阅读说明：本技术 有机半导体元件、有机半导体组合物、有机半导体膜、有机半导体膜的制造方法及用于这些的聚合物 (Organic semiconductor element, organic semiconductor composition, organic semiconductor film, method for producing organic semiconductor film, and polymer for use in these ) 是由 谷征夫 白兼研史 渡边哲也 冈本敏宏 竹谷纯一 于 2018-12-27 设计创作，主要内容包括：本发明提供一种具备含有特定的聚合物的有机半导体层的有机薄膜晶体管元件、优选作为该有机半导体层的有机半导体膜及其制造方法以及优选作为该有机半导体膜的构成材料的聚合物及组合物,该特定的聚合物具有包含特定的式所表示的结构的重复单元。(The present invention provides an organic thin film transistor element having an organic semiconductor layer containing a specific polymer having a repeating unit including a structure represented by a specific formula, an organic semiconductor film preferable as the organic semiconductor layer, a method for producing the same, and a polymer and a composition preferable as a constituent material of the organic semiconductor film.)

1. An organic semiconductor element comprising an organic semiconductor layer containing a polymer having a repeating unit having a structure represented by the following formula (1),

[ chemical formula 1]

In the formula (1), A¹¹And A¹²represents-O-, -N (R)^N) -or-P (R)^N)-；B¹¹～B¹⁸represents-N or-C (R)^M) At least one is-N ═ N; r^NAnd R^MAt least one of them represents a single bond or a linking group, and the others represent a hydrogen atom or a substituent; x¹¹～X¹⁴Represents an oxygen atom or a sulfur atom;

wherein there is no case where the polymer contains a repeating unit having an aliphatic 7-membered ring structure.

2. The organic semiconductor element according to claim 1,

the polymer has as repeating units: a group composed of a 5-or 6-membered monocyclic ring, a group composed of a condensed ring in which at least 2 monocyclic rings are condensed, an ethenylene group, an ethynylene group, or a group in which these groups are combined.

3. The organic semiconductor element according to claim 1 or 2,

the repeating unit having a structure represented by the formula (1) is a repeating unit having a structure represented by the following formula (2),

[ chemical formula 2]

In the formula (2), A¹¹And A¹²represents-O-, -N (R)^N) -or-P (R)^N)-；

R^NAnd R²¹～R²⁶At least one of them represents a single bond or a linking group, and the others represent a hydrogen atom or a substituent; x¹¹～X¹⁴With X of said formula (1)¹¹～X¹⁴The same is true.

4. The organic semiconductor element according to any one of claims 1 to 3,

the repeating unit containing the structure represented by the formula (1) is a repeating unit containing the structure represented by the following formula (3-1) or formula (3-2),

[ chemical formula 3]

In the formulae (3-1) and (3-2), A²¹And A²²represents-O-, -N (R)^N) -or-P (R)^N)-；R^NAnd R²¹～R²⁶Represents a hydrogen atom or a substituent; x²¹～X²⁴With X of said formula (1)¹¹～X¹⁴The same; l represents a single bond or a linking group; denotes the junction site.

5. The organic semiconductor element according to any one of claims 1 to 4, which is an organic thin film transistor element.

6. An organic semiconductor composition comprising a polymer and a solvent, wherein the polymer has a repeating unit having a structure represented by the following formula (1),

[ chemical formula 4]

In the formula (1), A¹¹And A¹²represents-O-, -N (R)^N) -or-P (R)^N)-；B¹¹～B¹⁸represents-N or-C (R)^M) At least one is-N ═ N; r^NAnd R^MAt least one of them represents a single bond or a linking group, and the others represent a hydrogen atom or a substituent; x¹¹～X¹⁴Represents an oxygen atom or a sulfur atom;

wherein there is no case where the polymer contains a repeating unit having an aliphatic 7-membered ring structure.

7. An organic semiconductor film comprising a polymer having a repeating unit comprising a structure represented by the following formula (1),

[ chemical formula 5]

In the formula (1), A¹¹And A¹²represents-O-, -N (R)^N) -or-P (R)^N)-；B¹¹～B¹⁸represents-N or-C (R)^M) At least one is-N ═ N; r^NAnd R^MAt least one of them represents a single bond or a linking group, and the others represent a hydrogen atom or a substituent; x¹¹～X¹⁴Represents an oxygen atom or a sulfur atom;

wherein there is no case where the polymer contains a repeating unit having an aliphatic 7-membered ring structure.

8. A method of manufacturing an organic semiconductor film, comprising: a step of forming an organic semiconductor film by applying or printing the organic semiconductor composition according to claim 6 on a substrate and drying the composition.

9. A polymer having a repeating unit comprising a structure represented by the following formula (1),

[ chemical formula 6]

In the formula (1), A¹¹And A¹²represents-O-, -N (R)^N) -or-P (R)^N)-；B¹¹～B¹⁸represents-N or-C (R)^M) At least one is-N ═ N; r^NAnd R^MAt least one of them represents a single bond or a linking group, and the others represent a hydrogen atom or a substituent; x¹¹～X¹⁴Represents an oxygen atom or a sulfur atom;

wherein there is no case where the polymer contains a repeating unit having an aliphatic 7-membered ring structure.

10. The polymer of claim 9 having as repeating units: a group composed of a 5-or 6-membered monocyclic ring, a group composed of a condensed ring in which at least 2 monocyclic rings are condensed, an ethenylene group, an ethynylene group, or a group in which these groups are combined.

11. The polymer of claim 9 or 10,

the repeating unit having a structure represented by the formula (1) is a repeating unit having a structure represented by the following formula (2),

[ chemical formula 7]

In the formula (2), A¹¹And A¹²represents-O-, -N (R)^N) -or-P (R)^N)-；

R^NAnd R²¹～R²⁶At least one of them represents a single bond or a linking group, and the others represent a hydrogen atom or a substituent; x¹¹～X¹⁴With X of said formula (1)¹¹～X¹⁴The same is true.

12. The polymer of any one of claims 9 to 11,

the repeating unit containing the structure represented by the formula (1) is a repeating unit containing the structure represented by the following formula (3-1) or formula (3-2),

[ chemical formula 8]

In the formulae (3-1) and (3-2), A²¹And A²²represents-O-, -N (R)^N) -or-P (R)^N)-；R^NAnd R²¹～R²⁶Represents a hydrogen atom or a substituent; x²¹～X²⁴With X of said formula (1)¹¹～X¹⁴The same; l represents a single bond or a linking group; denotes the junction site.

Technical Field

The present invention relates to an organic semiconductor element, an organic semiconductor composition, an organic semiconductor film, a method for producing an organic semiconductor film, and a polymer used for these.

Background

Semiconductor elements are used in devices using logic circuits such as displays such as liquid crystal displays and organic electroluminescence displays, RFID (radio frequency identification) and memories, and solar cells. Among them, an organic semiconductor element having an organic semiconductor film is advantageous over an inorganic semiconductor element having an inorganic semiconductor film because it can be reduced in weight and cost and is excellent in flexibility.

As the organic compound forming the organic semiconductor film, a compound having a repeating unit composed of a condensed ring structure containing a 5-membered monocyclic ring and an aliphatic 7-membered monocyclic ring as condensed rings (patent document 1) and a polymer having a repeating unit composed of a repeating unit containing a polycyclic moiety and a perylene bisimide structure (patent document 2) have been studied.

Prior art documents

Patent document

Patent document 1: japanese patent laid-open publication No. 2015-153780

Patent document 2: japanese Kohyo publication 2011-514913

Disclosure of Invention

Technical problem to be solved by the invention

The performance of the displays and the like has been rapidly improved, and improvement of semiconductor characteristics (for example, carrier mobility) is required for an organic semiconductor device mounted thereon. In order to cope with the demand for cost reduction and flexibility, it is also desired that the display device described above be stably driven and maintain the characteristics (durability) of the semiconductor characteristics in the atmosphere without providing a special protective layer or sealing layer.

However, in conventional organic semiconductor devices, including organic semiconductor devices using the compounds or polymers described in patent documents 1 and 2, the semiconductor characteristics tend to be greatly reduced in the atmosphere, and there is room for improvement in terms of both the semiconductor characteristics and the maintenance of the durability thereof.

The present invention provides an organic semiconductor device having excellent durability, which maintains desired semiconductor characteristics (e.g., high carrier mobility) even in the atmosphere. Another object of the present invention is to provide an organic semiconductor film which is preferable as an organic semiconductor layer in the organic semiconductor device, and a method for manufacturing the same. Another object of the present invention is to provide a polymer and a composition which are preferable as a constituent material of the organic semiconductor film.

Means for solving the technical problem

As a result of extensive studies, the present inventors have found that a specific polymer having a repeating unit having a structure represented by a specific formula (1) described later can be preferably used as an organic semiconductor in an organic semiconductor device; and an organic semiconductor film containing the polymer exhibits high carrier mobility and can suppress the decrease even in the atmosphere. The present invention has been completed based on these findings by further repeating the study.

The above object of the present invention is achieved by the following means.

< 1 > an organic semiconductor element comprising an organic semiconductor layer containing a polymer having a repeating unit comprising a structure represented by the following formula (1).

[ chemical formula 1]

In the formula (1), A¹¹And A¹²represents-O-, -N (R)^N) -or-P (R)^N)-。B¹¹～B¹⁸represents-N or-C (R)^M) At least one is-N ═ N. R^NAnd R^MAt least one of them represents a single bond or a linking group, and the others represent a hydrogen atom or a substituent. X¹¹～X¹⁴Represents an oxygen atom or a sulfur atom.

However, the above polymer does not contain a repeating unit having an aliphatic 7-membered ring structure.

< 2 > the organic semiconductor element as < 1 > wherein the polymer has, as a repeating unit, a group composed of a 5-or 6-membered monocyclic ring, a group composed of a condensed ring in which at least 2 of the above-mentioned monocyclic rings are condensed, an ethenylene group, an ethynylene group, or a group in which these groups are combined.

< 3 > the organic semiconductor element as < 1 > or < 2 >, wherein the repeating unit comprising the structure represented by formula (1) is a repeating unit comprising the structure represented by formula (2) below.

[ chemical formula 2]

In the formula (2), A¹¹And A¹²represents-O-, -N (R)^N) -or-P (R)^N)-。R^NAnd R²¹～R²⁶At least one of them represents a single bond or a linking group, and the others represent a hydrogen atom or a substituent. X¹¹～X¹⁴With X of the formula (1)¹¹～X¹⁴The same is true.

< 4 > the organic semiconductor element as defined in any one of < 1 > to < 3 >, wherein the repeating unit comprising the structure represented by formula (1) is a repeating unit comprising the structure represented by formula (3-1) or formula (3-2) below.

[ chemical formula 3]

In the formulae (3-1) and (3-2), A²¹And A²²represents-O-, -N (R)^N) -or-P (R)^N)-。R^NAnd R²¹～R²⁶Represents a hydrogen atom or a substituent. X²¹～X²⁴With X of the formula (1)¹¹～X¹⁴The same is true. L represents a single bond or a linking group. Denotes the junction site.

The organic semiconductor element described in any of < 5 > such as < 1 > to < 4 > is an organic thin film transistor element.

< 6 > an organic semiconductor composition comprising a polymer having a repeating unit comprising a structure represented by the following formula (1) and a solvent.

[ chemical formula 4]

In the formula (1), A¹¹And A¹²represents-O-, -N (R)^N) -or-P (R)^N)-。B¹¹～B¹⁸represents-N or-C (R)^M) At least one is-N ═ N. R^NAnd R^MAt least one of them represents a sheetA bond or a linking group, the remainder representing a hydrogen atom or a substituent. X¹¹～X¹⁴Represents an oxygen atom or a sulfur atom.

However, the above polymer does not contain a repeating unit having an aliphatic 7-membered ring structure.

< 7 > an organic semiconductor film comprising a polymer having a repeating unit comprising a structure represented by the following formula (1).

[ chemical formula 5]

In the formula (1), A¹¹And A¹²represents-O-, -N (R)^N) -or-P (R)^N)-。B¹¹～B¹⁸represents-N or-C (R)^M) At least one is-N ═ N. R^NAnd R^MAt least one of them represents a single bond or a linking group, and the others represent a hydrogen atom or a substituent. X¹¹～X¹⁴Represents an oxygen atom or a sulfur atom.

However, the above polymer does not contain a repeating unit having an aliphatic 7-membered ring structure.

< 8 > A method for producing an organic semiconductor film, which comprises a step of forming an organic semiconductor film by applying or printing the organic semiconductor composition < 6 > onto a substrate and drying the organic semiconductor composition.

< 9 > a polymer having a repeating unit comprising a structure represented by the formula (1).

[ chemical formula 6]

In the formula (1), A¹¹And A¹²represents-O-, -N (R)^N) -or-P (R)^N)-。B¹¹～B¹⁸represents-N or-C (R)^M) At least one is-N ═ N. R^NAnd R^MAt least one of them represents a single bond or a linking group, and the others represent a hydrogen atom or a substituent. X¹¹～X¹⁴Represents an oxygen atom or a sulfur atom.

However, the above polymer does not contain a repeating unit having an aliphatic 7-membered ring structure.

< 10 > the polymer according to < 9 > which has a group comprising a 5-or 6-membered monocyclic ring, a group comprising at least 2 condensed rings obtained by condensing the above-mentioned monocyclic rings, an ethenylene group, an ethynylene group or a combination of these groups as a repeating unit.

< 11 > the polymer as < 9 > or < 10 > wherein the repeating unit comprising the structure represented by the formula (1) is a repeating unit comprising the structure represented by the following formula (2).

[ chemical formula 7]

In the formula (2), A¹¹And A¹²represents-O-, -N (R)^N) -or-P (R)^N)-。

R^NAnd R²¹～R²⁶At least one of them represents a single bond or a linking group, and the others represent a hydrogen atom or a substituent. X¹¹～X¹⁴With X of the formula (1)¹¹～X¹⁴The same is true.

< 12 > the polymer as described in any of < 9 > to < 11 > wherein the repeating unit comprising the structure represented by the formula (1) is a repeating unit comprising the structure represented by the following formula (3-1) or formula (3-2).

[ chemical formula 8]

In the formulae (3-1) and (3-2), A²¹And A²²represents-O-, -N (R)^N) -or-P (R)^N)-。R^NAnd R²¹～R²⁶Represents a hydrogen atom or a substituent. X²¹～X²⁴With X of the formula (1)¹¹～X¹⁴The same is true. L represents a single bond or a linking group. Denotes the junction site.

Effects of the invention

The present invention can provide an organic semiconductor device having durability that can maintain desired excellent semiconductor characteristics even in the atmosphere. The present invention can also provide an organic semiconductor film which is preferable as an organic semiconductor layer in an organic semiconductor element exhibiting the above characteristics, and a method for manufacturing the same. The present invention can also provide a polymer and a composition which are preferable as a constituent material of the organic semiconductor film.

The above and other features and advantages of the present invention will become more apparent from the following description with reference to the accompanying drawings where appropriate.

Drawings

Fig. 1 is a schematic cross-sectional view showing a bottom gate-bottom contact organic thin film transistor device as an example of the semiconductor device of the present invention.

Fig. 2 is a schematic cross-sectional view showing a bottom gate-top contact organic thin film transistor device as an example of the semiconductor device of the present invention.

Detailed Description

In the present specification, the numerical range expressed by the term "to" means a range in which the numerical values recited before and after the term "to" are included as the lower limit value and the upper limit value.

In the present specification, the expression of the compound includes a salt thereof and an ion thereof, in addition to the compound itself. Further, compounds in which a part of the structure is changed within a range in which the intended effect is not impaired are included.

The compound not explicitly shown to be substituted or unsubstituted includes compounds having an arbitrary substituent within a range not impairing the intended effect. The same applies to a substituent, a linking group, a ring structure, and the like (hereinafter referred to as a substituent and the like).

In the present specification, when a plurality of substituents or the like represented by specific symbols are present, or when a plurality of substituents or the like are simultaneously specified, the substituents or the like may be the same or different from each other unless otherwise specified. The same applies to the number of substituents and the like. When a plurality of substituents and the like are close to each other (particularly, adjacent to each other), these may be connected to each other to form a ring unless otherwise specified.

In the present invention, when a plurality of repeating units represented by the same chemical structure are present in a polymer, the repeating units present in the polymer may be the same or different. This is also the same with respect to each group forming the repeating unit.

In the present invention, when the number of carbon atoms of a group is limited, the number of carbon atoms of the group refers to the total number of carbon atoms including a substituent, unless otherwise specified.

In the present invention, when a group is capable of forming an acyclic skeleton and a cyclic skeleton, the group includes a group of the acyclic skeleton and a group of the cyclic skeleton, unless otherwise specified. For example, alkyl includes straight chain alkyl, branched chain alkyl, and cyclic (cyclo) alkyl. When the group can form a cyclic skeleton, the lower limit of the number of atoms of the group forming the cyclic skeleton is 3 or more, preferably 5 or more, regardless of the lower limit of the number of atoms specifically described for the group. The cycloalkyl group includes bicycloalkyl, tricycloalkyl and the like.

Preferred embodiments of the present invention will be described below, but the present invention is not limited thereto.

[ organic semiconductor element ]

In the organic semiconductor device of the present invention, the organic semiconductor layer is formed using the polymer of the present invention described later.

The organic semiconductor element of the present invention is not particularly limited, but is preferably used as a non-light-emitting organic semiconductor device. The non-light-emitting organic semiconductor device is a device which does not aim at emitting light. Examples of such devices include an organic thin film transistor element that controls the amount of current or voltage, an organic photoelectric conversion element that converts light energy into electric power (a solid imaging element for photosensor use, a solar cell for energy conversion, or the like), an organic thermoelectric conversion element that converts thermal energy into electric power, a gas sensor, an organic rectifier element, an organic inverter, an information recording element, and the like. In a non-light-emitting organic semiconductor device, an organic semiconductor film is preferably made to function as an electronic element.

As a representative example of the organic semiconductor element, an organic thin film transistor element will be described. In the following embodiment, an embodiment in which the polymer of the present invention forms an organic semiconductor layer of an organic thin film transistor device will be described, but the present invention is not limited to this embodiment. That is, the organic semiconductor device of the embodiment in which the organic semiconductor layer contains the polymer of the present invention described later is included in the organic semiconductor device of the present invention. The organic semiconductor layer of each element can be formed in accordance with the following method for forming an organic semiconductor layer in an organic thin film transistor element.

In the following description of organic thin film transistor devices, the improvement and maintenance of carrier mobility, which is a basic characteristic of organic semiconductors, is mentioned. The organic semiconductor having high carrier mobility and capable of suppressing the drop thereof is not limited to the organic thin film transistor element, and can exhibit desired performance when applied to the respective organic semiconductor elements.

< organic thin film transistor element >

The organic thin film transistor element (also referred to as an organic TFT element) of the present invention includes an organic semiconductor film (also referred to as an organic semiconductor layer or a semiconductor active layer). Thus, the organic TFT device of the present invention exhibits high carrier mobility, and can be stably driven while effectively suppressing a drop with time even in the atmosphere.

In the present invention, the ambient temperature or humidity under the atmosphere is not particularly limited as long as it is the temperature or humidity in the environment in which the organic thin film transistor element is used, and examples of the temperature include room temperature (20 ℃) and humidity include 10 to 90 RH%.

The organic TFT device of the present invention is preferably used as an organic Field effect transistor device (FET), and more preferably as an insulated gate FET in which gate-channel (channel) is insulated.

The thickness of the organic thin film transistor device of the present invention is not particularly limited, and when a thinner transistor device is formed, for example, the thickness of the entire transistor device is preferably set to 0.1 to 0.5 μm.

The organic TFT element of the present invention may have the organic semiconductor film of the present invention, and may further have a source electrode, a drain electrode, a gate electrode, and a gate insulating film.

An organic TFT device of the present invention includes 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 and a drain electrode provided in contact with the organic semiconductor layer and connected to each other through the organic semiconductor layer on a substrate. In the organic TFT element, the organic semiconductor layer is provided adjacent to the gate insulating layer.

The organic thin film transistor device of the present invention is not particularly limited in its structure as long as it includes the above layers. For example, the semiconductor device may have any of a bottom contact type (bottom gate-bottom contact type and top gate-bottom contact type), a top contact type (bottom gate-top contact type and top gate-top contact type), and the like. The organic thin film transistor element of the present invention is more preferably of a bottom gate-bottom contact type or a bottom gate-top contact type (these are collectively referred to as a bottom gate type).

Hereinafter, an example of the organic TFT device of the present invention will be described with reference to the drawings.

Bottom gate-bottom contact organic thin film transistor device

Fig. 1 is a schematic cross-sectional view of a bottom gate-bottom contact organic TFT element 100 as an example of a semiconductor element of the present invention.

As shown in fig. 1, the organic TFT element 100 includes a substrate (base material) 10, a gate electrode 20, a gate insulating film 30, source and drain electrodes 40 and 42, an organic semiconductor film 50, and a sealing layer 60 in this order.

Hereinafter, the substrate (base material), the gate electrode, the gate insulating film, the source electrode, the drain electrode, the organic semiconductor film, the sealing layer, and the respective manufacturing methods will be described in detail.

(substrate)

The substrate functions to support a gate electrode, a source electrode, a drain electrode, and the like, which will be described later.

The type of the substrate is not particularly limited, and examples thereof include a plastic substrate, a silicon substrate, a glass substrate, and a ceramic substrate. Among them, a glass substrate or a plastic substrate is preferable from the viewpoint of applicability to each device and cost.

The thickness of the substrate is not particularly limited, but is, for example, preferably 10mm or less, more preferably 2mm or less, and particularly preferably 1.5mm or less. On the other hand, it is preferably 0.01mm or more, and more preferably 0.05mm or more.

(Gate electrode)

The gate electrode can be applied to a general electrode used as a gate electrode of an organic TFT element without any particular limitation.

The material (electrode material) for forming the gate electrode is not particularly limited, and examples thereof include metals such as gold, silver, aluminum, copper, chromium, nickel, cobalt, titanium, platinum, magnesium, calcium, barium, and sodium, and InO₂、SnO₂Or a conductive oxide such as Indium Tin Oxide (ITO), a conductive polymer such as polyaniline, polypyrrole, polythiophene, polyacetylene, or polydiacetylene, a semiconductor such as silicon, germanium, or gallium arsenic, or a carbon material such as fullerene, carbon nanotube, or graphite. Among them, the above metals are preferable, and silver or aluminum is more preferable.

The thickness of the gate electrode is not particularly limited, but is preferably 20 to 200 nm.

The gate electrode may function as the substrate, and in this case, the substrate may be omitted.

The method for forming the gate electrode is not particularly limited, and examples thereof include a method of vacuum vapor deposition (hereinafter, also simply referred to as vapor deposition) or sputtering the electrode material on the substrate, and a method of applying or printing an electrode-forming composition containing the electrode material. When the electrode is patterned, examples of the patterning method include printing methods such as inkjet printing, screen printing, offset printing, and relief printing (flexographic printing), and photolithography and mask vapor deposition.

(Gate insulating layer)

The gate insulating layer is not particularly limited as long as it is a layer having an insulating property, and may be a single layer or a plurality of layers.

The gate insulating layer is preferably formed of an insulating material, and examples of the insulating material include, but are not particularly limited to, polymethyl methacrylate, polystyrene, polyvinyl phenol, melamine resin, polyimide, polycarbonate, polyester, polyvinyl alcohol, polyvinyl acetate, polyurethane, polysulfone, polybenzoxazole, polysilsesquioxane, a polymer such as an epoxy resin or a phenol resin, an inorganic oxide such as silicon oxide, aluminum oxide, or titanium oxide, or a nitride such as silicon nitride. Among them, the polymer is preferable from the viewpoint of compatibility with the organic semiconductor film, and the inorganic oxide, particularly silicon dioxide, is preferable from the viewpoint of film uniformity.

These materials may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The thickness of the gate insulating film is not particularly limited, but is preferably 100 to 1000 nm.

The method for forming the gate insulating film is not particularly limited, and examples thereof include a method for applying a gate insulating film forming composition containing the above-mentioned material on a substrate on which a gate electrode is formed, and a method for depositing or sputtering the above-mentioned material.

(Source electrode and Drain electrode)

In the organic TFT device of the present invention, the source electrode is an electrode into which a current flows from the outside through a wiring. The drain electrode is an electrode for sending current to the outside through a wire.

The same material as the electrode material for forming the gate electrode can be used for forming the source electrode and the drain electrode. Among them, metals are preferable, and molybdenum, chromium, gold, or silver is more preferable.

The thickness of each of the source electrode and the drain electrode is not particularly limited, but is preferably 1nm or more, and particularly preferably 10nm or more. Further, it is preferably 500nm or less, particularly preferably 300nm or less.

The distance (gate length) L between the source electrode and the drain electrode can be determined as appropriate, but is preferably 200 μm or less, and more preferably 100 μm or less, for example. The gate width W can be determined as appropriate, but is preferably 5000 μm or less, and particularly preferably 1000 μm or less, for example. The ratio of the gate width W to the gate length L is not particularly limited, but is, for example, preferably 10 or more, and more preferably 20 or more.

The method for forming the source electrode and the drain electrode is not particularly limited, but examples thereof include a method of vacuum vapor depositing or sputtering an electrode material on a substrate on which a gate electrode and a gate insulating film are formed, and a method of coating or printing a composition for forming an electrode. When patterning is performed, the method of patterning is the same as that of the gate electrode described above.

(organic semiconductor layer)

An organic semiconductor layer in an organic TFT element contains a specific polymer (which may be referred to as a polymer of the present invention) having a repeating unit having a structure represented by the following formula (1).

In the present invention, the term "polymer" is used in the meaning of including an oligomer (for example, an oligomer having a repeating unit number of about 2 to 10). That is, the "polymer" is a compound having all of 2 or more repeating units having a structure represented by the following formula (1).

The organic semiconductor layer containing the polymer of the present invention can impart high carrier mobility to an organic thin film transistor element and maintain durability of the carrier mobility even in the atmosphere. The details of the reason are not determined, but are considered as follows. The polymer of the present invention has a repeating unit having a structure represented by the following formula (1) in which at least one of the ring-constituting carbon atoms forming the 3,4,9, 10-perylene bisimide skeleton is replaced with a nitrogen atom, and does not have a repeating unit having an aliphatic 7-membered ring structure. Thus, it is considered that the n-type semiconductivity of the polymer of the present invention is improved by pi-pi interaction of repeating units having high planarity with each other (particularly, the polymer main chain). Further, it is considered that the deterioration of the organic semiconductor layer (decomposition of the polymer of the present invention, etc.) due to exposure to oxygen or moisture under the atmosphere can be effectively suppressed. Therefore, the polymer of the present invention can improve the carrier mobility to a high level when used in an organic thin film transistor device, and can suppress the deterioration with time even in the atmosphere.

The polymer of the present invention is preferably used as an organic semiconductor material for an organic thin film transistor element among organic semiconductor elements.

(Polymer of the invention)

The polymer of the present invention has a repeating unit (sometimes referred to as a repeating unit (I)) having a structure represented by formula (1).

A repeating unit (I) comprising the structure represented by the formula (1)

[ chemical formula 9]

In the formula (1), A¹¹And A¹²Respectively represent-O-, -N (R)^N) -or-P (R)^N)-。A¹¹And A¹²Are each preferably-N (R)^N)-。A¹¹And A¹²May be the same or different from each other, but is preferably the same, more preferably all-N (R)^N)-。

R^NRepresents a hydrogen atom or a substituent, but a single bond or a linking group for incorporation into the polymer of the present invention can be employed. Details thereof will be described later.

With respect to as R^NThe substituent that can be used is not particularly limited. For example, a group selected from the following substituent group Z may be mentioned.

Substituent group Z

Examples of the alkyl group include a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a fluorine atom or a chlorine atom)), an alkyl group (preferably having 1(3) to 40 carbon atoms, more preferably 1(3) to 40 carbon atoms, particularly preferably 4 to 30 carbon atoms when the number in the parentheses represents a cycloalkyl group, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a 2-methylpropyl group, a butyl group, a pentyl group (Amyl group), a pentyl group, a 2, 2-dimethylpropyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl,Tridecyl, tetradecyl, pentadecyl, 2, 6-dimethyloctyl, eicosyl, 2-decyltetradecyl, 2-hexyldodecyl, 2-ethyloctyl, 2-butyldecyl, 1-octylnonyl, 2-ethyloctyl, 2-octyldecyl, 2-octyldodecyl, 7-hexylpentadecyl, 2-octyltetradecyl, 2-ethylhexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, benzyl, p-chlorobenzyl, trifluoromethyl, perfluoroethyl, 2,3,3,4,4, 4-heptafluorobutyl, C (C) ethyl, C (C) butyl, C (C)₅F₁₁C₂H₄-, 3-aminopropyl, 4-aminobutyl, 5-ethoxypentyl, (meth) acryloyloxypropyl, (meth) acryloyloxypentyl, 4-hydroxybutyl, 4-sulfobutyl, 10-phosphonodecyl, 2-hydroxyethoxymethyl, 2-imidazolylethoxymethyl, 4- (N, N-dimethylamino) butyl), alkenyl (preferably having 2 to 20, more preferably 2 to 12, particularly preferably 2 to 8 carbon atoms, e.g., vinyl, allyl, 2-butenyl, 1-pentenyl, 4-pentenyl, etc.), alkynyl (preferably having 2 to 20, more preferably 2 to 12, particularly preferably 2 to 8 carbon atoms, e.g., propargyl, 1-pentynyl, trimethylsilyl ethynyl, triethylsilyl ethynyl, etc, Triisopropylsilylethynyl group, 2-p-propylphenylethynyl group, etc.), an aryl group (preferably having 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, for example, phenyl group, naphthyl group, 2,4, 6-trimethylphenyl group, p- (tert-butyl) phenyl group, 4-methyl-2, 6-dipropylphenyl group, 4-fluorophenyl group, 4-trifluoromethylphenyl group, p-pentylphenyl group, p-octylphenyl group, 3, 4-dipentylphenyl group, p-heptyloxyphenyl group, 3, 4-diheptyloxyphenyl group), a heterocyclic group (also referred to as a heterocyclic group). Contains at least 1 hetero atom and 1 to 30 carbon atoms as ring-constituting atoms. Examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom, and the number of the hetero atom is not particularly limited, and is, for example, 1 to 2. The number of the ring-constituting carbon atoms is preferably 3 to 20, and more preferably 3 to 12. The heterocyclic group is preferably a 5-or 6-membered ring or a group having a condensed ring thereof. The heterocyclic group includes aromatic heterocyclic groups (Heteroaryl groups) and aliphatic heterocyclic groups. Examples thereof include thienyl, thiazolyl, imidazolyl, pyridyl, pyrimidyl, quinolyl, furyl and selenophenyl (C)₄H₃Se), piperidyl, morpholinyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, 2-hexylfuryl, pyranyl, tetrahydropyranyl, and the like. ) A

A silyl group (preferably 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, even more preferably 3 to 24 carbon atoms, for example, trimethylsilyl, triphenylsilyl, dimethylphenylsilyl, etc.), an alkoxy group (preferably 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, even more preferably 1 to 8 carbon atoms, for example, including methoxy, ethoxy, butoxy, etc.), an amino group (preferably 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, even more preferably 0 to 6 carbon atoms, for example, amino, methylamino, dimethylamino, diethylamino, dibenzylamino, anilino, etc.), an aryloxy group (preferably 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, even more preferably 6 to 12 carbon atoms, for example, phenoxy, 2-naphthoxy, etc.), an acyl group (preferably 1 to 20 carbon atoms, even more preferably 1 to 16 carbon atoms, even more preferably 1 to 12 carbon atoms, examples thereof include acetyl, hexanoyl, benzoyl, formyl and pivaloyl. ) And an alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 12 carbon atoms), and examples thereof include a methoxycarbonyl group and an ethoxycarbonyl group. ) And an aryloxycarbonyl group (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 10 carbon atoms), and examples thereof include a phenoxycarbonyl group and the like. ) And an acyloxy group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 10 carbon atoms), such as an acetoxy group, a benzoyloxy group, or a (meth) acryloyloxy group. ) And an amido group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 10 carbon atoms), and examples thereof include an acetamido group, a benzoylamino group and the like. ) And aminocarbonylamino groups (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 12 carbon atoms, including ureido groups, and the like). ) And an alkoxy group or an aryloxycarbonylamino group (preferably, having 2(7) to 20 carbon atoms, more preferably, having 2(7) to 16 carbon atoms, and particularly preferably, having 2(7) to 12 carbon atoms. The number in parentheses represents the number of carbon atoms in the case of an aryloxycarbonylamino group. Examples thereof include methoxycarbonylamino and phenoxycarbonylamino. ) Alkyl or arylsulfonylamino, alkylthio (preferably having 1 to 20 carbon atoms,more preferably 1 to 16, and particularly preferably 1 to 12, and examples thereof include methylthio, ethylthio, and octylthio. ) And an arylthio group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, and particularly preferably 6 to 12 carbon atoms), and examples thereof include a phenylthio group and the like. ) Alkyl or arylsulfinyl, alkyl or arylsulfonyl, siloxy, heterocyclyloxy (a group to which an-O-group is bonded to the above-mentioned heterocyclic group), carbamoyl, carbamoyloxy, heterocyclylthio (a group to which an-S-group is bonded to the above-mentioned heterocyclic group), sulfamoyl, aryl or heterocycloazo (a group to which an azo group is bonded to the above-mentioned heterocyclic group), imide group, phosphine group, phosphinyl group, phosphinyloxy group, phosphinylamino group, hydrazino group, imino group, cyano group, hydroxyl group, nitro group, mercapto group, sulfonic acid group, carboxyl group, hydroxamic acid group, sulfinic acid group, boric acid group (-B (OH))₂) Phosphonic acid group (-OPO (OH)₂) Phosphono (-PO (OH)₂) Sulfuric acid radical (-OSO)₃H)。

Wherein, with respect to as R^NThe group selected from the substituent group Z is preferably an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a heterocyclic group or a silicon group, more preferably an alkyl group (preferably having 1 to 24 carbon atoms), an aryl group (preferably having 6 to 20 carbon atoms) or a heteroaryl group (a group containing at least 1 or more of the above-mentioned heteroatoms as ring-constituting atoms, preferably a 5-or 6-membered ring or a condensed ring thereof, preferably a group having 3 to 20 carbon atoms as a ring-constituting atom), and further preferably an alkyl group (particularly preferably having 4 to 24 carbon atoms).

The above group selected from substituent group Z may further have a substituent. Examples of such a substituent include a group selected from substituent group Z.

The number of substituents that may be further substituted in the group further having substituents (also referred to as a combined group) is not particularly limited, and is, for example, preferably 1 to 6, more preferably 1 to 3.

The group formed by combination is not particularly limited, and examples thereof include groups in which the above groups selected from substituent group Z are preferably substituted with other groups selected from substituent group Z. Specifically, examples thereof include a halogen atom, an alkyl group, an aryl group, a heterocyclic group (heteroaryl group), an alkoxy group (including a hydroxyalkoxy group, a halogenated alkoxy group, and a heteroarylalkoxy group), an alkyl group having a group selected from the group consisting of an amino group, an acyloxy group, a hydroxyl group, a sulfuric acid group, and a phosphono group as a substituent, a halogenated aryl group, a (fluorinated) alkylaryl group, and an alkynyl group having a silicon group as a substituent. Further, there may be mentioned a group obtained by removing 1 hydrogen atom from a repeating unit having a structure represented by the formula (1).

More specifically, there may be mentioned the groups exemplified in the substituent group Z or the groups in the compounds exemplified below or the compounds used in examples.

Among the above groups, preferred are alkyl groups having an alkoxy group as a substituent or alkyl groups having an aryl group as a substituent, and particularly preferred are alkyl groups having an alkoxy group as a substituent.

With respect to as R^NAs the substituent that can be used, a (unsubstituted) alkyl group or an alkyl group having an alkoxy group as a substituent is more preferable.

When A is¹¹And A¹²Each has R^NWhen 2R^NMay be the same as or different from each other.

In the formula (1), B¹¹～B¹⁸Each represents-N or-C (R)^M) Is as follows. Herein, R is^MRepresents a hydrogen atom or a substituent, preferably a hydrogen atom. R^MIn addition to hydrogen atoms or substituents, it is also possible to use single bonds or linking groups for incorporation into the polymers of the invention. Details thereof will be described later.

With respect to as R^MThe substituent that can be used is not particularly limited, and examples thereof include those selected from the above substituent group Z. The group selected from the substituent group Z may further have a substituent. Examples of such a substituent include a group selected from substituent group Z. As the group further having a substituent, there may be mentioned R^NSpecific examples of the above-mentioned groups which can be used in combination include the groups mentioned above and the groups consisting of the rings of the formula (1)A group composed of a perylene bisimide skeleton in which at least one of carbon atoms is substituted with a nitrogen atom, and a group having a methine group bonded to a carbon atom of the perylene bisimide skeleton.

Wherein, with respect to as R^MAnd the substituents which can be used are preferably an alkyl group, an alkenyl group, an alkoxycarbonyl group, an aryl group, an alkoxy group, a heterocyclic group (particularly, a heteroaryl group), an amino group, a halogen atom, a cyano group, a carboxyl group, a nitro group or a mercapto group, more preferably an alkyl group, an alkenyl group, an aryl group, an alkoxy group, a heterocyclic group (particularly, a heteroaryl group), a halogen atom or a cyano group, and particularly preferably an alkyl group, an aryl group, a heterocyclic group (particularly, a heteroaryl group), a halogen atom or a cyano group.

As R^MAnd the substituents which can be used may form a ring. Examples of the form of the ring formed by the substituent include a form in which the substituents are bonded to each other to form a ring and a form in which a plurality of substituents share 1 atom to form a ring.

Examples of the mode in which substituents are bonded to each other to form a ring include 2 vinyl groups bonded to each other to R^MThe bonded carbon atoms together form a benzene ring. Further, as an embodiment in which a plurality of substituents share 1 atom to form a ring, for example, an embodiment in which 2 substituents are integrated to form a thioether group (-S-group) is given.

B¹¹～B¹⁸At least one of them is-N, preferably 1 to 4, more preferably 1 or 2, and particularly preferably 2.

B which can adopt — N ═ is not particularly limited, and B¹¹～B¹⁸Any of which may be-N ═ N. For example, B is preferred¹²、B¹³、B¹⁶And B¹⁷is-N ═ more preferably B¹²And B¹⁶One or both of which is-N ═ N.

As B¹¹～B¹⁸And the nitrogen atom of-N ═ that can be used may have a substituent. For example, an N-oxide group (N → O group), a salt having a counter anion, and the like can be given.

In the above repeating unit (I), A is¹¹And A¹²And can adopt-N (R)^N) -or-P (R)^N) R in (A-C)^NAnd as B¹¹～B¹⁸And C (R) that can be employed^M) R in ═ C^MAt least one of them represents a single bond or a linking group, and the others represent a hydrogen atom or a substituent. R^NAnd R^MThe single bond or linking group that at least one of can employ is typically bonded to other repeating units that form the polymer of the present invention. By R^NAnd R^MThe structure represented by formula (1) becomes a repeating unit of a desired polymer by a single bond or a linking group. When R is^NAnd R^MWhen a single bond or a linking group is used, a single bond is preferable.

Plural R^NAnd R^M(B¹¹～B¹⁸) The number of the single bond or the linking group used in (1) is at least 1, and for example, preferably 1 to 4, more preferably 1 or 2, and further preferably 2.

Plural R^NAnd R^MIn which R is a single bond or a linking group^NAnd R^MCan be A¹¹、A¹²And B¹¹～B¹⁸Any one of (R bonded to)^NOr R^M). For example, A is mentioned¹¹、A¹²、B¹²、B¹³、B¹⁶、B¹⁷And the like. When R is^NAnd R^MWhen a single bond or a linking group is used for 1 of the groups, A is preferably used¹¹Or A¹². When 2 adopt single bond or connecting group, A is preferred¹¹And A¹²Or B¹³And B¹⁷。

The combination of B using — N ═ and B using a single bond or a linking group is not particularly limited, but the combination of the above-mentioned preferred groups is preferable, and B is more preferable¹²And B¹⁶with-N ═ and B¹³And B¹⁷Combinations of single bonds or linking groups are employed. When A is¹¹And A¹²R in (1)^NWhen at least one of them is a single bond or a linking group, B¹¹～B¹⁸Any of them can adopt-N ═ B¹¹～B¹⁸Preferred modes of using-N-are as described above.

As R^NOr R^MThe linking group that can be used is not particularly limited as long as it is a site composed of a linking group capable of incorporating the structure represented by formula (1) into the polymer. Examples of such a linking group include R^NOr R^MAmong the above substituents, a group having a valence of 2 obtained by removing 1 hydrogen atom is preferably an alkylene group, -C (═ O) -NH-, -C (═ O) -O-, or the like.

In the formula (1), X¹¹～X¹⁴Each represents an oxygen atom or a sulfur atom, preferably an oxygen atom. More preferably X¹¹～X¹⁴Are all oxygen atoms.

Here, A is¹¹And A¹²And X¹¹～X¹⁴The combination of (A) is not particularly limited, but A is preferred¹¹And A¹²is-N (R)^N)-、X¹¹～X¹⁴All being a combination of oxygen atoms.

The repeating unit having a structure represented by formula (1) is preferably a repeating unit having a structure represented by formula (2).

[ chemical formula 10]

In the formula (2), A¹¹、A¹²And X¹¹～X¹⁴Are each as defined in formula (1) A¹¹、A¹²And X¹¹～X¹⁴The same applies, preferably also. And, A¹¹、A¹²And X¹¹～X¹⁴Preferred combinations of (a) and (b) are also as described above.

R²¹～R²⁶Each represents a hydrogen atom or a substituent. With respect to as R²¹～R²⁶And the substituents which can be employed have the meanings given above for R^MThe same substituents can be used, and the same is preferable. R²¹～R²⁶May be bonded to each other or to a carbon atom forming the isoquinoline skeleton to form a ring.

In the formula (2), A is¹¹And A¹²And can adopt-N (R)^N) -or-P (R)^N) R in (A-C)^NAnd R²¹～R²⁶At least one of them represents a single bond or a linking group. With respect to R^NAnd R²¹～R²⁶At least one of them is a single bond or a linking group, with the above-mentioned R^NAnd R^MThe same applies to single bonds or linking groups. Wherein R is²²And R²⁵It is particularly preferred to use a single bond or a linking group.

The repeating unit having a structure represented by formula (1) and the repeating unit having a structure represented by formula (2) are preferably a repeating unit having a structure represented by formula (3-1) or a repeating unit having a structure represented by formula (3-2), respectively.

[ chemical formula 11]

In the formulae (3-1) and (3-2), A²¹、A²²And X²¹～X²⁴Are each as defined in formula (1) A¹¹、A¹²And X¹¹～X¹⁴The same applies, preferably also. And, A²¹、A²²And X²¹～X²⁴Is also preferably combined with A¹¹、A¹²And X¹¹～X¹⁴The preferred combinations of (a) and (b) are the same.

R²¹～R²⁶Each represents a hydrogen atom or a substituent. With respect to as R²¹～R²⁶And the substituents which can be employed have the meanings given above for R^MThe same substituents can be used, and the same is preferable. R²¹～R²⁶May be bonded to each other or to a carbon atom forming the isoquinoline skeleton to form a ring.

L represents a single bond or a linking group, respectively. The meaning of the linking group which can be employed as L and as R^NOr R^MThe above-mentioned linking groups which can be used are the same, and preferably the same.

Denotes the junction site.

In the present invention, the repeating unit (I) includes the structure represented by formula (1), and includes a partial structure having the structure represented by formula (1) as a repeating unit, in addition to the embodiment in which the repeating unit is composed of only the structure represented by formula (1).

The mode of incorporating (introducing) the repeating unit (I) into the polymer is not particularly limited. That is, there may be mentioned a mode in which the structure represented by the formula (1) is bonded to another repeating unit forming the polymer of the present invention and incorporated into the polymer chain (forming the polymer chain), a mode in which the structure represented by the formula (1) is incorporated into a side chain (graft chain, Pendant chain (or the like)) in the repeating unit forming the polymer chain of the present invention, a mode in which the structure represented by the formula (1) is incorporated into a bridging portion (crosslinking portion) of the polymer chain of the present invention, a mode in which these are combined, and the like. In the present invention, the polymer chain is preferably incorporated.

In the above-mentioned embodiment in which the structure represented by formula (1) is incorporated into the side chain and the embodiment in which the structure represented by formula (1) is incorporated into the crosslinking site, the polymer chain having the structure represented by formula (1) (referred to as main chain with respect to the side chain and the crosslinking site) is not particularly limited, and may be appropriately determined in consideration of polymerizability with other repeating units, ease of incorporation of the structure represented by formula (1), and the like. Examples thereof include (meth) acrylate polymers, (meth) acrylamide polymers, urethane polymers, polyester polymers, and polymers obtained by combining these polymers.

Specific examples of the repeating unit (I) are shown below and in the examples, but the present invention is not limited to these.

In the following specific examples A is shown¹¹And A¹²Are all-N (R)^N) -or-P (R)^N) The repeating units of (A) but the following specific examples may also include¹¹And A¹²A compound wherein one or both of them is substituted with-O-. Herein as-P (R)^N) R in (A-C)^NExamples thereof include R in the following specific examples^N1Or R^N2The same groups.

In the following specific examples, a indicates a bonding site. R^N1And R^N2Wave lines in the columns represent slavesExample perylene bisimide Compounds with R removed^N1Or R^N2Compound part of the group R²¹、R²⁵～R²⁸The wavy line in the column indicates the portion of the perylene bisimide compound from which the corresponding R has been removed from the specific example. And TIPS represents a triisopropylsilyl group.

[ chemical formula 12]

[ chemical formula 13]

[ chemical formula 14]

[ chemical formula 15]

[ chemical formula 16]

[ chemical formula 17]

[ chemical formula 18]

[ chemical formula 19]

[ chemical formula 20]

[ chemical formula 21]

[ chemical formula 22]

[ chemical formula 23]

[ chemical formula 24]

Repeating units comprising an aliphatic 7-membered ring structure

The polymer of the present invention has a repeating unit (I) having a structure represented by the above formula (1), but does not include a repeating unit having an aliphatic 7-membered ring structure. In other words, the polymer of the present invention is composed of a repeating unit containing no aliphatic 7-membered ring structure. If the polymer of the present invention does not contain a repeating unit having an aliphatic 7-membered ring structure, high carrier mobility can be achieved. The details of the reason for this are not clear, but are considered as follows. That is, it is considered that this is because the planarity of the aliphatic 7-membered ring is poor, and therefore the planarity of the repeating unit having the aliphatic 7-membered ring structure is also impaired. As a result, the overlapping of the orbitals of the pi planes in the repeating unit is hindered, and the overlapping of the orbitals of the pi planes with respect to other repeating units in the polymer is also hindered.

In the present invention, the fact that the polymer does not contain a repeating unit having an aliphatic 7-membered ring structure means that the polymer chain (main chain) of the present invention does not contain a repeating unit having an aliphatic 7-membered ring structure incorporated therein. Therefore, in the polymer of the present invention, an aliphatic 7-membered ring structure may be incorporated in the end of the polymer chain, the graft chain, or the like. Preferably, the polymer of the present invention does not incorporate an aliphatic 7-membered ring structure in the polymer.

In the present invention, the polymer may incorporate an aromatic 7-membered ring structure. For example, an aromatic 7-membered ring structure such as Tropone (Tropone) or a ring structure containing an aromatic 7-membered ring such as azulene (Tropone cation) as a condensed ring can be incorporated.

In the present invention, the aliphatic 7-membered ring structure refers to a 7-membered ring structure (e.g., cycloheptane, cycloheptatriene) which does not exhibit aromatic properties, and the aromatic 7-membered ring structure refers to a 7-membered ring structure (e.g., cycloheptatriene cation) which exhibits aromatic properties. Here, aromatic means that the huckel rule is satisfied.

The repeating unit having an aliphatic 7-membered ring structure includes a repeating unit composed of only an aliphatic 7-membered ring and a condensed ring of an aliphatic 7-membered ring and another ring. Examples of such a repeating unit include a group having a valence of 2 represented by formula (a1) described in patent document 1.

Repeating units (II)

The polymer of the present invention preferably has, as the repeating unit (II), a group composed of a 5-or 6-membered monocyclic ring, a group composed of at least 2 condensed rings obtained by condensing the above monocyclic rings, an ethenylene group, an ethynylene group, or a combination thereof, in addition to the repeating unit (I) contained in the above. Here, the group composed of a ring means a 2-valent group obtained by removing 2 hydrogen atoms from the ring.

The 5-membered monocyclic ring forming a group consisting of a 5-membered or 6-membered monocyclic ring is not particularly limited, and examples thereof include a ring capable of conjugating with the repeating unit (I). Specifically, there may be mentioned a 5-membered hydrocarbon ring (for example, cyclopentadiene ring), a 6-membered aromatic hydrocarbon ring (that is, benzene ring), a 5-membered heterocyclic ring (preferably, aromatic heterocyclic ring) or a 6-membered heterocyclic ring (preferably, aromatic heterocyclic ring). Examples of the 5-membered heterocyclic ring include a pyrrole ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, a triazole ring, a furan ring, a thiophene ring, a selenophene ring, a silacyclopentadiene ring, and a thiadiazole ring, and examples of the 6-membered heterocyclic ring include a pyridine ring, a pyrimidine ring, a piperazine ring, and a triazine ring.

The above monocyclic ring may have a substituent. Examples of the substituent include a group selected from the above substituent group Z and an oxo group (═ O), and preferably a substituent that can be used as R or Z described later.

The condensed ring obtained by condensing at least 2 of the above-mentioned monocyclic rings is not particularly limited as long as it is a condensed ring obtained by appropriately combining the above-mentioned monocyclic rings, and examples thereof include a ring capable of being conjugated with the repeating unit (I). The condensed ring contains a group in which 2 monocyclic ring-constituting atoms are bonded to each other through a carbon-carbon double bond. The number of condensed monocyclic rings is not particularly limited as long as it is 2 or more, and is, for example, preferably 2 to 8, more preferably 2 to 6, and further preferably 2 or 3.

The condensed monocyclic ring may be of the same kind or of different kinds, and is not particularly limited in kind. Examples of the condensed rings include condensed rings in which only 5-membered monocyclic rings are condensed, condensed rings in which only 6-membered monocyclic rings are condensed, condensed rings in which only 7-membered monocyclic rings exhibiting aromatic properties (referred to as 7-membered aromatic monocyclic rings) are condensed, condensed rings in which 5-membered monocyclic rings and 6-membered monocyclic rings are condensed, and condensed rings in which 2 or more monocyclic rings selected from 5-membered monocyclic rings and 6-membered monocyclic rings and 7-membered aromatic monocyclic rings are condensed.

The condensed monocyclic ring preferably contains a 5-membered heterocyclic ring, and more preferably contains a thiophene ring.

Such condensed rings are preferably, for example, a benzimidazole ring, a benzoxazole ring, a benzothiazole ring, an indazole ring, a quinoline ring, a quinazoline ring, an azulene ring, the following formula (V)_D-2)～(V_D-17) and (V)_A-1)～(V_A-11) a shrink ring.

[ chemical formula 25]

[ chemical formula 26]

In the above formulae, a represents a bonding position with another repeating unit.

R and Z represent a hydrogen atom or a substituent. The substituent that can be used as R or Z is not particularly limited, and examples thereof include those selected from the above substituent group Z, among which a halogen atom (preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), an alkyl group or an alkynyl group is preferable. The alkyl group that can be used as R and Z is preferably an alkyl group having 1 to 35 carbon atoms, and more preferably an alkyl group having 1 to 26 carbon atoms. The alkyl group may contain-O-, -S-, -C (═ O) -and-NR-, in or at the end of the carbon chain^X1-at least one of (a) and (b). R^X1Represents a hydrogen atom or a substituent. -O-, -S-and-NR which can be contained in the carbon chain or in the end of the carbon chain^X1The total number of (a) to (b) is preferably an integer of 1 to 5, more preferably 1 to 3, and still more preferably 1. As R^X1The substituent that can be used is not particularly limited, and examples thereof include an alkyl group (preferably an alkyl group having 1 to 25 carbon atoms), a halogen atom (preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), or an aromatic hydrocarbon group (also referred to as an aryl group; preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms). R^X1Preferably a hydrogen atom or an alkyl group, more preferably an alkyl group.

R^GRepresents an alkyl group or an aromatic hydrocarbon group. The alkyl group is the same as that mentioned above for the alkyl group which can be used as R or Z. The aromatic hydrocarbon group preferably has 6 to 30 carbon atoms.

R^JRepresents a hydrogen atom, an alkyl group, a cyano group or a halogen atom. As R^JThe preferable embodiments of the alkyl group and the halogen atom that can be used are the same as those of the alkyl group and the halogen atom that can be used as Z.

Y²Represents an oxygen atom or a sulfur atom, preferably an oxygen atom.

The monocyclic group, the condensed ring group, and the combination of an ethenylene group and an ethynylene group are not particularly limited as long as they are 2-valent groups in which at least 2 of the above groups are combined. The number of the combined groups is not particularly limited as long as it is 2 or more, and is, for example, preferably 2 to 8, more preferably 2 to 6, and still more preferably 2 or 3.

The kind of the group to be combined is not particularly limited, and may be the same kind of group or different kinds of groups. Examples of the group to be combined include the following specific examples and combinations in the polymers 1 to 12 of examples, and the group composed of a 5-membered monocyclic ring-a group composed of a condensed ring or a vinylene-a group composed of a 5-membered monocyclic ring is preferable, and a 5-membered monocyclic ring or a thiophene ring is more preferable (for example, the above formula (V)_D-1) a group represented by).

Other repeating units (III)

The polymer of the present invention may have a repeating unit (III) other than the repeating units (I) and (II). As the repeating unit (III), a commonly used repeating unit can be used without particular limitation in consideration of reactivity with the repeating units (I) and (II) and the like.

The content of the repeating unit (I) in the polymer of the present invention is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 30 to 80% by mass. The content of the repeating unit (II) in the polymer is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 30 to 80% by mass in total. The content of the above-mentioned repeating unit (III) in the polymer may be appropriately determined within a range not impairing the effects of the present invention.

The weight average molecular weight of the polymer of the present invention is preferably 2000 to 1000000, more preferably 3000 to 200000.

In the present invention, the weight average molecular weight is measured by gel permeation chromatography (gpc (gel permetationchromatography) method) and calculated in terms of standard polystyrene. Specifically, for example, HLC-8121GPC (manufactured by TOSOH CORPORATION) is used for GPC, and 2 TSKgel GMH are used for the purpose of containment_HRThe calibration curve was prepared using 12 samples of "standard sample TSK standard," polystyrene "manufactured by TOSOH CORPORATION" of "F-128", "F-80", "F-40", "F-20", "F-10", "F-4", "F-2", "F-1", "A-5000", "A-2500", "A-1000" and "A-500", as the calibration curve.

The terminal structure of the polymer of the present invention is not particularly limited, and cannot be determined in a general manner depending on the presence or absence of another repeating unit, the type of a substrate used in synthesis, or the type of a quencher (reaction terminator) used in synthesis. Examples of the terminal structure include a hydrogen atom, a hydroxyl group, a halogen atom, an ethylenically unsaturated group, an alkyl group, an aromatic heterocyclic group (preferably, a thiophene ring), and an aromatic hydrocarbon group (preferably, a benzene ring).

The method for synthesizing the polymer of the present invention is not particularly limited, and the polymer can be synthesized by a general method. For example, it can be synthesized by synthesizing each precursor compound capable of introducing the repeating units (I) and (II) and subjecting each precursor to a cross-coupling reaction such as a suzuki coupling reaction or a Stille coupling reaction. For synthesizing the polymer of the present invention, for example, Japanese patent publication No. 2010-527327, Japanese patent publication No. 2007-516315, Japanese patent publication No. 2014-515043, Japanese patent publication No. 2014-507488, Japanese patent publication No. 2011-501451, Japanese patent publication No. 2010-018790, International publication No. 2012/174561, Japanese patent publication No. 2011-514399, Japanese patent publication No. 2011-514913, and the like can be referred to.

Specific examples of the polymer of the present invention are shown below and in examples, but the present invention is not limited to these examples. In the following specific examples, the repeating units (I) and (II) are collectively represented as 1 group of repeating units. For convenience of description, a mixture of cis-form and trans-form is described using the structure of the trans-form.

In the following specific examples, n, m and l represent the number of repeating units. For example, n, l and m are preferably 2 to 1000, more preferably 3 to 200, respectively.

[ chemical formula 27]

[ chemical formula 28]

[ chemical formula 29]

[ chemical formula 30]

The content of the polymer of the present invention in the organic semiconductor layer is preferably 10% by mass or more, more preferably 50% by mass or more, and further preferably 80% by mass or more. The content of the polymer of the present invention in the organic semiconductor layer can be set to 100 mass%. When the organic semiconductor layer contains a binder or the like described later, the content thereof is, for example, preferably 90% by mass or less, and more preferably 80% by mass or less.

The organic semiconductor layer may contain a binder polymer (also simply referred to as a binder) or an additive in addition to the polymer (organic semiconductor) of the present invention. As the additive, additives generally used in organic semiconductor layers can be used without particular limitation.

(Binder)

As the binder, a binder generally used in an organic semiconductor layer can be used without particular limitation.

Such a binder is not particularly limited, and examples thereof include insulating polymers such as polystyrene, poly (. alpha. -methylstyrene), polycarbonate, polyarylate, polyester, polyamide, polyimide, polyurethane, polysiloxane, polysulfone, polymethyl methacrylate, polymethacrylate, cellulose, polyethylene, and polypropylene, and copolymers thereof. In addition to these, for example, ethylene-propylene rubber, acrylonitrile-butadiene rubber, hydrogenated nitrile rubber, fluororubber, perfluoroelastomer, tetrafluoroethylene-propylene copolymer, ethylene-propylene-diene copolymer, styrene-butadiene rubber, polychloroprene rubber (polyneoprene), butyl rubber, methylphenyl silicone resin, methylphenyl vinyl silicone resin, a rubber or thermoplastic elastomer polymer such as a methyl vinyl silicone resin, a fluorosilicone resin, an acrylic rubber, an ethylene acrylic rubber, a chlorosulfonated polyethylene, a chlorinated polyethylene, an epichlorohydrin copolymer, a polyisoprene-natural rubber copolymer, a polyisoprene rubber, a styrene-isoprene block copolymer, a polyester urethane copolymer, a polyether ester thermoplastic elastomer, or a polybutadiene rubber. Examples of the polymer include a photoconductive polymer such as polyvinylcarbazole and polysilane, a conductive polymer such as polythiophene, polypyrrole, polyaniline, and polyparaphenylene vinylene, and a semiconductor polymer described in Chemistry of materials, 2014, 26, 647.

In consideration of the charge mobility, the binder preferably has a structure containing no polar group. Here, the polar group means a functional group having a heteroatom other than a carbon atom and a hydrogen atom. Among the above, polystyrene or poly (. alpha. -methylstyrene) is preferable as the binder having a structure not containing a polar group. Also, semiconductive polymers are also preferred.

The glass transition temperature of the binder is not particularly limited, and may be appropriately set according to the application and the like. For example, when strong mechanical strength is imparted to the organic semiconductor layer, it is preferable to increase the glass transition temperature. On the other hand, when flexibility is imparted to the organic semiconductor layer, it is preferable to lower the glass transition temperature.

The weight average molecular weight of the polymer used as the binder is not particularly limited, but is preferably 1,000 to 1,000 ten thousand, more preferably 3,000 to 500 ten thousand, and further preferably 5,000 to 300 ten thousand.

The binder polymer may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The content of the binder in the organic semiconductor layer is not particularly limited and can be appropriately set. For example, it is preferably 90% by mass or less, more preferably 70% by mass or less, and still more preferably 50% by mass or less. The content of the binder in the organic semiconductor layer may be 0 mass% or more, for example, preferably 10 mass% or more, more preferably 15 mass% or more, and still more preferably 20 mass% or more.

(additives)

The organic semiconductor layer may contain an additive in addition to the polymer of the present invention.

As the additive, additives generally used in an organic semiconductor layer of an organic semiconductor device can be used without particular limitation. For example, a surfactant, an antioxidant, a crystallization control agent, a crystal orientation control agent, or the like can be given. Examples of the surfactant and the antioxidant include those described in paragraphs 0136 and 0137 of jp 2015-195362 a, and the descriptions in these paragraphs are preferably incorporated in the present specification as they are.

May contain 1 kind of additive or more than 2 kinds.

The content of the additive in the organic semiconductor layer is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 1% by mass or less.

The thickness of the organic semiconductor layer can be suitably adjusted according to the organic semiconductor device to be used, and is, for example, preferably 10 to 500nm, more preferably 20 to 200 nm.

(method of Forming organic semiconductor layer)

For example, the organic semiconductor layer can be formed by preparing an organic semiconductor composition containing the polymer of the present invention and a solvent (hereinafter, also referred to as "organic semiconductor composition of the present invention"), coating or printing the composition on a substrate to form a coating film, and drying the coating film.

In the present invention, the case of applying the organic semiconductor composition to the substrate includes not only a mode in which the organic semiconductor composition is directly applied to the substrate but also a mode in which the organic semiconductor composition is applied to the upper side of the substrate through another layer provided on the substrate. The other layer to which the organic semiconductor composition is applied (a layer which is in contact with the organic semiconductor layer and serves as a base of the organic semiconductor layer) is necessarily defined depending on the structure of the organic thin film transistor element. For example, the gate insulating film is used in the case of a bottom gate type, and the source electrode or the drain electrode is used in the case of a top gate type (top gate-bottom contact type and top gate-top contact type).

As a method for coating the organic semiconductor composition of the present invention, a general method can be used, and examples thereof include a bar coating method, a spin coating method, a knife coating method, a doctor blade method, an ink jet printing method, a flexographic printing method, a gravure printing method, and a screen printing method. Further, as a method for applying the organic semiconductor composition, a method for forming an organic semiconductor film (so-called Gap cast) described in japanese patent application laid-open No. 2013-207085, a method for producing an organic semiconductor thin film (so-called edge casting method or continuous edge casting method) described in international publication No. 2014/175351, and the like can be preferably applied.

The drying (drying treatment) can be performed under appropriate conditions according to the type of each component contained in the organic semiconductor composition. Natural drying is possible, but from the viewpoint of improving productivity, heat treatment is preferable. The heating conditions are not limited, and for example, the heating temperature is preferably 30 to 250 ℃, more preferably 40 to 200 ℃, and still more preferably 50 to 150 ℃, and the heating time is preferably 10 to 300 minutes, and more preferably 20 to 180 minutes.

The organic semiconductor composition of the present invention may contain 1 kind of the polymer of the present invention alone or 2 or more kinds thereof, and the polymer of the present invention is usually dissolved in a solvent. In the organic semiconductor composition, the content of the polymer of the present invention is not particularly limited, and is preferably in the same range as the content in the organic semiconductor film, provided that the content is a content in a solid component other than the solvent.

The solvent contained in the organic semiconductor composition of the present invention is not particularly limited as long as it dissolves or disperses the polymer, and examples thereof include inorganic solvents and organic solvents. Among them, organic solvents are preferable. The solvent may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The organic solvent is not particularly limited, and examples thereof include hydrocarbon solvents such as hexane, octane and decane, aromatic hydrocarbon solvents such as toluene, xylene, mesitylene, ethylbenzene, decahydronaphthalene, 1-methylnaphthalene, 1-ethylnaphthalene, 1, 6-dimethylnaphthalene, tetrahydronaphthalene and anisole, ketone solvents such as acetone, methylethylketone, methylisobutylketone, cyclohexanone, acetophenone, propiophenone and butanone, halogenated hydrocarbon solvents such as dichloromethane, chloronaphthalene, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, 1, 2-dichlorobenzene, 1,2, 4-trichlorobenzene, chlorotoluene and 1-fluoronaphthalene, pyridine, Picoline (Picoline), quinoline, thiophene and 3-butylnaphthaleneThiophene or thieno [2,3-b ]]Heterocyclic solvents such as thiophene, halogenated heterocyclic solvents such as 2-chlorothiophene, 3-chlorothiophene, 2, 5-dichlorothiophene, 3, 4-dichlorothiophene, 2-bromothiophene, 3-bromothiophene, 2, 3-dibromothiophene, 2, 4-dibromothiophene, 2, 5-dibromothiophene, 3, 4-dibromothiophene and 3, 4-dichloro-1, 2, 5-thiadiazole, ester solvents such as ethyl acetate, butyl acetate, amyl acetate, 2-ethylhexyl acetate, gamma-butyrolactone and phenyl acetate, alcohol solvents such as methanol, propanol, butanol, pentanol, hexanol, cyclohexanol, phloxol and ethylene glycol, dibutyl ether, tetrahydrofuran, di-n-butyl etherAlkyl, dimethoxyethane, anisole, ethoxybenzene, propoxybenzene, isopropoxybenzene, butoxybenzene, 2-methylanisole, 3-methylanisole, 4-ethylanisole, dimethyl anisole (any of 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5-, 3, 6-) or 1, 4-benzodiazepineEther solvents such as alkanes, amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide, imide solvents such as 1-methyl-2-pyrrolidone and 1-methyl-2-imidazolidinone, sulfoxide solvents such as dimethyl sulfoxide, phosphate solvents such as trimethyl phosphate, nitrile solvents such as acetonitrile and benzonitrile, and nitro solvents such as nitromethane and nitrobenzene.

The content of the solvent in the organic semiconductor composition is preferably 90 to 99.99% by mass, more preferably 95 to 99.99% by mass, and still more preferably 96 to 99.95% by mass.

The organic semiconductor composition can contain the above-described binders and/or additives. The content of the binder and the additive in the organic semiconductor composition may be appropriately adjusted according to the form of the organic semiconductor layer to be formed, and is preferably set in the same range as the content of the binder in the organic semiconductor film.

The method for producing the organic semiconductor composition of the present invention is not particularly limited, and a general production method can be employed. For example, the organic semiconductor composition of the present invention can be prepared by adding predetermined amounts of the respective components to a solvent and appropriately stirring the mixture.

If necessary, heating may be performed during or after the respective components are appropriately stirred. The heating temperature is not particularly limited, and may be, for example, 150 to 40 ℃. When a solvent is used, a temperature less than the boiling point of the solvent within the above range is determined.

In the above, an example of an organic semiconductor layer used as an organic thin film transistor element has been described with respect to an organic semiconductor film containing the polymer of the present invention (referred to as an organic semiconductor film of the present invention), but the use of the organic semiconductor film of the present invention is not limited to the above, and an organic semiconductor layer provided in each of the organic semiconductor elements can be mentioned. Among them, the organic semiconductor film of the present invention is preferably used as an organic semiconductor layer of an organic thin film transistor element.

(sealing layer)

As described above, the organic semiconductor layer contains the organic semiconductor used in the present invention and is stably driven even in the atmosphere. Therefore, the organic thin film transistor element as a whole may not be sealed (blocked) against the atmosphere (oxygen) or moisture (the sealing layer may not be provided). In addition, the entire organic thin film transistor element can be sealed with a metallic sealing can or a sealant for the purpose of stable driving over a long period of time.

As the sealing layer, a sealing agent (sealing layer forming composition) generally used for organic TFT elements can be used. Examples of the sealant include inorganic materials such as glass and silicon nitride, high molecular weight materials such as Parylene (Parylene), and low molecular weight materials.

The sealing layer can be formed by a common method such as coating and drying using the above-described sealing agent.

The thickness of the sealing layer is not particularly limited, but is preferably 0.2 to 10 μm.

Bottom gate-top contact organic thin film transistor device

Fig. 2 is a schematic cross-sectional view showing a bottom gate-top contact organic thin film transistor device 200 as an example of the semiconductor device of the present invention.

As shown in fig. 2, the organic thin film transistor element 200 includes a substrate 10, a gate electrode 20, a gate insulating film 30, an organic semiconductor film 50, source and drain electrodes 40 and 42, and a sealing layer 60.

The organic thin-film transistor device 200 is the same as the organic thin-film transistor device 100 except that the layer configuration (stacking method) is different. Therefore, the substrate, the gate electrode, the gate insulating film, the source electrode, the drain electrode, the organic semiconductor layer, and the sealing layer are the same as those in the bottom gate-bottom contact organic thin film transistor device described above, and therefore, the description thereof is omitted.

[ use of organic semiconductor element ]

The application of the organic semiconductor element of the present invention is not particularly limited, and the organic semiconductor element can be used for, for example, electronic paper, display devices, sensors, electronic tags, and the like.