W is a divalent linking group represented by the formula (L-1) and R ^W is a linear alkyl group having 7 to 17 carbon atoms, R ^W is a linear 7 carbon atoms It is more preferable that it is an alkyl group of -14 from a viewpoint of raising carrier mobility, and it is especially preferable that it is a linear C7-C12 alkyl group.
A divalent linking group in which L ^W is represented by any one of formula (L-3), formula (L-13) or formula (L-18) and a bivalent represented by formula (L-1) is a divalent linking group linking group is attached the, and, if R ^W is a straight chain alkyl group, more preferably R ^W is an alkyl group having a carbon number of 4 to 17 linear, straight The alkyl group of 6 to 14 carbon atoms in the chain is more preferable from the viewpoint of chemical stability and carrier transportability, and the linear alkyl group of 6 to 12 carbon atoms is preferred from the viewpoint of enhancing carrier mobility Particularly preferred.
On the other hand, from the viewpoint of enhancing the solubility in an organic solvent, it is preferable that R ^W be a branched alkyl group.
When R ^W is an alkyl group having a substituent, examples of the substituent include a halogen atom and the like, with a fluorine atom being preferable. When R ^W is an alkyl group having a fluorine atom, all hydrogen atoms of the alkyl group may be substituted with a fluorine atom to form a perfluoroalkyl group. However, it is preferable that R ^W be an unsubstituted alkyl group.

When R ^W is an oligoethylene group having an oxyethylene group having a repeating number of 2 or more, the “oligooxyethylene group” represented by R is represented by — (OCH ₂ CH ₂ ) _v —OY in the present specification. A group is referred to (the repeating number v of the oxyethylene unit represents an integer of 2 or more, and the terminal Y represents a hydrogen atom or a substituent). When Y at the end of the oligooxyethylene group is a hydrogen atom, it is a hydroxy group. It is preferable that it is 2-4, and, as for repeat number v of an oxyethylene unit, it is more preferable that it is 2-3.
It is preferable that the terminal hydroxy group of the oligooxyethylene group is sealed, that is, Y represents a substituent. In this case, the hydroxy group is preferably sealed with an alkyl group having 1 to 3 carbon atoms, that is, Y is preferably an alkyl group having 1 to 3 carbon atoms, and Y is a methyl group or an ethyl group. Is more preferable, and a methyl group is particularly preferable.

When R ^W is a siloxane group or an oligosiloxane group having 2 or more silicon atoms, the number of repeating siloxane units is preferably 2 to 4, and more preferably 2 to 3. In addition, it is preferable that a hydrogen atom or an alkyl group be bonded to a silicon atom (Si atom). When an alkyl group is bonded to a silicon atom, the carbon number of the alkyl group is preferably 1 to 3, and for example, a methyl group or an ethyl group is preferably bonded. The same alkyl group may be bonded to a silicon atom, or different alkyl groups or hydrogen atoms may be bonded. Moreover, although all the siloxane units which comprise an oligo siloxane group may be same or different, it is preferable that all are the same.

When L ^W adjacent to R ^W is a divalent linking group represented by Formula (L-3), R ^W is also preferably a substituted or unsubstituted trialkylsilyl group. Among them, when R ^W is a substituted or unsubstituted trialkylsilyl group, the substituent of the silyl group is not particularly limited as long as it is a substituted or unsubstituted alkyl group, but is a branched alkyl group Is more preferred. It is preferable that carbon number of the alkyl group couple | bonded with a silicon atom is 1-3, for example, it is preferable that a methyl group, an ethyl group, or an isopropyl group couple | bonds. The same alkyl group may be bonded to a silicon atom, or different alkyl groups may be bonded. When R ^W is a trialkylsilyl group further having a substituent on the alkyl group, the substituent is not particularly limited.

In Formula (W), the total number of carbons contained in L ^W and R ^W is preferably 5 to 18. When the total number of carbons contained in L ^W and R ^W is equal to or more than the lower limit value of the above range, the carrier mobility becomes high, and the driving voltage becomes low. If the total number of carbon atoms contained in L ^W and R ^W is not more than the upper limit of the above range, solubility in an organic solvent is increased.
The total number of carbons contained in L ^W and R ^W is preferably 5 to 14, more preferably 6 to 14, still more preferably 6 to 12, and 8 to 12 Particularly preferred.

In the compounds represented by the formula (1), among R ^{1a to} R ^1f , the number of groups represented by the formula (W) is preferably 1 to 4 and 1 to 2 More preferably, two are particularly preferred.

In the present invention, in Formula (1), it is preferable that at least one of R ^1a and R ^1b be a group represented by Formula (W). As the substitution position in the formula (1), these positions are preferable because they are excellent in the chemical stability of the compound and are also preferable from the viewpoint of the highest occupied molecular orbital (HOMO) level and the packing of molecules in the film. It is considered to be for. In particular, a high carrier concentration can be obtained by using two places of R ^1a and R ^1b as a substituent in the formula (1).
In the formula (1), R ^{1c to} R ^1f independently represent a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, a substituted or unsubstituted alkynyl having 2 to 3 carbon atoms It is preferably a group, a substituted or unsubstituted alkenyl group having 2 to 3 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 2 carbon atoms, or a substituted or unsubstituted methylthio group.

-Compound represented by Formula (2)-

In formula (2), ^X2a and ^X2b respectively independently represent ^NR2i (> N- ^R2i ), O atom, or S atom. Each of X ^2a and X ^2b independently is preferably an O atom or an S atom from the viewpoint of synthesis ease. On the other hand, it is preferable from the viewpoint of enhancing carrier mobility that at least one of X ^2a and X ^2b is an S atom.
It is preferable that X ^2a and X ^2b be the same linking group. More preferably, X ^2a and X ^2b are both S atoms.
R ²ⁱ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an acyl group, preferably a hydrogen atom or an alkyl group, more preferably an alkyl group having 1 to 14 carbon atoms, and 1 carbon atom Particularly preferred is an alkyl group of -4.
When R ²ⁱ represents an alkyl group, it may be a linear alkyl group, a branched alkyl group or a cyclic alkyl group, but being a linear alkyl group enhances the linearity of the molecule and enhances the carrier mobility. From the viewpoint of being able to

In formula (2), A ^2a represents CR ^2g or N atom, A ^2b represents CR ^2h or N atom, and R ^2g and R ^2h each independently represent a hydrogen atom or a substituent. Or A ^2a is ^{CR 2 g,} preferably ^{A 2b} is ^{CR 2h, A 2a} is ^{CR 2 g,} and more preferably ^{A 2b} is ^{CR 2h.} A ^2a and A ^2b may be the same or different from each other, but are preferably the same.
In Formula (2), R ^2e and R ^2g may be bonded to each other to form a ring, or may not be bonded to each other to form a ring, but it is preferable that they be not bonded to each other to form a ring .
In formula (2), R ^2f and R ^2h may be bonded to each other to form a ring, or may not be bonded to each other to form a ring, but it is preferable that they be not bonded to each other to form a ring .

In formula (2), R ^{2a to} R ^2h each independently represent a hydrogen atom or a substituent, and at least one represents a substituent represented by formula (W).
As R ^{2a to} R ^2h each independently, as the substituent that can be taken, the above-mentioned substituent X can be mentioned. The definition of the substituent represented by formula (W) is as described above.
As R ^{2a to} R ^2h , each of which can be independently taken, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a heterocyclic group, an alkoxy group, an alkylthio group or a substituent represented by formula (W) is preferable. An alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms, 12 heterocyclic groups, an alkylthio group having 1 to 12 carbon atoms, and a group represented by the formula (W) are more preferable, and the below-mentioned linking group chain length is represented by a group having a length of 3.7 Å or less and the formula (W) A group is particularly preferred, and a group represented by formula (W) is more particularly preferred.

Among the compounds represented by the formula (2), among R ^{2a to} R ^2h , the number of the group represented by the formula (W) is 1 to 4, the carrier mobility is enhanced, and the solubility in organic solvents Is preferable from the viewpoint of increasing the ratio, more preferably one or two, and particularly preferably two.
Among R ^{2a to} R ^2h , the position of the group represented by formula (W) is not particularly limited, but being R ^2e or R ^2f enhances carrier mobility and enhances solubility in an organic solvent. It is preferable from the viewpoint.

Among R ^{2a to} R ^2h , the substituent other than the group represented by formula (W) is preferably 0 to 4, more preferably 0 to 2, and 0 or 1. Is more preferable, and 0 is particularly preferable.

When R ^{2a to} R ^2h are substituents other than the group represented by formula (W), the substituent is preferably a group having a linking group chain length of 3.7 Å (= 0.37 nm) or less, The linking group chain length is more preferably a group of 1.0 to 3.7 Å, and further preferably the linking group chain length is a group of 1.0 to 2.1 Å.
Here, the linking group chain length refers to the length from the C atom in the C (carbon atom) -R bond to the end of the substituent R. The structural optimization calculation can be performed using a density functional method (Gaussian 03 (US Gaussian Co.) / Basis function: 6-31 G ^* , exchange correlation functional: B3LYP / LANL2DZ). In addition, as molecular lengths of typical substituents, propyl group is 4.6 Å, pyrrole group is 4.6 Å, propynyl group is 4.5 Å, propenyl group is 4.6 Å, ethoxy group is 4.5 Å, methylthio group Is 3.7 Å, the ethenyl group is 3.4 Å, the ethyl group is 3.5 Å, the ethynyl group is 3.6 Å, the methoxy group is 3.3 Å, the methyl group is 2.1 Å, and the hydrogen atom is 1.0 Å.

When R ^{2a to} R ^2h are substituents other than the group represented by formula (W), each substituent is independently a substituted or unsubstituted alkyl group having 2 or less carbon atoms, or a substituted or non-substituted alkyl group having 2 or less carbon atoms It is preferable that it is a substituted alkynyl group, a substituted or unsubstituted alkenyl group having 2 or less carbon atoms, or a substituted or unsubstituted acyl group having 2 or less carbon atoms, and the substituted or unsubstituted alkyl group having 2 or less carbon atoms It is more preferable that
When the substituents in the case where R ^{2a to} R ^2h are substituents other than the group represented by Formula (W) each independently represent a substituted alkyl group having 2 or less carbon atoms, the substituent that the alkyl group can take is And a cyano group, a fluorine atom, a deuterium atom and the like, and a cyano group is preferable. The substituted or unsubstituted alkyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by the formula (W) is preferably a methyl group, an ethyl group or a methyl group substituted with a cyano group A methyl group or a methyl group substituted with a cyano group is more preferable, and a methyl group substituted with a cyano group is particularly preferable.
When the substituents in the case where R ^{2a to} R ^2h are substituents other than the group represented by Formula (W) each independently represent a substituted alkynyl group having 2 or less carbon atoms, the substituent that the alkynyl group can take is And deuterium atoms. Examples of the substituted or unsubstituted alkynyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by Formula (W) include ethynyl group and acetylene group substituted with deuterium atom Ethynyl group is preferred.
When the substituents in the case where R ^{2a to} R ^2h are substituents other than the group represented by formula (W) each independently represent a substituted alkenyl group having 2 or less carbon atoms, the substituent that the alkenyl group can take is And deuterium atoms. Examples of the substituted or unsubstituted alkenyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by Formula (W) include ethenyl group and ethenyl group substituted with deuterium atom And ethenyl is preferred.
When the substituents in the case where R ^{2a to} R ^2h are substituents other than the group represented by Formula (W) each independently represent a substituted acyl group having 2 or less carbon atoms, the substituent that the acyl group can take is And fluorine atoms. Examples of the substituted or unsubstituted acyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by Formula (W) include a formyl group, an acetyl group, and a fluorine-substituted acetyl group. Formyl groups are preferred.

-Compound represented by Formula (3)-

In Formula (3), R ^{3a to} R ^3f and R ^3g and R ^3h described later each independently represent a hydrogen atom or a substituent. However, at least one of R ^{3a to} R ^3h represents a group represented by Formula (W).
Examples of the substituent represented by R ^{3a to} R ^3h include the above-mentioned substituent X. The definition of the group represented by formula (W) is as described above.
As a substituent that R ^{3a to} R ^3f can be independently taken, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a heterocyclic group, an alkoxy group, an alkylthio group or a substituent represented by formula (W) is preferable. An alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms, 12 heterocyclic groups, alkylthio groups having 1 to 12 carbon atoms, or groups represented by formula (W) are more preferred.

In the formula ^(3), respectively the ^{X 3a} and ^{X 3b} independently, S atom, an O atom or ^{NR 3g (> NR 3g),} R 3g represents a hydrogen atom or a substituent. X is preferably an S atom or an O atom. In Formula (3), X ^3a and X ^3b are preferably the same.
R ^3g is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably an alkyl group having 1 to 14 carbon atoms, and particularly preferably an alkyl group having 4 to 12 carbon atoms. It is preferable that R ^3g be a long chain alkyl group in the above range, in particular, a long chain linear alkyl group, from the viewpoint of enhancing the linearity of the molecule and enhancing the carrier mobility.
When R ^3g represents an alkyl group, it may be a linear alkyl group, a branched alkyl group or a cyclic alkyl group, but being a linear alkyl group enhances the linearity of the molecule and enhances the carrier mobility. From the viewpoint of being able to

In the formula ^(3), are each ^{A 3a} and ^{A 3b} independently represent ^{CR 3h} or N atoms, preferably represents a ^{CR 3h.} In Formula (3), A ^3a and A ^3b may be the same or different from each other, but are preferably the same.
R ³ h is preferably a group having a linking group chain length of 3.7 Å or less, more preferably a group having a linking group chain length of 1.0 to 3.7 Å, and a linking group chain length of 1.0 to More preferably, it is a 2.1 Å group. The definition of linking group chain length is as described above.
R ^3h is a hydrogen atom, a substituted or unsubstituted alkyl group having 2 or less carbon atoms, a substituted or unsubstituted alkynyl group having 2 or less carbon atoms, a substituted or unsubstituted alkenyl group having 2 or less carbon atoms, or It is preferably a substituted or unsubstituted acyl group of 2 or less, more preferably a hydrogen atom, or a substituted or unsubstituted alkyl group having 2 or less carbon atoms, and particularly preferably a hydrogen atom.
When R ^3h represents a substituted alkyl group having 2 or less carbon atoms, ^examples of the substituent that the alkyl group may have include a cyano group, a fluorine atom, a deuterium atom and the like, with a cyano group being preferable. The substituted or unsubstituted alkyl group having 2 or less carbon atoms represented by R ^3h is preferably a methyl group, an ethyl group or a methyl group substituted with a cyano group, more preferably a methyl group or a methyl group substituted with a cyano group, cyano Particularly preferred is a group-substituted methyl group.
When R ^3h represents a substituted alkynyl group having 2 or less carbon atoms, ^examples of the substituent which the alkynyl group can take include a deuterium atom and the like. Examples of the substituted or unsubstituted alkynyl group having 2 or less carbon atoms represented by R ^3h include an ethynyl group or a deuterium atom-substituted acetylene group, with an ethynyl group being preferable.
When R ^3h represents a substituted alkenyl group having 2 or less carbon atoms, ^examples of the substituent which the alkenyl group may have include a deuterium atom and the like. ^Examples of the substituted or unsubstituted alkenyl group having 2 or less carbon atoms represented by R ^3h include an ethenyl group and an ethenyl group substituted with a deuterium atom, and is preferably an ethenyl group.
When R ^3h represents a substituted acyl group having 2 or less carbon atoms, ^examples of the substituent that the acyl group may have include a fluorine atom and the like. ^Examples of the substituted or unsubstituted acyl group having 2 or less carbon atoms represented by R ^3h include a formyl group, an acetyl group, or a fluorine-substituted acetyl group, with a formyl group being preferred.

-Compound represented by Formula (4)-

In formula (4), X ^4a and X ^4b each independently represent an O atom, an S atom or a Se atom.
X ^4a and X ^4b are each independently preferably an O atom or an S atom, and it is more preferable that at least one of X ^4a and X ^4b be an S atom from the viewpoint of enhancing carrier mobility. It is preferable that X ^4a and X ^4b be the same linking group. It is particularly preferable that both X ^4a and X ^4b be an S atom.

  In Formula (4), 4p and 4q respectively independently represent the integer of 0-2. It is preferable that 4p and 4q are each independently 0 or 1 from the viewpoint of achieving both carrier mobility and solubility, and it is more preferable that 4p = 4q = 0 or 4p = 4q = 1.

In formula (4), R ^{4a to} R ^4k and R ^4m each independently represent a hydrogen atom, a halogen atom, or a group represented by formula (W), and R ^{4a to} R ^4k and R ^4m At least one of them is a group represented by formula (W), provided that at least one of R ^4e and R ^4f is a group represented by formula (W), R ^4e and R ^4f are In the formula (W), L ^W is a divalent linking group represented by the above formula (L-2) or the formula (L-3). In addition, the definition of group represented by Formula (W) is as above-mentioned.

When at least one of R ^4e and R ^4f is a group represented by formula (W), it corresponds to the case where neither R ^4e nor R ^4f is a hydrogen atom nor a halogen atom.
When at least one of R ^4e and R ^4f is a group represented by formula (W), L ^W is represented by the above formula (L-3) in the formula (W) represented by R ^4e and R ^4f It is preferably a divalent linking group.
If at least one of R ^4e and ^{R 4f} is a group represented by formula ^{(W), R 4e} and ^{R 4f} are preferably both a group represented by the formula (W).
In ^the case of ^{R 4e} and ^{R 4f} are both hydrogen atom or a halogen ^atom, R ^4a to R ^4d, are each R 4g ^{to R 4k} and ^{R 4m} independently represented by a hydrogen atom, a halogen atom or the formula (W) And at least one of R ^{4a to} R ^4d , R ^{4g to} R ^4k, and R ^4m is a group represented by Formula (W).

As a halogen atom which ^{R4a- R4k} and ^R4m represent in Formula (4), a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be mentioned, It is a fluorine atom, a chlorine atom, or a bromine atom Preferably, a fluorine atom or a chlorine atom is more preferable, and a fluorine atom is particularly preferable.

Among R ^{4a to} R ^4k and R ^{4m in} the compound represented by the formula (4), the number of halogen atoms is preferably 0 to 4, more preferably 0 to 2, and 0 or 1 The number is more preferably zero, and particularly preferably zero.

Among the compounds represented by the formula (4), among R ^{4a to} R ^4k and R ^4m , one to four groups represented by the formula (W) enhance the carrier mobility, and the organic solvent It is preferable from the viewpoint of enhancing the solubility in water, is more preferably one or two, and particularly preferably two.
The position of the group represented by Formula (W) among R ^{4a to} R ^4k and R ^4m is not particularly limited. Among them, in the present invention, in the formula (4), R ^4a , R ^{4d to} R ^4g , R ^4j , R ^4k and R ^4m are each independently a hydrogen atom or a halogen atom, and R ^4b , R ^4c , R ^4h and R ⁴ⁱ are each independently a hydrogen atom, a halogen atom or a group represented by the formula (W), and at least one of R ^4b , R ^4c , R ^4h and R ⁴ⁱ is a formula (W) It is preferable from the viewpoint of enhancing carrier mobility and enhancing solubility in an organic solvent that the group is represented by
In the present invention, R ^4a , R ^{4c to} R ^4h and R ^4j each independently represent a hydrogen atom or a halogen atom, and R ^4b and R ⁴ⁱ each independently represent a hydrogen atom, a halogen atom or a formula (W). It is more preferable that at least one is a group represented by formula (W).
In the present invention, R ^4b and R ⁴ⁱ are both a group represented by Formula (W), and R ^4c and R ^4h are both a hydrogen atom or a halogen atom, or R ^4c and R ^4h are both a group More preferably, R ^4b and R ⁴ⁱ are both a hydrogen atom or a halogen atom.
In the present invention, R ^4b and R ⁴ⁱ are both a group represented by Formula (W), and R ^4c and R ^4h are both a hydrogen atom or a halogen atom, or R ^4c and R ^4h are both a group It is particularly preferred that R ^4b and R ⁴ⁱ are both a hydrogen atom or a halogen atom.
In formula (4), two or more of R ^{4a to} R ^4k and R ^4m may be bonded to each other to form a ring, or may not be bonded to each other to form a ring, but are bonded to each other to form a ring It is preferable not to form.

-Compound represented by Formula (5)-

In formula (5), X ^5a and X ^5b each independently represent NR ⁵ⁱ , O atom or S atom. Each of X ^5a and X ^5b independently is preferably an O atom or an S atom from the viewpoint of synthesis ease. On the other hand, it is preferable from the viewpoint of enhancing carrier mobility that at least one of X ^5a and X ^5b is an S atom. It is preferable that X ^5a and X ^5b be the same linking group. More preferably, X ^5a and X ^5b are both S atoms.
R ⁵ⁱ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, an aryl group or a heteroaryl group, preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an acyl group, a hydrogen atom Or an alkyl group is more preferable, an alkyl group having 1 to 14 carbon atoms is further preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.
When R ⁵ⁱ represents an alkyl group, it may be a linear alkyl group, a branched alkyl group or a cyclic alkyl group, but being a linear alkyl group enhances the linearity of the molecule and enhances the carrier mobility. From the viewpoint of being able to

In formula (5), A ^5a represents CR ^5g or N atom, A ^5b represents CR ^5h or N atom, and R ^5g and R ^5h each independently represent a hydrogen atom or a substituent. Or A ^5a is ^{CR 5 g,} preferably ^{A 5b} is ^{CR 5h, A 5a} it is more preferably ^{CR 5 g} and ^{A 5b} is ^{CR 5h.} A ^5a and A ^5b may be the same or different from each other, but are preferably the same.

In Formula (5), R ^5e and R ^5g may be bonded to each other to form a ring or may not be bonded to each other to form a ring, but it is preferable that they be not bonded to each other to form a ring.
In Formula (5), R ^5e and R ⁵ⁱ may be bonded to each other to form a ring, or may not be bonded to each other to form a ring, but it is preferable that they be not bonded to each other to form a ring.
In the formula (5), ^R5f and ^R5h may be bonded to each other to form a ring, or may not be bonded to each other to form a ring, but it is preferable that they are not bonded to each other to form a ring.
In Formula (5), R ^5f and R ⁵ⁱ may be bonded to each other to form a ring, or may not be bonded to each other to form a ring, but it is preferable that they be not bonded to each other to form a ring.

In the formula ^(5), in each of R 5a ^{to R 5h} independently represent a hydrogen atom or a ^substituent, at least 1 group represented by Exemplary ethynylphenylbiadamantane derivatives (W) of the R 5a ^{to R 5h.}
In addition, the substituent X mentioned above is mentioned as a substituent represented by R ^{< 5a} > -R ^<5h> . Moreover, the definition of group represented by Formula (W) is as above-mentioned.

Among the compounds represented by the formula (5), among R ^{5a to} R ^5h , one to four groups represented by the formula (W) enhance the carrier mobility and dissolve in an organic solvent. It is preferable from the viewpoint of enhancing the property, more preferably one or two, and particularly preferably two.
Among R ^{5a to} R ^5h , the position of the group represented by formula (W) is not particularly limited, but being R ^5e or R ^5f enhances carrier mobility and enhances solubility in an organic solvent. It is preferable from the viewpoint.
Among R ^{5a to} R ^5h , the substituent other than the group represented by Formula (W) is preferably 0 to 4, more preferably 0 to 2, and 0 or 1. Is more preferable, and 0 is particularly preferable.

The substituent when R ^{5a to} R ^5h is a substituent other than the group represented by formula (W) is preferably a group having a linking group chain length of 3.7 Å or less, and a linking group chain length of 1 The group is more preferably a group of from 0 to 3.7 Å, and still more preferably a group having a linking group chain length of from 1.0 to 2.1 Å. The definition of linking group chain length is as described above.
When R ^{5a to} R ^5h are substituents other than the group represented by formula (W), each substituent is independently a substituted or unsubstituted alkyl group having 2 or less carbon atoms, a substituted or non-substituted carbon group having 2 or less carbon atoms It is preferable that it is a substituted alkynyl group, a substituted or unsubstituted alkenyl group having 2 or less carbon atoms, or a substituted or unsubstituted acyl group having 2 or less carbon atoms, and a substituted or unsubstituted alkyl group having 2 or less carbon atoms It is more preferable that
When the substituents in the case where R ^{5a to} R ^5h are substituents other than the group represented by Formula (W) each independently represent a substituted alkyl group having 2 or less carbon atoms, the substituent that the alkyl group can take is And a cyano group, a fluorine atom, a deuterium atom and the like, and a cyano group is preferable. The substituted or unsubstituted alkyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by the formula (W) is a methyl group, an ethyl group or a methyl group substituted with a cyano group A methyl group or a cyano group-substituted methyl group is more preferable, and a cyano group-substituted methyl group is particularly preferable.
When the substituents in the case where R ^{5a to} R ^5h are substituents other than the group represented by Formula (W) each independently represent a substituted alkynyl group having 2 or less carbon atoms, the substituent which the alkynyl group can take is And deuterium atoms. The substituted or unsubstituted alkynyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the substituent represented by Formula (W) is an ethynyl group or an acetylene group substituted with a deuterium atom Mention may be made, with ethynyl being preferred.
When the substituents when R ^{5a to} R ^5h are substituents other than the group represented by formula (W) each independently represent a substituted alkenyl group having 2 or less carbon atoms, the substituent that the alkenyl group can take is And deuterium atoms. Examples of the substituted or unsubstituted alkenyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by Formula (W) include ethenyl group and ethenyl group substituted with deuterium atom And ethenyl is preferred.
When the substituents in the case where R ^{5a to} R ^5h are substituents other than the group represented by Formula (W) each independently represent a substituted acyl group having 2 or less carbon atoms, the substituent that the acyl group can take is And fluorine atoms. The substituted or unsubstituted acyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by Formula (W) is a formyl group, an acetyl group, or a fluorine-substituted acetyl group. Mention may be made, with the formyl group being preferred.

-Compound represented by Formula (6)-

In formula (6), X ^{6a to} X ^6d each independently represent NR ^6g , O atom or S atom, and R ^6g is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, an aryl group or a heteroaryl group Represents a group.
The X ^6a to X ^6d each independently is preferably from the standpoint of ease of synthesis is O or S atoms. On the other hand, it is preferable from the viewpoint of enhancing carrier mobility that at least one of X ^{6a to} X ^6d is an S atom. X ^6a to X ^6d is preferably the same linking group. It is more preferable that all of X ^{6a to} X ^6d be an S atom.
R ^6g represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, an aryl group or a heteroaryl group, preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an acyl group, The alkyl group is more preferably an alkyl group, further preferably an alkyl group having 1 to 14 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.
When R ^6g represents an alkyl group, it may be a linear alkyl group, a branched alkyl group or a cyclic alkyl group, but being a linear alkyl group enhances the linearity of the molecule and enhances the carrier mobility. From the viewpoint of being able to

In formula (6), R ^{6a to} R ^6f each independently represent a hydrogen atom or a substituent, and at least one represents a group represented by formula (W).
^As the substituent represented by R 6a ^{to R 6f,} include substituents X described above. Moreover, the definition of group represented by Formula (W) is as above-mentioned.
Among these, R ^{6a to} R ^6f are each independently represented by an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a heterocyclic group, an alkoxy group, or an alkylthio group, a formula (W) as a substituent Group is preferable, and an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms, carbon The heterocyclic group having 5 to 12 carbon atoms, the alkylthio group having 1 to 12 carbon atoms, or the group represented by the formula (W) is more preferable, and the below-mentioned linking group chain length is 3.7 Å or less, or the formula The group represented by (W) is more preferable, and the group represented by the formula (W) is particularly preferable.

Among the compounds represented by the formula (6), among R ^{6a to} R ^6f , one to four groups represented by the formula (W) enhance the carrier mobility and dissolve in an organic solvent It is preferable from the viewpoint of enhancing the property, more preferably one or two, and particularly preferably two.
Among R ^{6a to} R ^6f , the position of the group represented by formula (W) is not particularly limited, but R ^{6c to} R ^6f is preferable, and R ^6e or R ^6f is a carrier mobility. Is more preferable from the viewpoint of enhancing the solubility in organic solvents.

Among R ^{6a to} R ^6f , the substituent other than the group represented by formula (W) is preferably 0 to 4, more preferably 0 to 2, and 0 or 1. Is more preferable, and 0 is particularly preferable.
The substituent when R ^{6a to} R ^6f is a substituent other than the group represented by formula (W) is preferably a group having a linking group chain length of 3.7 Å or less, and a linking group chain length of 1 The group is more preferably a group of from 0 to 3.7 Å, and still more preferably a group having a linking group chain length of from 1.0 to 2.1 Å. The definition of linking group chain length is as described above.
Substituents in the case where R ^{6a to} R ^6f are substituents other than the group represented by Formula (W) are each independently a substituted or unsubstituted alkyl group having 2 or less primes, a substituted or non-substituted C 2 or less carbon atom It is preferable that it is a substituted alkynyl group, a substituted or unsubstituted alkenyl group having 2 or less carbon atoms, or a substituted or unsubstituted acyl group having 2 or less carbon atoms, and a substituted or unsubstituted alkyl group having 2 or less carbon atoms It is more preferable that
When the substituents in the case where R ^{6a to} R ^6f are substituents other than the group represented by formula (W) each independently represent a substituted alkyl group having 2 or less carbon atoms, the substituent that the alkyl group can take is And a cyano group, a fluorine atom, a deuterium atom and the like, and a cyano group is preferable. The substituted or unsubstituted alkyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by the formula (W) is a methyl group, an ethyl group or a methyl group substituted with a cyano group A methyl group or a cyano group-substituted methyl group is more preferable, and a cyano group-substituted methyl group is particularly preferable.
When the substituents in the case where R ^{6a to} R ^6f are substituents other than the group represented by Formula (W) each independently represent a substituted alkynyl group having 2 or less carbon atoms, the substituent that the alkynyl group can take is And deuterium atoms. Examples of the substituted or unsubstituted alkynyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by Formula (W) include ethynyl group and acetylene group substituted with deuterium atom Ethynyl group is preferred.
When the substituents in the case where R ^{6a to} R ^6f are substituents other than the group represented by Formula (W) each independently represent a substituted alkenyl group having 2 or less carbon atoms, the substituent that the alkenyl group can take is And deuterium atoms. Examples of the substituted or unsubstituted alkenyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by Formula (W) include ethenyl group and ethenyl group substituted with deuterium atom And ethenyl is preferred.
When the substituents in the case where R ^{6a to} R ^6f are substituents other than the group represented by Formula (W) each independently represent a substituted acyl group having 2 or less carbon atoms, the substituent that the acyl group can take is And fluorine atoms. Examples of the substituted or unsubstituted acyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by Formula (W) include a formyl group, an acetyl group, and a fluorine-substituted acetyl group. Formyl groups are preferred.

-Compound represented by Formula (7)-

In formula (7), X ^7a and X ^7c each independently represent an S atom, an O atom, a Se atom or NR ⁷ⁱ (> N—R ⁷ⁱ ), and X ^7b and X ^7d each independently represent an S atom, Represents an O atom or a Se atom. Each of X ^{7a to} X ^7d independently is preferably an O atom or an S atom from the viewpoint of synthesis ease. On the other hand, it is preferable from the viewpoint of enhancing carrier mobility that at least one of X ^{7a to} X ^7d is an S atom. X ^7a to X ^7d is preferably the same linking group. It is more preferable that all of X ^{7a to} X ^7d are S atoms.

In Formula (7), R ^{7a to} R ⁷ⁱ each independently represent a hydrogen atom or a substituent, and at least one of R ^{7a to} R ⁷ⁱ is a group represented by Formula (W).
^As the substituent represented by R 7a ^{to R 7i,} include substituents X described above. Moreover, the definition of group represented by Formula (W) is as above-mentioned.
R ⁷ⁱ is preferably a hydrogen atom or an alkyl group, more preferably an alkyl group having 5 to 12 carbon atoms, and particularly preferably an alkyl group having 8 to 10 carbon atoms.
When R ⁷ⁱ represents an alkyl group, it may be a linear alkyl group, a branched alkyl group or a cyclic alkyl group, but a linear alkyl group is preferable from the viewpoint of overlapping of HOMO orbitals.

Among the compounds represented by the formula (7), among R ^{7a to} R ⁷ⁱ , the number of the substituents represented by the formula (W) is 1 to 4, to enhance the carrier mobility, and to the organic solvent It is preferable from the viewpoint of enhancing the solubility, more preferably one or two, and particularly preferably two.
Among R ^{7a to} R ⁷ⁱ , the position of the group represented by Formula (W) is not particularly limited, but being R ^7d or R ^7h enhances the carrier mobility and enhances the solubility in an organic solvent. It is preferable from the viewpoint, and R ^7d and R ^7h are more preferable.
Among R ^{7a to} R ^{7i in} the formula (7), the number of substituents other than the group represented by the formula (W) is preferably 0 to 4, more preferably 0 to 2, and 0 Or 1 is more preferable, and 0 is particularly preferable.
When R ^{7a to} R ⁷ⁱ are substituents other than the group represented by Formula (W), the substituent is preferably a group having a linking group chain length of 3.7 Å or less, and the linking group chain length is 1 The group is more preferably a group of from 0 to 3.7 Å, and still more preferably a group having a linking group chain length of from 1.0 to 2.1 Å. The definition of linking group chain length is as described above.
When R ^{7a to} R ⁷ⁱ each is a substituent other than the group represented by Formula (W), each substituent is independently a substituted or unsubstituted alkyl group having 2 or less carbon atoms, a substitution or unsubstituted carbon number 2 or less It is preferably an unsubstituted alkynyl group, a substituted or unsubstituted alkenyl group having 2 or less carbon atoms, or a substituted or unsubstituted acyl group having 2 or less carbon atoms, and a substituted or unsubstituted alkyl having 2 or less carbon atoms More preferred is a group.
When the substituents in the case where R ^{7a to} R ⁷ⁱ are substituents other than the group represented by Formula (W) each independently represent a substituted alkyl group having 2 or less carbon atoms, the substituent that the alkyl group can take is And a cyano group, a fluorine atom, a deuterium atom and the like, and a cyano group is preferable. The substituted or unsubstituted alkyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by the formula (W) is a methyl group, an ethyl group or a methyl group substituted with a cyano group A methyl group or a cyano group-substituted methyl group is more preferable, and a cyano group-substituted methyl group is particularly preferable.
When the substituents in the case where R ^{7a to} R ⁷ⁱ are substituents other than the group represented by Formula (W) each independently represent a substituted alkynyl group having 2 or less carbon atoms, the substituent which the alkynyl group can take is And deuterium atoms. Examples of the substituted or unsubstituted alkynyl group having 2 or less carbon atoms represented by the substituent when the substituent is a substituent other than the substituent represented by Formula (W) include an ethynyl group and an acetylene group substituted with a deuterium atom. And ethynyl is preferred.
When the substituents in the case where R ^{7a to} R ⁷ⁱ are substituents other than the group represented by formula (W) each independently represent a substituted alkenyl group having 2 or less carbon atoms, the substituent that the alkenyl group can take is And deuterium atoms. Examples of the substituted or unsubstituted alkenyl group having 2 or less carbon atoms represented by the substituent when the substituent is a substituent other than the substituent represented by the formula (W) include ethenyl group and ethenyl group substituted with deuterium atom And ethenyl is preferred.
When the substituents in the case where R ^{7a to} R ⁷ⁱ are substituents other than the group represented by Formula (W) each independently represent a substituted acyl group having 2 or less carbon atoms, the substituent that the acyl group can take is And fluorine atoms. Examples of the substituted or unsubstituted acyl group having 2 or less carbon atoms represented by the substituent when the substituent is a substituent other than the substituent represented by Formula (W) include a formyl group, an acetyl group, and a fluorine-substituted acetyl group. Formyl groups are preferred.

-Compound represented by Formula (8)-

In formula (8), X ^8a and X ^8c each independently represent S atom, O atom, Se atom or NR ⁸ⁱ , and X ^8b and X ^8d each independently represent S atom, O atom or Se atom . It is preferable from a viewpoint of synthetic | combination ease that X ^{< 8a} > -X <^8d> is respectively independently O atom or S atom. On the other hand, it is preferable from the viewpoint of enhancing carrier mobility that at least one of X ^{8a to} X ^8d is an S atom. X ^{8a to} X ^8d are preferably the same linking group. It is more preferable that all of X ^{8a to} X ^8d be an S atom.

In formula (8), R ^{8a to} R ⁸ⁱ each independently represent a hydrogen atom or a substituent, and at least one of R ^{8a to} R ⁸ⁱ is a group represented by formula (W).
^As the substituent represented by R 8a ^{to R 8i,} include substituents X described above. Moreover, the definition of group represented by Formula (W) is as above-mentioned.
R ⁸ⁱ is preferably a hydrogen atom or an alkyl group, more preferably an alkyl group having 5 to 12 carbon atoms, and particularly preferably an alkyl group having 8 to 10 carbon atoms.
When R ⁸ⁱ represents an alkyl group, it may be a linear alkyl group, a branched alkyl group or a cyclic alkyl group, but a linear alkyl group is preferable from the viewpoint of overlapping of HOMO orbitals.

Among the compounds represented by the formula (8), among R ^{8a to} R ⁸ⁱ , the number of the substituents represented by the formula (W) is 1 to 4, to enhance the carrier mobility, and to the organic solvent It is preferable from the viewpoint of enhancing the solubility, more preferably one or two, and particularly preferably two.
Among R ^{8a to} R ⁸ⁱ , the position of the group represented by formula (W) is not particularly limited, but being R ^8c or R ^8g enhances the carrier mobility and enhances the solubility in an organic solvent It is preferable from the viewpoint, and R ^8c and R ^8g are more preferable.
Further, among R ^{8a to} R ^{8i in} the formula (8), the number of substituents other than the group represented by the formula (W) is preferably 0 to 4, and more preferably 0 to 2. , 0 or 1 is more preferable, and 0 is particularly preferable.

The substituent when R ^{8a to} R ⁸ⁱ are substituents other than the group represented by formula (W) is preferably a group having a linking group chain length of 3.7 Å or less, and a linking group chain length of 1 The group is more preferably a group of from 0 to 3.7 Å, and still more preferably a group having a linking group chain length of from 1.0 to 2.1 Å. The definition of linking group chain length is as described above.
When R ^{8a to} R ⁸ⁱ are substituents other than the group represented by formula (W), each substituent is independently a substituted or unsubstituted alkyl group having 2 or less carbon atoms, a substitution or unsubstituted carbon number 2 or less It is preferably an unsubstituted alkynyl group, a substituted or unsubstituted alkenyl group having 2 or less carbon atoms, or a substituted or unsubstituted acyl group having 2 or less carbon atoms, and a substituted or unsubstituted alkyl having 2 or less carbon atoms More preferred is a group.
When the substituents when R ^{8a to} R ⁸ⁱ are substituents other than the group represented by Formula (W) each independently represent a substituted alkyl group having 2 or less carbon atoms, the substituent that the alkyl group can take is And a cyano group, a fluorine atom, a deuterium atom and the like, and a cyano group is preferable. The substituted or unsubstituted alkyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by the formula (W) is a methyl group, an ethyl group or a methyl group substituted with a cyano group A methyl group or a cyano group-substituted methyl group is more preferable, and a cyano group-substituted methyl group is particularly preferable.
When the substituents in the case where R ^{8a to} R ⁸ⁱ are substituents other than the group represented by Formula (W) each independently represent a substituted alkynyl group having 2 or less carbon atoms, the substituent that the alkynyl group can take is And deuterium atoms. Examples of the substituted or unsubstituted alkynyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by Formula (W) include ethynyl group and acetylene group substituted with deuterium atom Ethynyl group is preferred.
When the substituents when R ^{8a to} R ⁸ⁱ are substituents other than the group represented by formula (W) each independently represent a substituted alkenyl group having 2 or less carbon atoms, the substituent that the alkenyl group can take is And deuterium atoms. Examples of the substituted or unsubstituted alkenyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by Formula (W) include ethenyl group and ethenyl group substituted with deuterium atom And ethenyl is preferred.
When the substituents in the case where R ^{8a to} R ⁸ⁱ are substituents other than the group represented by Formula (W) each independently represent a substituted acyl group having 2 or less carbon atoms, the substituent that the acyl group can take is And fluorine atoms. Examples of the substituted or unsubstituted acyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by Formula (W) include a formyl group, an acetyl group, and a fluorine-substituted acetyl group. Formyl groups are preferred.

-Compound represented by Formula (9)-

In Formula (9), ^X9a and ^X9b respectively independently represent O atom, S atom, or Se atom. Among them, S atom is preferable.
R ^9c , R ^9d and R ^{9g to} R ^9j each independently represent a hydrogen atom, a halogen atom or a substituent represented by the formula (W). The definition of the group represented by formula (W) is as described above.
R ^9a , R ^9b , R ^9e and R ^9f each independently represent a hydrogen atom or a substituent. ^{Incidentally,} R ^9a, R ^9b, as the substituent represented by ^{R 9e} and ^{R 9f,} include the substituents X described above.
R ^9c , R ^9d and R ^{9g to} R ^9j each independently represent a hydrogen atom, a halogen atom or a group represented by the formula (W) (wherein L ^W represents a group represented by the formula (L-3) or a group represented by 5) a group represented by any of Formula (L-7) to Formula (L-9) and Formula (L-12) to Formula (L-24). Among ^them, R ^{9c, R 9d} and ^R 9 g ^{to R 9j} is more preferably a hydrogen atom.
In addition, as L ^W , a group represented by any one of Formula (L-3), Formula (L-5), Formula (L-13), Formula (L-17) or Formula (L-18) Is preferred.
Preferably, at least one of R ^{9a to} R ⁹ⁱ represents a group represented by Formula (W).

Among the compounds represented by the formula (9), among R ^{9a to} R ⁹ⁱ , the number of the substituents represented by the formula (W) is 1 to 4, to enhance the carrier mobility, and to the organic solvent It is preferable from the viewpoint of enhancing the solubility, more preferably one or two, and particularly preferably two.
Among R ^{9a to} R ⁹ⁱ , the position of the group represented by formula (W) is not particularly limited, but being R ^9b or R ^9f enhances the carrier mobility and enhances the solubility in an organic solvent R ^{9 b} and R ^{9 f} are more preferable in view of the viewpoint.
Further, among R ^{9a to} R ^{9i in} the formula (9), the number of substituents other than the group represented by the formula (W) is preferably 0 to 4, and more preferably 0 to 2. , 0 or 1 is particularly preferable, and 0 is more particularly preferable.

-Compound represented by Formula (10)-

In the formula ^(10), in each of R 10a ^{to R 10h} independently, represent a hydrogen atom or a ^substituent, at least one of R 10a ^{to R 10h} represents a group represented by formula (W). ^As the substituent represented by R 10a ^{to R 10h,} include substituents X described above. Moreover, the definition of the substituent represented by Formula (W) is as above-mentioned.
Among them, R ^{10a to} R ^10h each independently represent a hydrogen atom, a halogen atom or a substituent, and at least one of R ^{10a to} R ^10h is a substituted or unsubstituted arylthio group or a substituted or unsubstituted heteroaryl. It is preferable that it is a ruthio group, a substituted or unsubstituted alkyloxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group or a substituted or unsubstituted alkylamino group.
In R ^{10a to} R ^10h of the formula (10), at least one of R ^10b and R ^10f is a substituted or unsubstituted arylthio group, a substituted or unsubstituted heteroarylthio group, a substituted or unsubstituted alkyloxycarbonyl group Preferably a substituted or unsubstituted aryloxycarbonyl group or a substituted or unsubstituted alkylamino group, more preferably a substituted or unsubstituted arylthio group or a substituted or unsubstituted heteroarylthio group Further preferably, all of R ^10b and R ^10f are a substituted or unsubstituted arylthio group or a substituted or unsubstituted heteroarylthio group, and a substituted or unsubstituted phenylthio group or a group selected from the following group A Particularly preferred is a heteroarylthio group And most preferably a substituted or unsubstituted phenylthio group or a heteroarylthio group represented by the following Formula (A-17), Formula (A-18) or Formula (A-20).

The arylthio group is preferably a group in which a sulfur atom is linked to an aryl group having 6 to 20 carbon atoms, more preferably a naphthylthio group or a phenylthio group, and particularly preferably a phenylthio group.
As the heteroarylthio group, a group in which a sulfur atom is linked to a 3- to 10-membered ring heteroaryl group is preferable, and a group in which a sulfur atom is linked to a 5- or 6-membered ring heteroaryl group is more preferable. The group represented by any of Formula (A-14) to Formula (A-27) is particularly preferable.

In group A, R ′ ′ and R ′ ′ ^N each independently represent a hydrogen atom or a substituent.
In group A, each R ′ preferably independently represents a hydrogen atom or a group represented by formula (W).
In Group A, R ′ ′ ^N is preferably a substituent, more preferably an alkyl group, an aryl group or a heteroaryl group, and substituted with an alkyl group, an aryl group substituted with an alkyl group, or an alkyl group Preferred is a substituted heteroaryl group, and is a 5-membered member substituted with an alkyl group having 1 to 4 carbon atoms, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms Heteroaryl groups are particularly preferred.

  As the alkyloxycarbonyl group, a group in which a carbonyl group is linked to an alkyl group having 1 to 20 carbon atoms is preferable. As for carbon number of an alkyl group, 2-15 are more preferable, and 5-10 are especially preferable.

  The aryloxycarbonyl group is preferably a group in which a carbonyl group is linked to an aryl group having 6 to 20 carbon atoms. 6-15 are more preferable, and, as for carbon number of an aryl group, 8-12 are especially preferable.

As an alkylamino group, the group which the amino group connected with a C1-C20 alkyl group is preferable. As for carbon number of an alkyl group, 2-15 are more preferable, and 5-10 are especially preferable.
Among R ^{10a to} R ^10h , a substituted or unsubstituted arylthio group, a substituted or unsubstituted heteroarylthio group, a substituted or unsubstituted alkyloxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group or a substituted or unsubstituted aryloxycarbonyl group It is preferable that it is 0-4, and, as for substituents (Hereafter, it is also called other substituents.) Other than the alkylamino group of these, It is more preferable that it is 0-2 and it is 0 or 1. More preferably, it is particularly preferably 0.

Each of X ^10a and X ^10b independently represents an S atom, an O atom, a Se atom or NR ^x (> N—R ^x ). It is preferable from the viewpoint of enhancing carrier mobility that at least one of X ^10a and X ^10b is an S atom. It is preferable that X ^10a and X ^10b be the same linking group. More preferably, both of X ^10a and X ^10b are S atoms.
Each R ^x independently represents a hydrogen atom or a group represented by the formula (W). The definition of the group represented by formula (W) is as described above.

-Compound represented by Formula (11)-

In formula (11), X ^11a and X ^11b each independently represent an S atom, an O atom, a Se atom or NR ¹¹ⁿ , and R ^{11a to} R ^11k and R ^11m and R ¹¹ⁿ each independently represent a hydrogen atom or a substituent And at least one of R ^{11a to} R ^11k , R ^11m and R ¹¹ⁿ represents a group represented by Formula (W). As a substituent, the above-mentioned substituent X is mentioned. The definition of the substituent represented by formula (W) is as described above.

In the formula (11), it is preferable from the viewpoint of enhancing carrier mobility that at least one of X ^11a and X ^11b is an S atom. It is preferable that ^X11a and ^X11b be the same linking group. It is more preferable that both X ^11a and X ^11b be S atoms.
In R ^{11a to} R ^11k and R ^{11m in} formula (11), at least one of R ^11c and R ¹¹ⁱ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted heteroarylthio It is preferably a group, a substituted or unsubstituted alkyloxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group or a substituted or unsubstituted alkylamino group, and more preferably a substituted or unsubstituted alkyl group, More preferably, both of R ^11c and R ¹¹ⁱ are a substituted or unsubstituted alkyl group.

-Compound represented by Formula (12)-

In formula (12), X ^12a and X ^12b each independently represent an S atom, an O atom, a Se atom or NR ¹²ⁿ , and R ^{12a to} R ^12k and R ^12m and R ¹²ⁿ each independently represent a hydrogen atom or a substituent And at least one of R ^{12a to} R ^12k , R ^12m and R ¹²ⁿ represents a group represented by formula (W). As a substituent, the above-mentioned substituent X is mentioned. The definition of the substituent represented by formula (W) is as described above.

In the formula (12), it is preferable from the viewpoint of enhancing carrier mobility that at least one of X ^12a and X ^12b is an S atom. It is preferable that X ^12a and X ^12b be the same linking group. It is more preferable that both X ^12a and X ^12b be an S atom.
In R ^{12a to} R ^12k and R ^{12m in} formula (12), at least one of R ^12c and R ¹²ⁱ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted heteroarylthio It is preferably a group, a substituted or unsubstituted alkyloxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group or a substituted or unsubstituted alkylamino group, and more preferably a substituted or unsubstituted alkyl group, More preferably, both of R ^12c and R ¹²ⁱ are a substituted or unsubstituted alkyl group.

-Compound represented by Formula (13)-

In formula (13), X ^13a and X ^13b each independently represent an S atom, an O atom, a Se atom or NR ¹³ⁿ , and R ^{13a to} R ^13k and R ^13m and R ¹³ⁿ each independently represent a hydrogen atom or a substituent And at least one of R ^{13a to} R ^13k , R ^13m and R ¹³ⁿ represents a group represented by formula (W). As a substituent, the above-mentioned substituent X is mentioned. The definition of the group represented by formula (W) is as described above.

In the formula (13), it is preferable from the viewpoint of enhancing carrier mobility that at least one of X ^13a and X ^13b is an S atom. It is preferable that X ^13a and X ^13b be the same linking group. It is more preferable that both X ^13a and X ^13b be an S atom.
In R ^{13a to} R ^13k and R ^{13m in} formula (13), at least one of R ^13c and R ¹³ⁱ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted heteroarylthio It is preferably a group, a substituted or unsubstituted alkyloxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group or a substituted or unsubstituted alkylamino group, and more preferably a substituted or unsubstituted alkyl group, More preferably, both of R ^13c and R ¹³ⁱ are a substituted or unsubstituted alkyl group.

-Compound represented by Formula (14)-

In the formula ^(14), the X 14a ^{to X 14c} each independently, S atom, O atom, a Se atom or a ^{NR 14i, R} 14a ^{~R 14i} each independently represent a hydrogen atom or a ^{substituent, R 14a -At} least one of R ¹⁴ⁱ represents a group represented by Formula (W). As a substituent, the above-mentioned substituent X is mentioned. The definition of the group represented by formula (W) is as described above.
When at least one of R ^{14a to} R ^14h is a group represented by Formula (W) and R ^W is an alkyl group, L ^W is a group represented by Formula (L-2) to Formula (L-25). It is preferable that it is a group represented by either of.

From the viewpoint of enhancing carrier mobility, it is preferable that in the formula (14), at least one of X ¹⁴ a to X ^{14 c} is an S atom. It is preferable that X < ^14a > -X < ^14c > is the same coupling group. X ^14a to X ^14c is more preferably both are S atoms.
As L ^W when R ^W is an alkyl group, Formula (L-2) to Formula (L-5), Formula (L-13), Formula (L-17), or Formula (L-18) The group represented by either of is preferable, and the group represented by any one of Formula (L-3), Formula (L-13), or Formula (L-18) is more preferable.
^R 14a ^{to R 14h} of formula ^(14), at least one of ^{R 14b} and ^{R 14 g,} is preferably a group represented by the formula ^(W), any of ^{R 14b} and ^{R 14 g} is represented by the formula ( It is more preferable that it is a group represented by W).

-Compound represented by Formula (15)-

Wherein ^{(15), X} 15a ~X ^15d are each independently a S atom, O atom, a Se atom or a ^{NR 15g, R} 15a ^{~R 15g} each independently represent a hydrogen atom or a ^{substituent, R 15a} ~ At least one of R ^15g represents a group represented by formula (W). As a substituent, the above-mentioned substituent X is mentioned. The definition of the group represented by formula (W) is as described above.

From the viewpoint of enhancing carrier mobility, it is preferable that in the formula (15), at least one of X ^{15a to} X ^15d is an S atom. X ^15a to X ^15d is preferably the same linking group. X ^15a to X ^15d is more preferably both are S atoms.
^R 15a ^{to R 15f} of formula ^(15), at least one of ^{R 15b} and ^{R 15e,} is preferably a group represented by the formula ^(W), any of ^{R 15b} and ^{R 15e} is the formula ( It is more preferable that it is a group represented by W).

-Compound represented by Formula (16)-

In formula (16), X ^{16a to} X ^16d each independently represent an S atom, an O atom, a Se atom or NR ^16g . R ^{16a to} R ^16g each independently represent a hydrogen atom or a substituent, and at least one of R ^{16a to} R ^16g represents a group represented by Formula (W). As a substituent, the above-mentioned substituent X is mentioned. The definition of the group represented by formula (W) is as described above.
R ^16c and R ^{16f each} represent a hydrogen atom, a halogen atom or a group represented by the formula (W) (wherein L ^W represents a group represented by the formula (L-3), the formula (L-5) or the formula (L-7) And the group represented by any one of Formula (L-9) and Formula (L-12) to Formula (L-24). Each of R ^16a , R ^16b , R ^16d , R ^16e and R ^16g preferably independently represents a hydrogen atom or a substituent.
In Formula (16), L ^W represents Formula (L-3), Formula (L-5), Formula (L-7) to Formula (L-9), and Formula (L-12) to Formula (L) When R ^16c and R ^16f are a group represented by Formula (W), Formula (L-3), Formula (L-5), Formula (L-) 13) is preferably a group represented by any of Formula (L-17) and Formula (L-18).

From the viewpoint of enhancing carrier mobility, it is preferable that in the formula (16), at least one of X ^{16a to} X ^16d is an S atom. X ^16a to X ^16d is preferably the same linking group. It is more preferable that all of X ^{16a to} X ^16d be an S atom.
^R 16a ^{to R 16f} of formula ^(16), at least one of ^{R 16a} and ^{R 16d,} is preferably a group represented by the formula ^(W), none of ^{R 16a} and ^{R 16d} is the formula ( It is more preferable that it is a group represented by W).
Further, R ^16c and R ^16f are preferably hydrogen atoms.

The organic semiconductor compound (T) preferably has an alkyl group on the fused polycyclic aromatic ring in the above fused polycyclic aromatic group, more preferably an alkyl group having 6 to 20 carbon atoms, and 7 carbon atoms It is further preferred to have an alkyl group of -14. It is excellent by the carrier mobility and thermal stability of the organic thin-film transistor obtained as it is the said aspect.
Further, the organic semiconductor compound (T) preferably has one or more alkyl groups on the fused polycyclic aromatic ring in the fused polycyclic aromatic group, and more preferably has 2 to 4 alkyl groups. It is more preferable to have two alkyl groups. It is excellent by the carrier mobility and thermal stability of the organic thin-film transistor obtained as it is the said aspect.

  The molecular weight of the organic semiconductor compound (T) is not particularly limited, but is preferably 3,000 or less, more preferably 2,000 or less, still more preferably 1,000 or less, and 850 It is particularly preferred that By setting the molecular weight to the above upper limit or less, the solubility in a solvent can be enhanced. On the other hand, from the viewpoint of the film quality stability of the thin film, the molecular weight is preferably 300 or more, more preferably 350 or more, and still more preferably 400 or more.

  The synthesis method of the organic semiconductor compound (T) is not particularly limited, and can be synthesized with reference to known methods. As a method of synthesizing the compounds represented by the above formulas (1) to (16), for example, Journal of American Chemical Society, 116, 925 (1994), Journal of Chemical Society, 221 (1951), Org. Lett. , 2001, 3, 3471, Macromolecules, 2010, 43, 6264, Tetrahedron, 2002, 58, 10197, JP 2012-513459, JP 2011-46687, Journal of Chemical Research. miniprint, 3,601-635 (1991), Bull. Chem. Soc. Japan, 64, 3682-3686 (1991), Tetrahedron Letters, 45, 2801-2803 (2004), European Patent Publication No. 2251342, European Patent Publication No. 2301926, European Patent Publication No. 2301921, Korean Patent Publication No. 10-2012-0120886, J.F. Org. Chem. , 2011, 696, Org. Lett. , 2001, 3, 3471, Macromolecules, 2010, 43, 6264, J. Am. Org. Chem. , 2013, 78, 7741, Chem. Eur. J. , 2013, 19, 3721, Bull. Chem. Soc. Jpn. , 1987, 60, 4187; Am. Chem. Soc. , 2011, 133, 5024, Chem. Eur. J. 2013, 19, 3721, Macromolecules, 2010, 43, 6264-6267, J. Org. Am. Chem. Soc. , 2012, 134, 16548-16550, and the like.

  From the viewpoint of carrier mobility of the organic thin film transistor, the organic semiconductor compound (T) is at least one compound represented by any one of Formula (1) to Formula (9), Formula (14) or Formula (15). It is preferable to include a species, and it is more preferable to include at least one compound represented by any one of Formula (1) to Formula (9) or Formula (15).

  Although the preferable specific example of an organic-semiconductor compound (T) is shown below, it is needless to say that it is not limited to these.

(Polymer-based organic semiconductor compounds)
The polymer-based organic semiconductor is not particularly limited, but may be, for example, a heteroarene polymer, a donor-acceptor (DA) type polymer and the like from the viewpoint of giving high crystallinity and high carrier mobility. Here, heteroarenes mean monocyclic aromatic heterocycles and fused aromatic heterocycles, and as heteroarene polymers, for example, polythiophene (polyselenophene), Chem. Rev. 2007, 107, 1296- Those described in 1323 can be mentioned. Among these, from the viewpoint of high mobility, donor-acceptor (DA) type polymers are preferable.
Hereinafter, a donor-acceptor (DA) type polymer which can be suitably used for the organic thin film transistor of the present invention will be described.

(Donor-Acceptor (DA) type polymer)
The donor-acceptor (DA) type polymer is not particularly limited, but for example, a compound having a molecular weight of 2,000 or more having a repeating unit represented by the following formula (P1) (hereinafter simply referred to as “formula (P1) It is preferable to use the organic semiconductor compound represented.

In formula (P1), A represents an electron acceptor unit including a partial structure having at least one of an sp 2 nitrogen atom, a carbonyl group, and a thiocarbonyl group in a ring structure.
D represents a divalent aromatic heterocyclic group having at least one N atom, O atom, S atom, or Se atom in the ring structure, or a divalent aromatic carbonized ring composed of two or more condensed ring structures This represents an electron donor unit containing a hydrogen group as a partial structure.

(Electron acceptor unit (“A” of formula (P1)))
In Formula (P1), A represents an electron acceptor unit including a partial structure having at least one of a sp 2 nitrogen atom, a carbonyl group and a thiocarbonyl group in a ring structure.
A preferably has at least one structure selected from the group consisting of the structures represented by the following formulas (A-1) to (A-12) as a partial structure, and A has the following formula (A-1) It is more preferable that it is a structure represented by at least one selected from the group consisting of: (A-12).

Wherein (A1) ~ formula (A-12), X is independently, O atom, S atom, Se atom or an ^{NR A1.} Y each independently represents an O atom or an S atom. Each Z _a independently represents a CR ^A2 or N atom. W each independently represents C (RA ² ) ₂ , NR ^A1 , N atom, CRA ² , O atom, S atom, or Se atom. R ^A1 is independently, -O -, - S-, and, ^{-NR A3} - at least one contain an even alkyl group of monovalent group represented by the following formula (1-1) Or a binding site to another structure. R ^A2 is each independently an alkyl group which may contain at least one of a hydrogen atom, a halogen atom, -O-, -S-, and -NR ^A3-; Or a bonding site to another structure. Each R ^AA3 independently represents a hydrogen atom or a substituent. Each * independently represents a binding site to another structure.

In formula (1-1), Ar represents an aromatic heterocyclic group or an aromatic hydrocarbon group having 5 to 18 carbon atoms. L _a represents an alkylene group having 1 to 20 carbon atoms which may contain at least one of —O—, —S— and —NR ^{1 S} —. L _b represents an alkyl group having 1 to 100 carbon atoms which may contain at least one of -O-, -S- and -NR ^2S- . R ^1S and R ^2S each independently represent a hydrogen atom or a substituent. l represents an integer of 1 to 5; When l is 2 or more, a plurality of L _b may be the same as or different from each other. * Represents a binding site to another structure.

Wherein (A1) ~ formula (A-12), X is independently, O atom, S atom, Se atom, or represents ^{NR A1,} preferably S atom or ^{NR A1.}
Each Y independently represents an O atom or an S atom, and an O atom is preferable.
Z _a each independently represent a ^{CR A2} or N atom, ^{CR A2} are preferred.
W each independently represents C (RA ² ) ₂ , NR ^A1 , N atom, CR ^A2 , O atom, S atom, or Se atom, and C (RA ¹ ) ₂ , CR ^A2 or S atom is preferable.
R ^A1 is independently, -O -, - S-, and, ^{-NR A3} - at least one which may contain an alkyl group, a monovalent group represented by the above formula (1-1) of , or represents a binding site with another structure, -O -, - S-, and, ^{-NR A3} - at least one which may contain alkyl groups of, or, the formula (1-1) The monovalent group represented by is preferable.
R ^A1 is -O -, - S-, and, ^{-NR A3} - when referring to at least one comprise also an alkyl group of, preferably an alkyl group having 2 to 30 carbon atoms, carbon atoms 8-25 Alkyl groups are more preferred. The alkyl group may be linear or branched.
Here, that the alkyl group contains -O- means that -O- is introduced in the carbon-carbon bond of the alkyl group, or -O- is introduced to one end of the alkyl group ( Means an alkoxy group). The case where the alkyl group contains -S- or -NR ^A3- also has the same meaning.
Note that the binding site of the other structures in the R ^A1, the binding site of other structure represented by the above formula (A1) ~ formula (A-12) in the *.
R ^A2 is each independently an alkyl group which may contain at least one of a hydrogen atom, a halogen atom, -O-, -S-, and -NR ^A3-; Represents a bonding site to a monovalent group or other structure, and is preferably a bonding site to a hydrogen atom or another structure.
R ^A2 is -O -, - S-, and, ^{-NR A3} - when referring to at least one comprise also an alkyl group of, preferably an alkyl group having 2 to 30 carbon atoms, carbon atoms 8-25 Alkyl groups are more preferred. The alkyl group may be linear or branched.
Here, that the alkyl group contains -O- means that -O- is introduced in the carbon-carbon bond of the alkyl group, or -O- is introduced to one end of the alkyl group ( Means an alkoxy group). The case where the alkyl group contains -S- or -NR ^A3- also has the same meaning.
When R ^A2 represents a halogen atom, an F atom, a Cl atom, a Br atom, or an I atom is preferable, and an F atom is more preferable.
Note that the binding site of other structures in R ^A2, a binding site to the other structure represented by the above formula (A-1) ~ formula (A-12) in the *.
Each R ^AA3 independently represents a hydrogen atom or a substituent. The substituent in R ^{A3 has the same meaning as} the substituent in R ^1S and R ^2S described later.

In formula (1-1), Ar represents an aromatic heterocyclic group or an aromatic hydrocarbon group having 5 to 18 carbon atoms.
Examples of the aromatic hydrocarbon group having 5 to 18 carbon atoms in Ar include two or more of a benzene ring group, a biphenyl group, a naphthalene ring group, or an aromatic hydrocarbon in which three rings are condensed (for example, a fluorene ring) The group which removed the hydrogen atom is mentioned. Among these, from the viewpoint of more excellent carrier mobility, a benzene ring group, a biphenyl group or a naphthalene ring group is preferable, and a benzene ring group is preferable.
The aromatic heterocyclic group for Ar may be a single ring or may have a condensed ring structure of two or more rings, but is a single ring from the viewpoint of more excellent carrier mobility. Is preferred. The aromatic heterocyclic group for Ar is preferably a 5- to 7-membered ring. The hetero atom contained in the aromatic heterocyclic group is preferably N atom, O atom, S atom or Se atom, and more preferably S atom.
L _a represents an alkylene group having 1 to 20 carbon atoms which may contain at least one of —O—, —S— and —NR ^{1 S} —. Here, that the alkylene group contains -O- means that -O- is introduced into the carbon-carbon bond of the alkylene group or -O- is introduced to one end or both ends of the alkylene group. I mean the case. The case where an alkylene group contains -S- or -NR ^1S- also has the same meaning.
The alkylene group representing L _a may be linear, branched or cyclic, but is preferably a linear or branched alkylene group.
The carbon number of the alkylene group representing L _a is 1 to 20, but it is preferably 1 to 15 and more preferably 1 to 10 from the viewpoint that the carrier mobility is more excellent. .
Note that when the alkylene group representing L _a is a branched chain, for the carbon number of the branch portion, is intended to include the number of carbon atoms of the alkylene group representing the L _a. However, _{L a} is ^{-NR 1S} - include, and if the ^{R 1S} contains a carbon ^atom, the carbon number of ^{R 1S} shall not be included in the carbon number of the alkylene group representing _{L a.}
L _b represents an alkyl group having 1 to 100 carbon atoms which may contain at least one of -O-, -S- and -NR ^2S- . Here, that the alkyl group includes -O- means that -O- is introduced in the middle of the carbon-carbon bond of the alkyl group, or one end of the alkyl group (that is, the connecting portion with the above "Ar" The case where -O- is introduce | transduced is meant. The case where the alkyl group contains -S- or -NR ^2S- also has the same meaning.
The alkyl group representing L _b may be linear, branched or cyclic, but from the viewpoint of being more excellent in carrier mobility and temporal stability under high temperature and high humidity, straight chain A linear or branched alkyl group is preferred, and a branched alkyl group is more preferred. In addition, the alkyl group representing L _b may be a halogenated alkyl group having a halogen atom (preferably, F atom, Cl atom, Br atom, I atom, more preferably F atom) as a substituent.
The carbon number of the alkyl group representing L _b is 1 to 100, preferably 2 to 60, more preferably 2 to 30, and still more preferably 8 to 25.
When the alkyl group representing L _b is branched, the carbon number of the branched portion is included in the carbon number of the alkyl group representing L _b . However, when L _b contains —NR ^{2 S} — and R ^{2 S} contains a carbon atom, the carbon number of R ^{2 S} is not included in the carbon number of the alkylene group representing L _b .
R ^1S and R ^2S each independently represent a hydrogen atom or a substituent. As a substituent, an alkyl group (preferably, a linear or branched alkyl group having 1 to 10 carbon atoms), a halogen atom (preferably, an F atom, a Cl atom, a Br atom, an I atom), an aryl group (preferably Preferably, it represents an aryl group having 6 to 20 carbon atoms. Among these, R ^1S and R ^2S are each independently preferably a hydrogen atom or an alkyl group, and more preferably an alkyl group.
l represents an integer of 1 to 5, preferably 1 or 2. When l is 2 or more, a plurality of L _b may be the same as or different from each other.
Moreover, when l is an integer less than 5, Ar may have another substituent. Examples of the substituent include the same substituents as the above R ^1S and R ^2S .
* Represents a binding site to another structure.

The organic semiconductor compound represented by Formula (P1) is at least one selected from the group consisting of structures represented by Formula (A-1) to Formula (A-12) in which A in Formula (P1) is It is preferable to have a structure as a partial structure, and formulas (A-1), (A-3), (A-4), (A-5), (A-6), and (A-8). It is more preferable to have at least one structure selected from the group consisting of structures represented by formula (A-12) and formula (A-12) as a partial structure, and formula (A-1), formula (A-3), formula (A-12) A-5), at least one structure selected from the group consisting of the structures represented by Formula (A-6), Formula (A-8) and Formula (A-12) as a partial structure Preferably, at least one structure selected from the group consisting of structures represented by Formula (A-1) and Formula (A-3) is a partial structure Particularly preferably has, the structure represented by the formula (A-3) is most preferable.
Further, the organic semiconductor compound represented by the formula (P1) has a structure in which A in the formula (P1) is represented by each formula in each of the above-mentioned embodiments, as compared with the embodiment having the structure represented by each formula The aspect whose structure of A is represented by each formula is more preferable.

Although the example of the structure represented by Formula (A-1)-Formula (A-12) is shown below, this invention is not limited by the following illustration. In following Structural formula, R ^{<A1 >} is synonymous with R ^{< A1>} in Formula (A-1)-a formula (A-12), and its preferable aspect is also the same.
Also, * represents a binding site to another structure.

(Electron donor unit (“D” in formula (P1)))
D is a divalent aromatic heterocyclic group having at least one N atom, O atom, S atom, or Se atom in a ring structure, or a divalent aromatic hydrocarbon consisting of a condensed ring structure of two or more rings It is an electron donor unit containing a group as a partial structure.

As a bivalent aromatic heterocyclic group having at least one N atom, O atom, S atom or Se atom in the ring structure, a bivalent aromatic heterocyclic group having at least one S atom in the ring structure Is preferred.
The divalent aromatic heterocyclic group may be a single ring or may have a condensed ring structure of two or more rings, and a combination of two or more single ring divalent aromatic heterocyclic groups. Or a combination of two or more monocyclic bivalent aromatic heterocyclic groups and a bivalent aromatic heterocyclic group having one or more condensed rings of two or more rings. preferable.
The divalent aromatic heterocyclic group may further have a substituent, and preferred examples of the substituent include at least one of -O-, -S-, and -NR ^D3- Alkyl group (for example, an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms is preferable, and an alkyl group having 1 to 20 carbon atoms is more preferable), an alkenyl group (preferably 2 to 30 carbon atoms) ), Alkynyl group (preferably having 2 to 30 carbon atoms), aromatic hydrocarbon group (preferably having 6 to 30 carbon atoms), and aromatic heterocyclic group (preferably 5 to 7-membered ring). , O atom, N atom, S atom and Se atom are preferable, and halogen atom (F atom, Cl atom, Br atom and I atom are preferable, F atom or Cl atom is more preferable, and F atom is particularly preferable). , The above equation (1-1) It includes monovalent groups represented.
^RD3 is synonymous with ^RD3 in Formula (D-1) mentioned later, and its preferable aspect is also the same.

Although the example of the said bivalent aromatic heterocyclic group is shown below, this invention is not limited by the following illustration. In the following structural formulae, a hydrogen atom may be an alkyl group, an alkenyl group, an alkynyl group, an aromatic hydrocarbon group, an aromatic group which may contain at least one of -O-, -S- and -NR ^D3- It may be substituted by a heterocyclic group, a halogen atom, or a group represented by the above formula (1-1), and R ^D1 has the same meaning as R ^D1 in the formula (D-1) described later, and is preferable The aspect is also the same, and * represents a binding site to another structure. The -O -, - S-, and, ^{-NR D3} - As the alkyl group which may comprise at least one of, preferably an alkyl group having 1 to 30 carbon atoms, an alkyl group having 1 to 20 carbon atoms Is more preferred. ^RD3 is synonymous with ^RD3 in Formula (D-1) mentioned later, and its preferable aspect is also the same.

The aromatic hydrocarbon group having a condensed ring structure of two or more rings is preferably an aromatic hydrocarbon group having 10 to 20 carbon atoms, and is a fluorene group, a naphthylene group, or an aromatic carbon atom in which three or four rings are condensed. A group obtained by removing two hydrogen atoms from hydrogen is more preferable, and a group obtained by removing two hydrogen atoms from an anthracene ring, a phenanthrene ring, a chrysene ring, or a pyrene ring is more preferable.
The aromatic hydrocarbon Suisomoto may further have a substituent, and as preferred substituents, -O -, - S-, and, -NR D3 ^- alkyl which may contain at least one of Groups, halogen atoms, and monovalent groups represented by the above formula (1-1). Preferred examples of the alkyl group and the halogen atom which may contain at least one of -O-, -S- and -NR ^D3 -are the same as those described for the divalent aromatic heterocyclic group above. It is similar. ^RD3 is synonymous with ^RD3 in Formula (D-1) mentioned later, and its preferable aspect is also the same.

  In Formula (P1), D is preferably a structure represented by Formula (D-1).

In the formula (D1), X 'are each independently, O atom, S atom, Se atom or an ^{NR D1.} R ^D1 each independently represents a monovalent organic group which may be a monovalent group represented by the above formula (1-1). Each Z _d independently represents an N atom or CR ^D2 . Each R ^D2 independently represents a hydrogen atom or a monovalent organic group which may be a monovalent group represented by the above formula (1-1). M represents a single bond, a divalent aromatic heterocyclic group, a divalent aromatic hydrocarbon group, an alkenylene group, an alkynylene group, or a divalent group formed by combining these. M is substituted with an alkyl group which may contain at least one of -O-, -S- and -NR ^D3- , or a monovalent group represented by the above formula (1-1) It may be done. Each R ^D3 independently represents a hydrogen atom or a substituent. p and q each independently represent an integer of 0 to 4; Each * independently represents a binding site to another structure.
In addition, in said Formula (D-1), each repeating unit and said M are connected so that rotation is possible in a joint axis.
That is, for example, in the formula (D-1) (and the notations of formulas (2) to (6) described later), repeating units of a 5-membered ring linked with p and repeating units of a 5-membered ring linked with q Although the directions are opposite to each other, the expression (D-1) (and the expressions of the expressions (P2) to (P6) described later) is a meaning also including a structure in which these are directed in the same direction. .

Wherein (D1), X 'are each independently, O atom, S atom, Se atom, or represents ^{NR D1,} O atom, S atom, or, preferably a Se atom, an S atom It is more preferable that
Z _d independently represents N atom or CR ^D2 , more preferably CR ^D2 .
R ^D1 each independently represents a monovalent organic group, -O -, - S-, and, ^{-NR D3} - alkyl group which may comprise at least one of (e.g., 1 to 30 carbon atoms Alkyl group or alkoxy group having 1 to 30 carbon atoms is preferable, and alkyl group having 8 to 30 carbon atoms is more preferable), alkynyl group (preferably having 2 to 30 carbon atoms), and aromatic hydrocarbon group (for carbon number) 6 to 30 is preferable, aromatic heterocyclic group (5 to 7-membered ring is preferable. As a hetero atom, O atom, N atom, S atom, Se atom is preferable), halogen atom (F atom, Cl atom) Preferably an atom, Br atom or I atom, more preferably F atom or Cl atom, and particularly preferably F atom) or a monovalent group represented by the above formula (1-1), Alkyl group, halogen atom, or above And more preferably a monovalent group represented by the formula (1-1).
Each R ^D2 independently represents a hydrogen atom or a monovalent organic group, and is an alkyl group that may contain at least one of a hydrogen atom, -O-, -S-, and -NR ^D3- (for example, An alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms is preferable, and an alkyl group having 1 to 20 carbon atoms is more preferable), an alkynyl group (preferably having 2 to 30 carbon atoms), and an alkenyl group. (C2-C30 is preferable.), Aromatic hydrocarbon group (C6-C30 is preferable), aromatic heterocyclic group (5- to 7-membered ring is preferable. As a hetero atom, O atom, N) Atom, S atom, Se atom is preferable), halogen atom (F atom, Cl atom, Br atom, I atom is preferable, F atom or Cl atom is more preferable, F atom is particularly preferable), or the above formula Table (1-1) It is preferably a monovalent group, a hydrogen atom, an alkyl group, more preferably a halogen atom, or a monovalent group represented by the above formula (1-1).
M represents a single bond, a divalent aromatic heterocyclic group, a divalent aromatic hydrocarbon group, an alkenylene group, an alkynylene group, or a divalent group formed by combining these. M is substituted with an alkyl group which may contain at least one of -O-, -S- and -NR ^D3- or a monovalent group represented by the formula (1-1) It may be
The divalent aromatic heterocyclic group for M may be a single ring or may have a condensed ring structure of two or more rings. Examples of the divalent aromatic heterocyclic group preferably used in the present invention are the same as the examples of the divalent aromatic heterocyclic group having a condensed ring structure of two or more rings as described above.
The divalent aromatic hydrocarbon group for M is preferably an aromatic hydrocarbon group having a carbon number of 6 to 20, and is a phenylene group, a biphenylene group, a fluorene group, a naphthylene group, or an aromatic ring formed by condensation of three or four rings. A group obtained by removing two hydrogen atoms from a group hydrocarbon is more preferable, and a group obtained by removing two hydrogen atoms from a fluorene group, a naphthylene group, an anthracene ring, a phenanthrene ring, a chrysene ring or a pyrene ring is more preferable.
The divalent aromatic heterocyclic group or the divalent aromatic hydrocarbon group for M may further have a substituent, and preferred examples of the substituent include -O-, -S-, and And an alkyl group which may contain at least one of -NR ^D3- (for example, an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms is preferable, and an alkyl group having 1 to 20 carbon atoms is And more preferably a halogen atom (F atom, Cl atom, Br atom, I atom is preferable, F atom or Cl atom is more preferable, and F atom is particularly preferable), represented by the above formula (1-1) A monovalent group is mentioned.
As an alkenylene group in M, a C2-C10 alkenylene group is preferable, a C2-C4 alkenylene group is more preferable, and an ethenylene group is more preferable.
As an alkynylene group in M, a C2-C10 alkynylene group is preferable, a C2-C4 alkynylene group is more preferable, and an ethynylene group is more preferable.
Each R ^D3 independently represents a hydrogen atom or a substituent. The substituent in R ^{D3 has the same meaning as} the substituent in R ^1S and R ^2S above.
p and q are each independently an integer of 0 to 4, preferably an integer of 1 to 3, and more preferably an integer of 1 to 2. Preferably, p and q have the same value. Moreover, it is preferable that p + q is 2-4.
However, when p + q is 0, M is a divalent aromatic heterocyclic group having at least one N atom, O atom, S atom, or Se atom in the ring structure, or a condensed of two or more rings. It is preferable to include a divalent aromatic hydrocarbon group consisting of a ring structure as a partial structure.

Although the example of a structure of D is shown below, this invention is not limited by the following illustration. In the following structural formulae, a hydrogen atom may be an alkyl group which may contain at least one of -O-, -S- and -NR ^D3- , or a group represented by the above formula (1-1) may be substituted by, R ^D1 has the same meaning as R ^D1 in the formula (D1), and also the same preferred embodiment, * represents a binding site with another structure. The -O -, - S-, and, ^{-NR D3} - As the alkyl group which may comprise at least one of, preferably an alkoxy group of the alkyl group or C1-30 C1-30 And an alkyl group having 8 to 30 carbon atoms is more preferable. R ^D3 has the same meaning as ^{R D3} in the above formula (D-1), a preferable embodiment thereof is also the same.

(Repeating units represented by Formula (P2) to Formula (P6))
The repeating unit represented by the above formula (P1) is preferably a repeating unit represented by any of the following formulas (P2) to (P6), and either of the following formula (P2) or the following formula (P3) It is more preferable that it is a repeating unit represented by か, and it is particularly preferable that it is a repeating unit represented by the following formula (P3).

The formula (P2) in ~ (P6), X is independently, O atom, S atom, Se atom or an ^{NR A1.}
R ^A1 is independently, -O -, - S-, and, ^{-NR A3} - at least one which may contain an alkyl group, a monovalent group represented by the above formula (1-1) of Or a binding site to another structure.
Y each independently represents an O atom or an S atom.
Each Z _a independently represents a CR ^A2 or N atom.
R ^A2 independently represents an alkyl group which may contain at least one of a hydrogen atom, a halogen atom, -O-, -S-, and -NR ^A3- , or a binding site to another structure Represents
Each R ^AA3 independently represents a hydrogen atom or a substituent.
X 'are each independently, O atom, S atom, Se atom or an ^{NR D1.}
R ^D1 each independently represents a monovalent organic group which may be a monovalent group represented by the above formula (1-1).
Each Z _d independently represents an N atom or CR ^D2 . Each R ^D2 independently represents a hydrogen atom or a monovalent organic group which may be a monovalent group represented by the above formula (1-1).
M represents a single bond, a divalent aromatic heterocyclic group, a divalent aromatic hydrocarbon group, an alkenylene group, an alkynylene group, or a divalent group formed by combining these. M is substituted with an alkyl group which may contain at least one of -O-, -S- and -NR ^D3- , or a monovalent group represented by the above formula (1-1) It may be done.
Each R ^D3 independently represents a hydrogen atom or a substituent.
p and q each independently represent an integer of 0 to 4;

In formulas (P2) to (P6), X, Y, Z _a , R ^A1 , R ^A2 and R ^A3 represent X, Y, Z in the above formulas (A-1) to (A-12) _{a 1} , R ^A1 , R ^A2 and R ^A3 respectively have the same meanings, and preferred embodiments are also the same.
In the formula (P2) to the formula (P6), X ′, Z _d , R ^D1 , R ^D2 , R ^D3 , M, p, and q are X ′, Z _d , and Q in the above formula (D-1). Each of R ^D1 , R ^D2 , R ^D3 , M, p, and q has the same meaning, and preferred embodiments are also the same.

(Preferred embodiment of organic semiconductor compound)
The content of the repeating unit represented by the formula (P1) in the organic semiconductor compound is preferably 60 to 100% by mass, and more preferably 80 to 100% by mass, based on the total mass of the organic semiconductor compound. The amount is more preferably 90 to 100% by mass, and it is particularly preferably formed only from the repeating unit represented by the formula (P1). In addition, being formed only from the repeating unit represented by Formula (P1) substantially means that content of the repeating unit represented by Formula (P1) is 95 mass% or more, and 97 It is preferable that it is mass% or more, and it is more preferable that it is 99 mass% or more.
When the content of the repeating unit represented by the formula (P1) is within the above range, an organic semiconductor layer having more excellent carrier mobility can be obtained.
Moreover, the organic semiconductor compound may contain the repeating unit represented by Formula (P1) individually by 1 type, and may contain 2 or more types.

  The organic semiconductor compound is a compound having two or more repeating units represented by the formula (P1), may be an oligomer having a repeating unit number n of 2 to 9, and a polymer having a repeating unit number n of 10 or more ((1) It may be a polymer). Among these, a polymer having a repeating unit number n of 10 or more is preferable from the viewpoint of carrier mobility and physical properties of the obtained organic semiconductor layer.

  From the viewpoint of carrier mobility, the molecular weight of the compound having a repeating unit represented by the formula (P1) is preferably 2,000 or more, more preferably 5,000 or more, and 10,000 or more. Some are more preferable, 20,000 or more is particularly preferable, and 30,000 or more is most preferable. Also, from the viewpoint of solubility, it is preferably 1,000,000 or less, more preferably 300,000 or less, still more preferably 150,000 or less, and particularly preferably 100,000 or less. preferable.

In the present invention, when the compound having the repeating unit represented by the formula (P1) has a molecular weight distribution, the molecular weight of the compound means a weight average molecular weight.
In the present invention, the weight average molecular weight and the number average molecular weight of the compound having a repeating unit represented by the formula (P1) are measured by gel permeation chromatography (GPC (Gel Permeation Chromatography)) and converted to standard polystyrene. Is required. Specifically, for example, GPC uses HLC-8121GPC (manufactured by Tosoh Corp.), and 2 columns of TSKgel GMH _HR- H (20) HT (manufactured by Tosoh Corp., 7.8 mm ID × 30 cm). As used herein, 1,2,4-trichlorobenzene is used as an eluent. The conditions are a sample concentration of 0.02% by mass, a flow rate of 1.0 ml / min, a sample injection amount of 300 μl, a measurement temperature of 160 ° C., and an IR (infrared) detector. Moreover, the standard curve is a Tosoh Co., Ltd. product "standard sample TSK standard, polystyrene": "F-128", "F-80", "F-40", "F-20", "F-10", It prepares from 12 samples of "F-4", "F-2", "F-1", "A-5000", "A-2500", "A-1000", and "A-500".

In the organic semiconductor layer, the compound having a repeating unit represented by the formula (P1) may be contained alone or in combination of two or more.
In addition, the structure of the end of the compound having a repeating unit represented by the formula (P1) is not particularly limited, and the presence or absence of other structural units, the type of substrate used at the time of synthesis, the quenching agent at the time of synthesis Depending on the kind of agent), for example, hydrogen atom, hydroxy group, halogen atom, ethylenic unsaturated group, alkyl group, aromatic heterocyclic group (preferably thiophene ring), aromatic hydrocarbon group (benzene) Ring is preferred).

  The method for synthesizing the compound having a repeating unit represented by the formula (P1) is not particularly limited, and may be synthesized with reference to a known method. For example, JP-A-2010-527327, JP-A-2007-516315, JP-A-2014-515043, JP-A-2014-507488, JP-A-2011-501451, JP-A-2010-18790, WO2012 / 174561, The precursor of the electron acceptor unit and the precursor of the electron donor unit are synthesized with reference to the documents such as Table 2011-514399, JP-A-2011-514913, etc., and each precursor is subjected to Suzuki coupling or Stille coupling. Etc. can be synthesized by cross-coupling reaction.

  Although the preferable specific example of the organic-semiconductor compound represented by Formula (P1) below is shown, this invention is not limited by the following illustration.

(Surfactant)
A surfactant can be added to the organic semiconductor layer to further improve the film thickness uniformity of the coating film.
When the organic thin film transistor is subjected to a heating process, the surfactant may flow and become unevenly distributed, thereby causing distortion in the organic semiconductor layer and generating a crack. Therefore, it is preferable to use a surfactant having a glass transition temperature of 50 ° C. or higher.
The surfactant having a glass transition temperature of 50 ° C. or higher may be introduced into the organic semiconductor layer or into the intermediate layer together with the negative expansion material. By using the above surfactant, the film thickness uniformity can be further improved without generating a crack and without reducing the carrier mobility and the maintenance rate thereof under high temperature and high humidity conditions.

The glass transition temperature (Tg) of the polymer is obtained by performing DSC measurement on each of the following methods and conditions using a differential scanning calorimeter (DSC) Q100 (manufactured by TA Instruments).
DSC measurement was performed in a cycle of heating (first time) → cooling (first time) → heating (second time), and DSC curves were obtained at the time of the first cooling and at the time of the second heating. The Tg determined from the DSC curve obtained at the second heating was employed. When Tg was determined from the DSC curve, Tg was read from the inflection point of the DSC curve.
Measurement conditions Measurement range: -30 ° C to 230 ° C
Heating / cooling rate: 10 ° C / min

As a surfactant having a glass transition temperature of 50 ° C. or higher, for example, PMMA-b-PDMS (copolymer of polymethyl methacrylate and polydimethylsiloxane), PMMA-b-PS (copolymer of polymethyl methacrylate and polystyrene) ), PMMA-b-POSS (copolymer of polymethyl methacrylate and silsesquioxane methacrylate), PMMA-b-PEO (copolymer of polymethyl methacrylate and polyethylene oxide), PMMA-b-PPO (polymethyl methacrylate) Block copolymers containing a polymer chain having a glass transition temperature of 50 ° C. or higher, such as copolymers of polypropylene and polypropylene oxide, and PS-b-PEO (copolymer of polystyrene and polyethylene oxide). That is, in the block copolymer, at least one block having a glass transition temperature of 50 ° C. or more may be included.
Among them, a surfactant having a glass transition temperature of 80 ° C. or more (preferably, a block copolymer containing a polymer chain having a Tg of 80 ° C. or more) is more preferable. The upper limit is not particularly limited, but is often 120 ° C. or less.
When a block copolymer containing a polymer chain is used as a surfactant having a glass transition temperature of 50 ° C. or higher, the weight average molecular weight is not particularly limited, but 10,000 to 200,000 is preferable, and 10,000 to 9.5. 10,000 is more preferable.
When the organic semiconductor layer contains a surfactant, the content of the surfactant is preferably 0.01 to 30% by mass, and 0.1 to 10% by mass with respect to the total solid content. More preferable.
Also, the surfactant may be contained in the intermediate layer. When the intermediate layer contains a surfactant, the content of the surfactant is preferably 0.01 to 30% by mass, and more preferably 0.1 to 10% by mass, based on the total solid content. preferable.
When the surfactant is contained in any of the intermediate layer and the organic semiconductor layer, the content of the surfactant may be in the above range with respect to the total solid content of the intermediate layer and the organic semiconductor layer. .

<Source electrode, drain electrode>
In the OTFT of the present invention, the source electrode is an electrode into which current flows from the outside through the wiring. In addition, the drain electrode is an electrode that sends a current to the outside through the wiring, and is usually provided in contact with the organic semiconductor layer.
As a material of a source electrode and a drain electrode, the conductive material used for the conventional organic thin-film transistor can be used, For example, the conductive material etc. which were demonstrated by the said gate electrode are mentioned.

  The source electrode and the drain electrode can be formed by the same method as the method for forming the gate electrode.

A lift-off method or an etching method can be adopted as the photolithography method.
In particular, since the gate insulating layer is excellent in resistance to the etching solution and the peeling solution, the source electrode and the drain electrode can be preferably formed also by the etching method. The etching method is a method in which an unnecessary portion is removed by etching after depositing a conductive material. When patterning is performed by the etching method, peeling of the conductive material left on the base at the time of resist removal, reattachment to the base of the resist residue and the conductive material removed can be prevented, and the shape of the electrode edge portion is excellent. In this respect, it is preferable to the lift-off method.

  In the lift-off method, a resist is applied to a part of the base, a conductive material is formed into a film on this, and the resist etc. is removed or removed with a solvent to remove the entire conductive material on the resist. Is a method of forming a film of a conductive material only on the portion which has not been applied.

The thickness of each of the source electrode and the drain electrode is arbitrary, but is preferably 1 nm or more, and particularly preferably 10 nm or more. Moreover, 500 nm or less is preferable and 300 nm or less is especially preferable.
The distance (channel length) between the source electrode and the drain electrode is arbitrary, but is preferably 100 μm or less, and particularly preferably 50 μm or less. The channel width is preferably 5000 μm or less, and particularly preferably 1000 μm or less.

<Overcoat layer>
The OTFT of the present invention may have an overcoat layer. The overcoat layer is usually a layer formed as a protective layer on the surface of the OTFT. It may be a single layer structure or a multilayer structure.
The overcoat layer may be an organic overcoat layer or an inorganic overcoat layer.
The material for forming the organic overcoat layer is not particularly limited, and examples thereof include: polystyrene, acrylic resin, polyvinyl alcohol, polyolefin, polyimide, polyurethane, organic polymers such as polyacetylene and epoxy resin, and organic polymers thereof The derivative etc. which introduce | transduced the crosslinkable group, the water repellent group, etc. are mentioned. These organic polymers and their derivatives can also be used in combination with a crosslinking component, a fluorine compound, a silicon compound and the like.
The material for forming the inorganic overcoat layer is not particularly limited, and examples thereof include metal oxides such as silicon oxide and aluminum oxide, and metal nitrides such as silicon nitride.
One of these materials may be used, or two or more thereof may be used in any combination and ratio.

There is no restriction | limiting in the formation method of overcoat layer, It can form by well-known various methods.
For example, an organic overcoat layer is prepared, for example, by applying a solution containing a material to be an overcoat layer to the underlying layer and drying it after applying a solution containing a material to be an overcoat layer, exposing after being dried, It can be formed by a method such as development and patterning. In addition, patterning of overcoat layer can also be directly formed by the printing method, the inkjet method, etc. FIG. In addition, after the patterning of the overcoat layer, the overcoat layer may be crosslinked by exposure or heating.
On the other hand, the inorganic overcoat layer can be formed by a dry method such as a sputtering method or a vapor deposition method or a wet method such as a sol-gel method.

<Other layers>
The OTFT of the present invention may be provided with layers and members other than the above.
As another layer or member, a bank etc. are mentioned, for example. The bank is used for the purpose of blocking the discharge liquid at a predetermined position or the like when forming a semiconductor layer, an overcoat layer or the like by an inkjet method or the like. For this reason, the banks usually have liquid repellency. Examples of the bank formation method include a method of performing liquid repellent treatment such as a fluorine plasma method after patterning by a photolithography method and a method of curing a photosensitive composition containing a liquid repellent component such as a fluorine compound.
In the case where the gate insulating layer is formed of an organic material in the organic thin film transistor of the present invention, the latter method of curing the photosensitive composition containing a liquid repellent component can be affected by the liquid repellent treatment. It is preferable because it has less sex. Note that a technique may be used in which the background is provided with a liquid-repellent contrast and the same role as the bank is given without using the bank.

<Manufacturing method>
(Method of manufacturing organic semiconductor layer / intermediate layer with material for organic thin film transistor or material set for organic thin film transistor)
The method for producing the organic thin film transistor described above (hereinafter sometimes referred to as the method of the present invention) is not particularly limited, and each member (gate insulating layer, source electrode, drain electrode) can be produced by the method described above.
In addition, as a method of forming the organic semiconductor layer and the intermediate layer in the organic thin film transistor, for example, after forming a coating film by a material for an organic thin film transistor which is a composition containing an organic semiconductor compound, a negative expansion material and a binder, phase separation phenomenon The organic semiconductor compound and the negative expansion material may be separately phase separated in the film thickness direction to simultaneously form the organic semiconductor layer and the intermediate layer, or before or after forming the organic semiconductor layer. Later, a layer containing a negative expansion material and a binder carrying a negative expansion material may be separately laminated.
Hereinafter, the above two methods will be described in detail.

First, the method of using the above-mentioned organic thin film transistor material is a method of forming the intermediate layer and the organic semiconductor layer by utilizing the phase separation phenomenon between the organic semiconductor compound and the negative expansion material.
Usually, the organic semiconductor compound and the negative expansion material are not mixed due to the difference in their structures, so when they are mixed, they are separated into the phase of the organic semiconductor compound and the phase of the negative expansion material. Therefore, when a coating film is produced using a material for an organic thin film transistor which is a composition containing an organic semiconductor compound, a negative expansion material and a binder, a high concentration region of the negative expansion material precipitated by specific gravity is formed below the coating film. On the other hand, the crystal layer of the organic semiconductor compound is formed on the upper side of the coating film, and as a result, the intermediate layer and the organic semiconductor layer can be formed.
In particular, when the organic thin film transistor material contains a binder, the phase separation is more likely to proceed. In addition, the negative expansion material is generally localized at a high concentration on the lower side of the coating together with the binder.

From the viewpoint of imparting coatability, crystallinity of the organic semiconductor layer, phase separation and the like, it is preferable to contain a solvent in the material for an organic thin film transistor. The content of the solvent is preferably 70% by mass or more, more preferably 80% by mass or more, and more preferably 90% by mass or more based on the total mass of the organic thin film transistor material.
Examples of the solvent include the following.
As a solvent, an organic solvent, water, and these mixed solvents are mentioned, for example.
Examples of the organic solvent include hydrocarbon solvents such as hexane, octane, decane, toluene, xylene, mesitylene, ethylbenzene, tetralin, decalin and 1-methylnaphthalene, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and dichloromethane , Halogenated hydrocarbon solvents such as chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene and chlorotoluene, ester solvents such as ethyl acetate, butyl acetate and amyl acetate, methanol, propanol, butanol, pentanol Alcohol solvents such as hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, ethylene glycol etc., dibutyl ether, tetrahydric acid Ether solvents such as rofuran, dioxane, anisole, amide / imide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1-methyl-2-imidazolidinone, dimethylsulfone Examples include sulfoxide solvents such as phoxide and the like, nitrile solvents such as acetonitrile and benzonitrile, and the like.

  The organic solvents may be used alone or in combination of two or more. As the organic solvent, toluene, xylene, mesitylene, tetralin, methyl ethyl ketone, cyclopentanone, dichloromethane, chloroform, chlorobenzene, dichlorobenzene, anisole, benzonitrile and the like are particularly preferable.

In the organic thin film transistor material, the content of the negative expansion material is preferably contained in an amount of 1 to 30% by mass with respect to the total solid content of the organic thin film transistor material, and further 5 to 20% by mass. preferable.
In the organic thin film transistor material, the content of the organic semiconductor compound is preferably 10 to 70% by mass, and more preferably 20 to 60% by mass, with respect to the total solid content of the organic thin film transistor material.
In the organic thin film transistor material, the content of the binder is preferably 10 to 70% by mass, and more preferably 20 to 60% by mass with respect to the total solid content of the organic thin film transistor material.
In addition, the above-mentioned surfactant having a glass transition temperature of 50 ° C. or more may be contained in the material for an organic thin film transistor, and in this case, the content of the above surfactant is the total solid content of the material for an organic thin film transistor The amount is preferably 0.01 to 30% by mass, and more preferably 0.01 to 10% by mass.

A known method (for example, a bar coating method, a spin coating method, a knife coating method, a doctor blade method) can be adopted as a method of applying the material for the organic thin film transistor.
The application conditions are not particularly limited. It may be applied at around room temperature (25 ° C.), or may be applied in a heated state to increase the solubility of the organic semiconductor compound in the application solvent. The coating temperature is preferably 15 to 150 ° C., more preferably 15 to 100 ° C., still more preferably 15 to 50 ° C., and particularly preferably around room temperature (20 to 30 ° C.).
In the spin coating method, the number of rotations is preferably 100 to 3,000 rpm.

  In addition, you may dry a coating film after application as needed. The drying conditions may be any conditions that can volatilize and remove the solvent, and examples thereof include methods such as room temperature standing, heating drying, air drying, and reduced pressure drying.

In addition, when separately forming an intermediate layer containing a negative expansion material and a binder supporting a negative expansion material before or after forming the organic semiconductor layer, a composition containing at least an organic semiconductor compound, a binder, and a negative It is possible to form using the material set for organic thin film transistors provided with the composition which contains an expansion material at least. Specifically, for example, after a composition containing an organic semiconductor compound and a solvent is applied on a predetermined substrate to form an organic semiconductor layer, a composition containing a binder, a negative expansion material and a solvent is further added as an organic semiconductor A method of forming an intermediate layer by coating on a layer, or a composition containing a binder, a negative expansion material and a solvent is coated on a predetermined substrate to form an intermediate layer, and then an organic semiconductor compound and a solvent are further added. The method of apply | coating the composition containing on an intermediate | middle layer and forming an organic-semiconductor layer is mentioned. When the above-mentioned surfactant having a glass transition temperature of 50 ° C. or more is blended, it may be blended in either of the organic semiconductor layer and the intermediate layer.
As the binder for forming the intermediate layer, ethylene propylene rubber, polyurethane, polyisoprene, polyisobutylene, silicone rubber and the like can be used besides the above-mentioned binder polymer.
The method of applying these compositions is as described above, and after the application of each composition, a drying treatment may be carried out as necessary.
When the organic semiconductor layer and the intermediate layer are separately formed, or when the negative expansion material is contained in the gate insulating layer according to the second embodiment described later and the intermediate layer is not formed, the organic semiconductor layer is formed. It is preferable to blend a binder with the organic semiconductor compound from the viewpoint of coating property and the like. As a binder, the above-mentioned binder used for the material for organic thin-film transistors can be used.
In the present specification, the organic semiconductor layer and the intermediate layer are separately formed, and a binder is used to form the organic semiconductor layer, and the binder forms a layer independently of the organic semiconductor layer by the phase separation phenomenon. If it is formed continuously (adjacent) to the intermediate layer, this binder is regarded as the binder of the intermediate layer.

<< second aspect >>
Hereinafter, each configuration of the second aspect shown in FIG. 1 (B) described above and a method for manufacturing the same will be described in detail.
The OTFT of the second embodiment is obtained by arranging the gate electrode 5, the gate insulating layer 12, the source electrode 3 and the drain electrode 4, and the organic semiconductor layer 1 in this order on the substrate 6. The second aspect has the same configuration as that of the first aspect except that the negative expansion material in the gate insulating layer is contained, and therefore the description is omitted in the following, and mainly the gate insulating layer 12 will be described in detail.

The gate insulating layer in the second aspect includes a negative expansion material.
The definition of the negative expansion material is as described above.
As described above, the gate insulating layer contains an insulating material (for example, an organic material such as an organic polymer, or an inorganic material such as an inorganic oxide).

  In the gate insulating layer in the second aspect, the content of the negative expansion material is preferably 1 to 50% by mass, and more preferably 5 to 40% by mass with respect to the total solid content. More preferably, it is contained at 10 to 30% by mass. By being contained in the said range, the thermal stress to an organic-semiconductor layer can be suppressed, and the crack generation of an organic-semiconductor layer is suppressed more effectively.

  The thickness of the gate insulating layer 12 in the second embodiment is preferably 0.01 to 100 μm, more preferably 0.05 to 5 μm, and particularly preferably 0.1 to 1 μm. By setting it as the said range, the high ON-OFF ratio and the crack generation inhibitory effect can be acquired as an electrical property.

  In the second aspect, the organic semiconductor layer adjacent to the gate insulating layer preferably contains a surfactant having a glass transition temperature of 50 ° C. or more. By containing the above surfactant in the organic semiconductor layer, it is possible to further improve the film thickness uniformity without generating a crack and without lowering the carrier mobility and the maintenance rate thereof under high temperature and high humidity conditions. Can.

The method for producing the gate insulating layer in the second embodiment is not particularly limited, and, for example, a composition for forming a gate insulating layer containing an insulating material and a negative expansion material is applied on a predetermined substrate, and as necessary And drying methods.
Note that the composition for forming a gate insulating layer may contain the above-described solvent.

<Application of OTFT>
The OTFT of the present invention is preferably mounted on a display panel and used. As a display panel, a liquid crystal panel, an organic electroluminescent panel, an electronic paper panel etc. are mentioned, for example.

  Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts used, proportions, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be construed as limited by the following examples.

Example 1
<Preparation of a composition for forming an organic semiconductor layer>
The composition for forming an organic semiconductor layer of Example 1 by mixing and stirring an organic semiconductor compound (OSC-1) and a binder (polystyrene of Mw = 500,000) so that the solid content mass ratio is 1: 1. Was prepared. The composition for organic-semiconductor layer formation was prepared as a 0.5 mass% solid concentration solution which uses toluene as a solvent.

  In addition, the various polymers used by the present Example are standard polystyrene conversion values measured by GPC (gel permeation chromatography) method. The measurement of weight-average molecular weight and number-average molecular weight by GPC is carried out by dissolving the polymer in THF (Tetrahydrofuran) and using high-speed GPC (HLC-8220GPC, manufactured by Tosoh Corporation) as a column, TSKgel Super HZ4000 (manufactured by TOSOH, 4.6 mmI) D. x 15 cm), using THF as eluent.

<Preparation of composition for forming gate insulating layer (containing negative expansion material)>
30% by mass of a polyimide solution (7% solution, Sun Ever SE-130B manufactured by Nissan Chemical Industries, Ltd.) as a binder and zirconium tungstate as a negative expansion material (the following synthetic product; average particle size 200 nm, aspect ratio 10, silane coupling surface treatment The composition for forming a gate insulating layer (containing a negative expansion material) was prepared by dissolving 0.24% by mass of A) in anisole which is a solvent, and the composition for forming a gate insulating layer of Example 1 was obtained.
As the zirconium tungstate, one synthesized according to the following procedure was used with reference to the document (ACS Appl. Mater. Interfaces, 2013, 5 (19), pp 9478-9487).

(Preparation of zirconium tungstate)
And _{0.08M ZrO (ClO 4) 2 ·} xH 2 O, in _{0.10M Na 2 WO 4 · 2H 2} O with 7M HCl, and the reaction was performed for 12 hours at 160 ° C. After the reaction, the white precipitate was taken out, washed with ion-exchanged water, and the precipitate was repeated six times with a centrifuge. After drying at 75 ° C. for 24 hours, it was ground in a mortar. Finally, the white powder was sintered at 600 degrees for 30 minutes to obtain zirconium tungstate nanoparticles.
Furthermore, 5 g of nanoparticles were added to 50 ml of absolute ethanol and stirred, and then ultrasonic waves were applied for 10 minutes. 10 g of a 10% ethanol solution of hexyltrimethoxysilane (silane coupling agent, manufactured by Shin-Etsu Silicone Co., Ltd.) adjusted to pH 4 was added and reacted at 60 ° C. for 2 hours. After repeating precipitation and absolute ethanol washing three times by centrifugation, it was dried in a vacuum oven at 60 ° C. for 24 hours to obtain surface-treated zirconium tungstate nanoparticles.

<Manufacture of organic thin film transistor (bottom gate, bottom contact structure)>
By using the composition for forming an organic semiconductor layer and the composition for forming a gate insulating layer obtained as described above, an organic thin film transistor (Example 1) having a bottom gate and bottom contact structure shown in FIG. The procedure was

A 1 mm thick doped silicon substrate (which also serves as the gate electrode 5) was used as the substrate 6, and the gate insulating layer 12 was formed thereon.
The gate insulating layer 12 was formed as a film with a thickness of 0.7 μm by applying the composition for forming a gate insulating layer (containing a negative expansion material) on the substrate 6 and drying it.

  Next, as shown in FIG. 1B, a silver electrode (thickness 150 nm, gate width W = 100 μm, gate length L = 100 μm) arranged in a comb shape is used as a source electrode 3 and a drain electrode 4 as a mask. It was formed by vacuum evaporation using.

Next, the composition for forming an organic semiconductor layer was applied by spin coating (rotation number 800 rpm) at 25 ° C. so as to cover the gate insulating layer 12, the source electrode 3 and the drain electrode 4. Then, the organic semiconductor layer 1 was formed into a film by heating on a hot plate at 60 ° C. for 120 minutes.
Thus, the organic semiconductor layer 1 having a thickness of 300 nm was formed, and the organic thin film transistor (bottom gate and bottom contact type) of Example 1 was obtained.

[Examples 2 and 3]
Organic thin film transistors of Examples 2 and 3 were produced by the same method as Example 1 except that the compounding amount of the negative expansion material contained in the composition for forming a gate insulating layer was changed as shown in Table 1.

[Examples 4, 5, 6]
Except that the negative expansion material contained in the composition for forming a gate insulating layer is changed from zirconium tungstate to zirconium phosphate (ZrO) ₂ P ₂ O ₇ (average particle diameter 80 nm, aspect ratio 3.8, manufactured by Toagosei Co., Ltd.) The organic thin film transistors of Examples 4, 5 and 6 were produced in the same manner as in Examples 1, 2 and 3, respectively.

[Examples 7, 8, 9]
The same as Examples 1, 2 and 3 except that the negative expansion material contained in the composition for forming a gate insulating layer is changed from zirconium tungstate to silica (average particle diameter 60 nm, aspect ratio 1.0, manufactured by Showa Denko KK) The organic thin film transistors of Examples 7, 8 and 9 were produced by the method of the above.

[Examples 10, 11, 12]
Examples 10, 11, and 12 are respectively the same as Examples 1, 2 and 3 except that the organic semiconductor compound contained in the composition for forming an organic semiconductor layer is changed from OSC-1 to OSC-2 of the following structure. Twelve organic thin film transistors were fabricated.

[Example 13]
Preparation of Organic Thin Film Transistor Material 1
0.5% by mass of an organic semiconductor compound (OSC-3 shown below), 0.5% by mass of polystyrene (Mw = 500,000) as a binder, zirconium tungstate as a negative expansion material (synthetic product; A material 1 for an organic thin film transistor is produced by dissolving an average particle diameter: 200 nm, an aspect ratio: 10, and a silane coupling surface treatment of 0.056% by mass in anisole which is a solvent. It was adjacent to the organic semiconductor layer (organic semiconductor film) and the organic semiconductor layer, and was used for formation of the intermediate layer containing a negative expansion material.
The material for an organic thin film transistor 1 causes a phase separation of components when deposited on a predetermined base material, and an organic semiconductor layer which is a crystal layer of an organic semiconductor compound and a polystyrene layer containing a negative expansion material in the lower layer And form.

<Preparation of composition for forming gate insulating layer>
A composition for forming a gate insulating layer (without a negative expansion material) was prepared with the following composition, and used to form the gate insulating layer 2 of the organic thin film transistor of Example 13.
6.3 g of poly (4-vinylphenol) (manufactured by Nippon Soda Co., Ltd., trade name: VP-8000, Mn 11000, degree of dispersion 1.1) and 2,2-bis (3,5-dihydroxymethyl- as a crosslinking agent 2.7 g of 4-hydroxy) propane was dissolved in a mixed solvent of 91 g of 1-butanol / ethanol = 1/1 at room temperature. The solution was filtered with a membrane filter of 0.2 μm in diameter made of PTFE. To the obtained filtrate was added 0.18 g of diphenyliodonium hexafluorophosphate salt as an acid catalyst, and this was used as a composition for forming a gate insulating layer (without a negative expansion material).

<Manufacture of organic thin film transistor (bottom gate, bottom contact structure)>
Using the material 1 for an organic thin film transistor obtained as described above and the composition for forming a gate insulating layer, the organic thin film transistor (Example 13) of the bottom gate / bottom contact structure shown in FIG. Made in

A 1 mm thick doped silicon substrate (also serving as the gate electrode 5) was used as the substrate 6, and the gate insulating layer 2 was formed thereon.
The gate insulating layer 2 is formed by first applying a composition for forming a gate insulating layer on the substrate 6, drying it to form a film, and then heating to 100 ° C. to form a crosslinked structure. It was a 7 μm membrane.

  Next, as shown in FIG. 1A, an electrode (thickness 150 nm, gate width W = 100 μm, gate length L = 100 μm) made of silver arranged in a comb shape as a source electrode 3 and a drain electrode 4 is masked. It was formed by vacuum evaporation using.

Next, the organic thin film transistor material 1 was applied by spin coating (rotation number 800 rpm) at 25 ° C. so as to cover the gate insulating layer 2, the source electrode 3 and the drain electrode 4 to form a coating film. In the coating, components are separated after film formation, and negative expansion occurs in the organic semiconductor layer 1 which is a crystal layer of the organic semiconductor compound and the lower layer adjacent thereto (that is, the interface region between the gate insulating layer 2 and the organic semiconductor layer 1). A polystyrene layer (intermediate layer) 7 containing the material was formed.
Thus, an organic semiconductor layer 1 with a thickness of 300 nm and an intermediate layer 7 with a thickness of 120 nm were formed to obtain an organic thin film transistor (bottom gate / bottom contact type) of Example 13.

[Examples 14 and 15]
The organic thin film transistors of Examples 14 and 15 were produced in the same manner as in Example 13 except that the compounding amount of the negative expansion material contained in the organic thin film transistor material 1 was changed as shown in Table 1.

[Examples 16, 17, 18]
Organic thin film transistors of Examples 16, 17 and 18 were produced in the same manner as in Examples 1, 2 and 3, except that the composition for forming an organic semiconductor layer was changed to the following composition.

<Preparation of composition for forming an organic semiconductor layer (without negative expansion material, with surfactant)>
0.5% by mass of an organic semiconductor compound (OSC-1), 0.5% by mass of a binder (polystyrene with Mw = 500,000), and a surfactant (PMMA-b-PDMS: co-polymerization of polymethyl methacrylate and polydimethylsiloxane) A composition for forming an organic semiconductor layer was prepared by dissolving 0.025 mass% of a polymer (manufactured by Polymer Sorce, weight average molecular weight 60,000 glass transition temperature 100 ° C.) in anisole as a solvent.

[Examples 19, 20, 21]
The surfactant contained in the composition for forming an organic semiconductor layer of Examples 16, 17 and 18 was changed from PMMA-b-PDMS to BYK-323 (silicon-based surface conditioner (manufactured by Bick Chemie Japan Ltd.), glass transition temperature It changed into 20 degrees C or less (liquid at normal temperature normal pressure), TFT structure was changed from bottom gate * bottom contact structure to top gate * top contact structure, and the organic thin-film transistor of Example 19, 20, 21 was produced, respectively.
Hereinafter, the manufacturing procedure of the organic thin-film transistor of top gate top contact structure is explained in full detail.

An organic semiconductor layer composition obtained as described above was spin-coated at 25 ° C. (rotation speed: 1000 rpm) using a 1 mm thick doped silicon substrate (also serving as the gate electrode 5) as the substrate 6 The organic semiconductor layer 1 was formed to have a thickness of 300 nm.
Next, as shown in FIG. 2C, a silver electrode (thickness 150 nm, gate width W = 100 μm, gate length L = 100 μm) arranged in a comb shape is used as a source electrode 3 and a drain electrode 4 as a mask. It was formed by vacuum evaporation using.
Then, the gate insulating film composition (containing a negative expansion material) obtained above is applied by spin coating (rotation speed 800 rpm) at 25 ° C. so as to cover the organic semiconductor layer 1, the source electrode 3 and the drain electrode 4. , Coating film was formed. Furthermore, an electrode (thickness 50 nm, 100 μm) made of gold was formed as a gate electrode by vacuum evaporation using a mask. Thus, organic thin film transistors (bottom gate and bottom contact type) of Examples 19 to 21 were obtained.

[Examples 22 to 24]
Example 1 except that the composition for forming an organic semiconductor layer was changed to the following composition and film forming method, and the composition for forming a gate insulating layer was changed to the one used in Example 13 (without negative expansion material) The organic thin-film transistor of Examples 22-24 was produced by the method similar to.

Preparation of Organic Thin Film Transistor Material 2
0.5% by mass of an organic semiconductor compound (OSC-1), 0.5% by mass of polystyrene (Mw = 500,000) as a binder, zirconium tungstate as a negative expansion material (synthetic product (described above); average Particle size: 200 nm, aspect ratio: 10, silane coupling surface treatment: 0.056% by mass, surfactant (PMMA-b-PDMS: copolymer of polymethyl methacrylate and polydimethylsiloxane (manufactured by Polymer soruce) A material 2 for an organic thin film transistor is produced by dissolving 0.025 mass% of a weight average molecular weight of 60,000 glass transition temperature 100 ° C.) in a solvent, and an organic semiconductor layer (organic semiconductor film of Example 22). And an organic semiconductor layer and used to form an intermediate layer containing a negative expansion material.

<The film-forming method of the material 2 for organic thin-film transistors>
The material for an organic thin film transistor was applied by spin coating (rotation number 800 rpm) at 25 ° C. so as to cover the gate insulating layer 2, the source electrode 3 and the drain electrode 4 to form a coating film. In the coating, components are separated after film formation, and negative expansion occurs in the organic semiconductor layer 1 which is a crystal layer of the organic semiconductor compound and the lower layer adjacent thereto (that is, the interface region between the gate insulating layer 2 and the organic semiconductor layer 1). A polystyrene layer (intermediate layer) 7 containing the material was formed.
Thus, the organic semiconductor layer 1 with a thickness of 300 nm and the intermediate layer 7 with a thickness of 120 nm were formed.

[Example 25]
An organic thin film transistor of Example 25 was produced in the same manner as in Example 1 except that the composition for forming an organic semiconductor layer was changed to the same organic thin film transistor material 2 and the film forming method as in Example 22.

Comparative Example 1
<Manufacture of organic thin film transistor (bottom gate, bottom contact structure)>
Using the same composition for forming an organic semiconductor layer as in Example 1 and the same composition for forming a gate insulating layer as in Example 13, an organic thin film transistor having a bottom gate and bottom contact structure shown in FIG. 1) was made according to the following procedure.
The organic thin film transistor of Comparative Example 1 has a configuration in which the negative expansion material is not contained in any layer.

A 1 mm thick doped silicon substrate (also serving as the gate electrode 5) was used as the substrate 6, and the gate insulating layer 2 was formed thereon.
The gate insulating layer 2 is formed by first applying a composition for forming a gate insulating layer on the substrate 6, drying it to form a film, and then heating to 100 ° C. to form a crosslinked structure. It was a 7 μm membrane.

  Next, as shown in FIG. 1A, an electrode (thickness 150 nm, gate width W = 100 μm, gate length L = 100 μm) made of silver arranged in a comb shape as a source electrode 3 and a drain electrode 4 is masked. It was formed by vacuum evaporation using.

Next, the composition for forming an organic semiconductor layer was applied by spin coating (rotation number 800 rpm) at 25 ° C. so as to cover the gate insulating layer 2, the source electrode 3 and the drain electrode 4. Then, the organic semiconductor layer 1 was formed into a film by heating on a hot plate at 60 ° C. for 120 minutes.
Thus, the organic semiconductor layer 1 having a thickness of 300 nm was formed, and the organic thin film transistor (bottom gate / bottom contact type) of Comparative Example 1 was obtained.

Comparative Example 2
An organic thin film transistor of Comparative Example 2 was produced in the same manner as in Example 1 except that the composition for forming a gate insulating layer was changed to one used in Example 13 (without negative expansion material).

  In addition, in preparation of the composition for organic-semiconductor layer formation of Examples 1-25 and Comparative Examples 1 and 2, when an organic-semiconductor compound is dissolved, it stirs, heating about 50 degreeC as needed. Then, each component was dissolved.

<Evaluation test>
The performance of each obtained organic thin film transistor was examined by evaluating the presence or absence of a crack, carrier mobility, temporal stability under high temperature and high humidity conditions, and film thickness uniformity by the following method.

(Evaluation of crack occurrence)
After heat was applied to the produced organic thin film transistor under the condition of 150 ° C. for 1 hour, the occurrence of the crack of the organic semiconductor layer was evaluated visually. When a crack occurred "NG", when a crack did not occur, it was "OK".
The obtained results are shown in the following table.

(Carrier mobility evaluation)
The voltage of -40V between the source electrode 3 a drain electrode 4 of each organic thin film transistor manufactured by applying, varied between the gate voltage + 10V to-60V, the carrier mobility using the following equation representing the drain current I _d The μ was calculated.
I _d = (w / 2 L) μC _i (V _g −V _th ) ²
In the equation, L represents a gate length, w represents a gate width, C _i represents a capacity per unit area of the gate insulating layer 2, V _g represents a gate voltage, and V _th represents a threshold voltage.
The carrier mobility μ is preferably as high as possible, and is preferably 0.5 or more for practical use.
The obtained results are shown in the following table.

(Temperature stability under high temperature and high humidity)
After storing each manufactured each organic thin-film transistor for 24 hours under 70 degreeC and humidity 80%, carrier mobility was measured by the method similar to said "carrier mobility evaluation." From the measurement results, the carrier mobility maintenance rate (the following formula) was evaluated in the following five levels, and used as an indicator of temporal stability under high temperature and high humidity. The larger the value, the higher the stability over time under high temperature and high humidity, and for practical use it needs to be "B" or more, and more preferably "A" or more.
Carrier mobility retention after storage under high temperature and high humidity (%) = {Carrier mobility (after storage under high temperature and high humidity) / Carrier mobility (before storage under high temperature and high humidity) × 100
"A": 90% or more "B": 75% or more and less than 90% "C": 50% or more and less than 75% "D": 25% or more and less than 50% "E": less than 25% It shows in the table.

(Film uniformity evaluation)
After coating, the cross section of the device was cut out by FIB (Focused Ion Beam System (Ga ion beam)), and SEM observation was performed to evaluate uniformity in the film thickness direction. From the measurement results, the film thickness uniformity evaluation was evaluated in the following three stages, and used as an index.
"A": The film thickness of each layer can be formed within ± 50% of the average film thickness "B": The film can be formed without inter-layer mixing "C": inter-layer mixing occurs

In Table 1, the “addition amount (mass%) of negative expansion material” in the gate insulating layer column represents the content of the negative expansion material with respect to the total solid content of the layer.
Moreover, "the addition amount (mass%) of surfactant" in an organic-semiconductor layer / intermediate | middle layer column represents content of surfactant with respect to the organic-semiconductor composition whole quantity.
Further, “organic semiconductor compound / binder (solid content concentration ratio)” in the organic semiconductor layer / intermediate layer column represents the solid content concentration ratio of the organic semiconductor compound to the binder contained in the composition for forming an organic semiconductor layer.
Moreover, "the addition amount (mass%) of a negative expansion material" in an organic-semiconductor layer / middle layer column represents content of the negative expansion material with respect to middle layer whole solid content.

  As shown in Table 1, in the organic thin film transistor of the present invention, it was confirmed that no crack occurs in the organic semiconductor layer even after the heating process.

  Further, in comparison with Examples 1 to 9 in which the negative expansion material is introduced into the gate insulating layer, in the case of using zirconium tungstate as the negative expansion material, the carrier mobility and the maintenance rate thereof under high temperature and high humidity conditions are It was confirmed to be better. In general, when a negative expansion material is included in the gate insulating layer, the surface free energy is increased, and the coatability of the organic semiconductor layer formed in the upper layer tends to be lowered to lower the carrier mobility of the organic thin film transistor It is assumed. However, in the case of using zirconium tungstate in particular, no influence on the carrier mobility was observed. Furthermore, the gate insulating layer is stably maintained without thermal expansion for a long time under high temperature and high humidity conditions, so that the maintenance rate under high temperature and high humidity conditions is also excellent.

  Moreover, when Examples 1-3 and Examples 10-12 are contrasted respectively, it was confirmed that carrier mobility is more excellent when a low molecular weight type organic semiconductor compound is used.

Further, as apparent from the comparison of Examples 1 to 3 and Examples 13 to 15 and Examples 22 to 24, negative expansion materials and a glass transition temperature of 50 ° C. or more are obtained in the preparation of the organic semiconductor compound and the intermediate layer. By using together with a surfactant (preferably, a block copolymer containing a polymer chain having a glass transition temperature of 50.degree. C. or higher), no crack is generated, and carrier mobility and its high temperature and high humidity condition It was confirmed that the film thickness uniformity was further improved without reducing the maintenance rate at
Furthermore, as apparent from Examples 16 to 18, even when a negative expansion material is added to the gate insulating layer, a surfactant (preferably glass) having a glass transition temperature of 50 ° C. or higher in the organic semiconductor layer It was confirmed that the above-mentioned effect can be obtained by adding a block copolymer containing a polymer chain having a transition temperature of 50 ° C. or more.
On the other hand, as apparent from the comparison of Examples 1 to 3 and 19 to 21, when the surfactant having a glass transition temperature of less than 50 ° C. is used, the film thickness uniformity is further improved, but the high temperature The maintenance rate under high humidity conditions decreased.
As Comparative Example 2 shows, a surfactant having a glass transition temperature of 50 ° C. or higher (preferably, a block copolymer containing a polymer chain having a glass transition temperature of 50 ° C. or higher) without using a negative expansion material. As compared to Comparative Example 1 in which only the negative expansion material and the surfactant were not used, more cracks were generated and the carrier mobility (before heating) was also increased. It gets lower. That is, the above-mentioned surfactant having a glass transition temperature of 50 ° C. or higher does not cause a crack for the first time when it is used as a negative expansion material, and the carrier mobility and the maintenance rate thereof under high temperature and high humidity conditions The film thickness uniformity can be further improved without lowering the

  On the other hand, since the organic thin film transistor of the comparative example does not contain the negative expansion material in the peripheral portion of the organic semiconductor layer, the organic semiconductor layer was cracked after the heating process.

[Examples 26, 27, 28]
In Examples 13, 14 and 15 in which the organic semiconductor layer and the intermediate layer were produced using the organic thin film transistor material, a negative expansion material is included on the gate insulating layer using the composition for forming the intermediate layer instead of the organic thin film transistor material. An organic thin film transistor of each of Examples 26, 27 and 28 was produced by the same method except that an intermediate layer was formed, and an organic semiconductor layer was separately provided on the upper layer thereof using the composition for forming an organic semiconductor layer.
Specifically, an intermediate layer is formed by dissolving 1 mass% of zirconium tungstate (average particle diameter 200 nm, aspect ratio 10) and 0.5 mass% of ethylene propylene rubber (EP22 manufactured by JSR) as a binder in anisole A composition was prepared and applied onto the gate insulating layer 2 by spin coating to form a 100 nm thick layer. An organic semiconductor layer (thickness 300 nm) was formed thereon using the same composition for forming an organic semiconductor layer as in Example 1 above.
The various performances (presence or absence of a crack, carrier mobility (before heating), maintenance rate under high temperature and high humidity, film thickness uniformity) of the obtained organic thin film transistor were evaluated and found to be equivalent to Examples 13, 14 and 15. It was confirmed that the performance of

  Reference Signs List 1 organic semiconductor layer, 2, 12 gate insulating layer, 3 source electrode, 4 drain electrode, 5 gate electrode, 6 substrate, 7 intermediate layer

Claims (10)

A gate electrode, an organic semiconductor layer, a gate insulating layer provided between the gate electrode and the organic semiconductor layer, and a source electrode provided in contact with the organic semiconductor layer and connected via the organic semiconductor layer An organic thin film transistor having a drain electrode and a drain electrode,
An organic thin film transistor comprising a negative expansion material in the gate insulating layer. The organic thin film transistor according to claim 1 , wherein the negative expansion material has an aspect ratio of 2 to 50. A gate electrode, an organic semiconductor layer, a gate insulating layer provided between the gate electrode and the organic semiconductor layer, and a source electrode provided in contact with the organic semiconductor layer and connected via the organic semiconductor layer An organic thin film transistor having a drain electrode and a drain electrode,
An organic thin film transistor comprising a negative expansion material having an aspect ratio of 2 to 50 in an intermediate layer disposed adjacent to the organic semiconductor layer . The organic thin-film transistor of any one of Claims 1-3 whose average particle diameter of the said negative expansion material is 10-1000 nm. The organic thin film transistor according to any one of claims 1 to 4 , wherein the negative expansion material is zirconium tungstate. The organic thin film transistor according to any one of claims 1 to 5 , wherein the gate insulating layer is formed of an organic material. The organic thin film transistor according to any one of claims 1 to 6 , wherein the organic semiconductor layer contains a surfactant having a glass transition temperature of 50 ° C or higher.   A material for an organic thin film transistor, comprising at least an organic semiconductor compound, a binder and a negative expansion material. A material set for an organic thin film transistor, comprising: a composition containing at least an organic semiconductor compound; and a composition containing at least a binder and a negative expansion material having an aspect ratio of 2 to 50 . A gate electrode, an organic semiconductor layer, a gate insulating layer provided between the gate electrode and the organic semiconductor layer, and a source electrode provided in contact with the organic semiconductor layer and connected via the organic semiconductor layer A method of manufacturing an organic thin film transistor, comprising:
A material for an organic thin film transistor according to claim 8 or a set of a material for an organic thin film transistor according to claim 9 , formed adjacent to the organic semiconductor layer and the organic semiconductor layer, and having a binder and an aspect ratio of 2 A method of manufacturing an organic thin film transistor, comprising forming an intermediate layer containing 50 negative expansion materials.