JP6205074B2 - ORGANIC SEMICONDUCTOR DEVICE AND ITS MANUFACTURING METHOD, COMPOUND, ORGANIC SEMICONDUCTOR FILM FORMING COMPOSITION, AND ORGANIC SEMICONDUCTOR FILM - Google Patents

Description

  The present invention relates to an organic semiconductor element and a method for producing the same, a compound, a composition for forming an organic semiconductor film, and an organic semiconductor film.

Because it can be reduced in weight, cost, and flexibility, it can be used in field effect transistors (FETs) and RFID (radio frequency identifiers, RF tags) used in liquid crystal displays and organic EL (organic electroluminescence) displays. For example, an organic transistor having an organic semiconductor film (organic semiconductor layer) is used.
As a conventional organic semiconductor, the one described in Patent Document 1 is known.

JP 2010-177643 A

The problem to be solved by the present invention is to provide an organic semiconductor device having high mobility, excellent thermal stability, and reduced mobility variation, and a method for manufacturing the same.
Another problem to be solved by the present invention is to provide a novel compound suitable as an organic semiconductor.
Furthermore, another problem to be solved by the present invention is to form an organic semiconductor film having high mobility, excellent thermal stability, and suppressed variation in mobility, and the organic semiconductor film. The object is to provide a composition for forming an organic semiconductor film.

The above-mentioned problems of the present invention have been solved by means described in the following <1>, <6>, <10>, <19>, or <20>. It is described below together with <2> to <5>, <7> to <9>, <11> to <18>, and <21> to <25>, which are preferred embodiments.
<1> An organic semiconductor element comprising an organic semiconductor layer containing an organic semiconductor represented by the following formula 1,

  In Formula 1, each X independently represents any of O, S, Se, and NR, each R independently represents a substituent, and each ring A independently represents a 5-membered or 6-membered monocyclic fragrance. Represents an aromatic hydrocarbon ring or an aromatic heterocyclic ring, m represents an integer of 1 to 5, and when m is 2 to 5, a plurality of rings A may be the same or different, and n represents an integer of 0 or more. When m is 1, at least one of R represents an aromatic hydrocarbon group or an aromatic heterocyclic group, and when m is 4 or 5, three or more R are an aromatic hydrocarbon group or an aromatic heterocyclic group. It does not become a cyclic group.

<2> In Formula 1, each ring A independently represents a benzene ring, a furan ring, a thiophene ring, a selenophene ring, or a pyrrole ring, and the symmetry of the partial structure in which R in Formula 1 is removed is C ₂ , the organic semiconductor element according to <1>, which is C _2v or C _2h ,
<3> The organic semiconductor element according to <1> or <2>, wherein the organic semiconductor represented by Formula 1 is an organic semiconductor represented by Formula 2 below.

  In formula 2, T represents any structure selected from the group consisting of the following T-1 to T-35, R ′ each independently represents a substituent, n represents an integer of 0 to 6, When T is T-1 or T-2, at least one of R ′ represents an aromatic hydrocarbon group or an aromatic heterocyclic group, and when T is any of T-20 to T-35, three The above R ′ does not become an aromatic hydrocarbon group or an aromatic heterocyclic group.

  In T-1 to T-35, X independently represents any of O, S, Se, and NR '.

  <4> The organic semiconductor element according to <3>, wherein R ′ is represented by the following formula 3.

  In formula 3, each L is independently a divalent linking group represented by any of the following formulas L-1 to L-12, or any of two or more of the following formulas L-1 to L-12 Represents a divalent linking group in which two or more divalent linking groups are bonded, and Z is independently an oligooxyethylene group having 2 or more repeating hydrogen atoms, alkyl groups, and oxyethylene units. Represents an oligosiloxane group having 2 or more silicon atoms, or a trialkylsilyl group, wherein Z represents a trialkylsilyl group because L adjacent to Z is represented by the following formula L-3 Only when it is a group, a hydrogen atom is represented by the fact that L adjacent to Z is represented by the following formula L-1, L-2, L-3, L-10, L-11, or L-12. Only if it is a linking group.

In Formula L-1 to Formula L-12, * and a wavy line part represent a bonding position with another structure, and R ^L1 in Formula L-1, Formula L-2, and Formula L-10 to Formula L-12 is respectively Independently, it represents a hydrogen atom or a substituent.

  <5> The organic semiconductor element according to any one of <1> to <4>, wherein X independently represents O or S,

<6> A compound represented by the above formula 2,
<7> The compound according to <6>, wherein R ′ is represented by Formula 3 above,
<8> The compound according to <6> or <7>, wherein X each independently represents O or S,
<9> The compound according to any one of <6> to <8>, which is an organic semiconductor,
<10> An organic semiconductor film-forming composition comprising an organic semiconductor represented by the above formula 1 and a solvent,
<11> In Formula 1, each ring A independently represents a benzene ring, a furan ring, a thiophene ring, a selenophene ring, or a pyrrole ring, and the symmetry of the partial structure in which R in Formula 1 is removed is The composition for forming an organic semiconductor film according to <10>, which is C ₂ , C _2v , or C _2h ,

<12> The organic semiconductor film-forming composition according to <10> or <11>, wherein the organic semiconductor represented by Formula 1 is the organic semiconductor represented by Formula 2 above.
<13> The composition for forming an organic semiconductor film according to <12>, wherein R ′ is represented by the above formula 3,
<14> The composition for forming an organic semiconductor film according to any one of <10> to <13>, wherein each X independently represents O or S.
<15> The organic semiconductor film according to any one of <10> to <14>, wherein the concentration of the organic semiconductor represented by Formula 1 is 0.5 to 15% by mass with respect to the entire composition. Forming composition,
<16> The composition for forming an organic semiconductor film according to any one of <10> to <15>, wherein the solvent has a boiling point of 100 ° C. or higher.
<17> The composition for forming an organic semiconductor film according to any one of <10> to <16>, further comprising a polymer binder,
<18> The composition for forming an organic semiconductor film according to any one of <10> to <17>, wherein the viscosity of the composition is 5 mPa · s to 50 mPa · s,
<19> A method for producing an organic semiconductor element, comprising a coating step of coating the composition for forming an organic semiconductor film according to any one of <10> to <18> on a substrate,

<20> An organic semiconductor film comprising the organic semiconductor represented by the above formula 1,
<21> In the above formula 1, each ring A independently represents a benzene ring, a furan ring, a thiophene ring, a selenophene ring, or a pyrrole ring, and the symmetry of the partial structure in which R in formula 1 is removed is , C ₂ , C _2v , or C _2h , the organic semiconductor film according to <20>,
<22> The organic semiconductor film according to <20> or <21>, wherein the organic semiconductor represented by the formula 1 is an organic semiconductor represented by the formula 2.
<23> The organic semiconductor film according to <22>, wherein R ′ is represented by Formula 3 above,
<24> The organic semiconductor film according to any one of <20> to <23>, wherein each X independently represents O or S.
<25> The organic semiconductor film according to any one of <20> to <24>, which is formed by a solution coating method.

ADVANTAGE OF THE INVENTION According to this invention, it was able to provide the organic-semiconductor element which was high mobility, was excellent in thermal stability, and the dispersion | variation in mobility was suppressed, and its manufacturing method.
Moreover, according to this invention, the novel compound suitable as an organic semiconductor was able to be provided.
Furthermore, according to the present invention, an organic semiconductor film having high mobility, excellent thermal stability, and suppressed variation in mobility, and formation of an organic semiconductor film capable of suitably forming the organic semiconductor film are provided. The composition for use could be provided.

It is a cross-sectional schematic diagram of one aspect | mode of the organic-semiconductor element of this invention. It is a cross-sectional schematic diagram of another one aspect | mode of the organic-semiconductor element of this invention.

Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the specification of the present application, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. The organic EL element in the present invention refers to an organic electroluminescence element.
In the notation of a group (atomic group) in this specification, the notation which does not describe substitution and unsubstituted includes what has a substituent with what does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In addition, the chemical structural formula in this specification may be expressed as a simplified structural formula in which a hydrogen atom is omitted.
In the present invention, the term “mobility” means carrier mobility, and means either or both of electron mobility and hole mobility.
In the present invention, “mass%” and “wt%” are synonymous, and “part by mass” and “part by weight” are synonymous.
In the present invention, a combination of preferred embodiments is more preferred.

(Organic semiconductor elements and compounds)
The organic semiconductor element of the present invention is characterized by having an organic semiconductor layer containing an organic semiconductor represented by the above formula 1 (hereinafter also referred to as “specific organic semiconductor compound” or “specific compound”).

As a result of intensive studies, the inventors of the present invention contain the above-mentioned specific organic semiconductor compound, whereby the obtained organic semiconductor element and organic semiconductor film have high mobility, excellent thermal stability, and mobility variation. It has been found that it is suppressed, and the present invention has been completed.
Although the detailed mechanism of the effect is unknown, the above specific organic semiconductor compound tends to have a large overlap of HOMO (Highest Occupied Molecular Orbital) between molecules, high mobility, excellent thermal stability, and It is estimated that the variation in mobility is suppressed.

<Specific organic semiconductor compound>
In the present invention, the specific organic semiconductor compound is represented by the following formula 1.

In Formula 1, each X independently represents any of O, S, Se, and NR, each R independently represents a substituent, and each ring A independently represents a 5-membered or 6-membered monocyclic fragrance. Represents an aromatic hydrocarbon ring or an aromatic heterocyclic ring, m represents an integer of 1 to 5, and when m is 2 to 5, a plurality of rings A may be the same or different, and n represents an integer of 0 or more. When m is 1, at least one of R represents an aromatic hydrocarbon group or an aromatic heterocyclic group, and when m is 4 or 5, three or more R are an aromatic hydrocarbon group or an aromatic heterocyclic group. It does not become a cyclic group.

The specific organic semiconductor compound of the present invention is a novel compound.
Moreover, the specific organic semiconductor compound of this invention can be used suitably for an organic semiconductor element, an organic semiconductor film, and the composition for organic-semiconductor film formation.
In the specific organic semiconductor compound of the present invention, the heteroatoms of the heteroaromatic ring existing at both ends of the ring A are arranged outward with respect to the ring A. By having such a specific structure, it is presumed that an organic semiconductor layer or film having high mobility, excellent thermal stability, and suppressed mobility variation can be obtained.

In Formula 1, each ring A independently represents a 5-membered or 6-membered monocyclic aromatic hydrocarbon ring or aromatic heterocyclic ring. A benzene ring is illustrated as an aromatic hydrocarbon ring. Although it does not specifically limit as a hetero atom of an aromatic heterocyclic ring, S, O, N, Se is illustrated, As an aromatic heterocyclic ring, a thiophen ring, a furan ring, a pyran ring, a pyrrole ring, a pyridine ring, a pyrazine ring, Examples include a pyrimidine ring, a pyridazine ring, a selenophene ring, and an imidazole ring.
Among these, each ring A is independently preferably a benzene ring, a thiophene ring, a selenophene ring, or a pyrrole ring, more preferably a benzene ring, a thiophene ring, or a furan ring, and a benzene ring or a thiophene ring. More preferably.
In addition, when there are a plurality of rings A, that is, when m is 2 or more, the plurality of rings A may be the same or different, and are not particularly limited.

The specific organic semiconductor compound is a compound containing an aromatic hydrocarbon group or an aromatic heterocyclic group (condensed polycyclic aromatic group containing 3 or more condensed rings) containing 3 or more and 7 or less condensed rings. The structure obtained by removing the substituent R from the specific organic semiconductor compound is also referred to as a “condensed polycyclic aromatic group”.
In Formula 1, m represents an integer of 1 to 5. m is preferably 1 to 4, and more preferably 2 to 4. That is, the number of rings in the condensed polycyclic aromatic group excluding the substituent R from the specific organic semiconductor compound is 3 to 7, preferably 3 to 6, preferably 4 to 4, from the viewpoint of mobility as an organic semiconductor. 6 is more preferable.

The partial structure in which R is removed from the specific organic semiconductor compound, that is, the symmetry of the condensed polycyclic aromatic group excluding R as a substituent from the specific organic semiconductor is C ₂ , C _2v , or C _2h Is preferred. This is because when the symmetry is C ₂ , C _2v , or C _2h, it is easy to form a regular crystal structure and high mobility is easily exhibited.
Regarding the symmetry of the condensed ring structure, the description of “Molecular symmetry and group theory” (by Masao Nakazaki, Tokyo Kagaku Dojin) is considered.

In Formula 1, each R independently represents a substituent. When n is 2 or more, a plurality of R may be the same or different.
R is a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group or a tricycloalkyl group), an alkenyl group, an alkynyl group, an aryl group (aromatic hydrocarbon group), a heterocyclic group (heterocyclic group). Including aromatic heterocyclic group and aliphatic heterocyclic group), cyano group, hydroxy group, nitro group, carboxy group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group , Acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group , Sulfamoylamino groups, alkyl and aryls Phonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, Aryl and heterocyclic azo groups, imide groups, phosphino groups, phosphinyl groups, phosphinyloxy groups, phosphinylamino groups, phosphono groups, silyl groups (including mono-, di-, and trialkylsilyl groups), hydrazino Group, ureido group, boronic acid group (—B (OH) ₂ ), phosphato group (—OPO (OH) ₂ ), sulfato group (—OSO ₃ H), and other known substituents. R may be further substituted with a substituent. Examples of the substituent include the groups exemplified for R.

Among these, R is preferably a halogen atom, an alkyl group, an alkoxy group, an alkynyl group, an acyl group, an acyloxy group, an aryl group, or a heterocyclic group, an alkyl group, an aryl group (aromatic hydrocarbon group), or An aromatic heterocyclic group is more preferable.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
As an alkyl group, a C2-C18 alkyl group is preferable, a C3-C15 alkyl group is more preferable, and a C4-C12 alkyl group is still more preferable. The alkyl group may be linear, branched or cyclic, and may be a combination thereof, but is preferably a linear or branched alkyl group, and is a linear alkyl group. It is more preferable.
As an alkoxy group, it is preferable that it is a C2-C18 alkoxy group, it is more preferable that it is a C3-C15 alkoxy group, and it is still more preferable that it is a C4-C12 alkoxy group. The alkyl group part of the alkoxy group may be linear, branched or cyclic, and may be a combination thereof, but is preferably a linear or branched alkyl group.
As an alkynyl group, a C2-C18 alkynyl group is preferable, A C3-C15 alkynyl group is more preferable, A C4-C12 alkynyl group is still more preferable.
The acyl group (R—C (═O) —) is preferably an acyl group having 2 to 18 carbon atoms, more preferably an acyl group having 3 to 15 carbon atoms, and more preferably an acyl group having 4 to 12 carbon atoms.
As the acyloxy group (R— (═O) —O—), an acyloxy group having 2 to 18 carbon atoms is preferable, an acyloxy group having 3 to 15 carbon atoms is more preferable, and an acyloxy group having 4 to 12 carbon atoms is still more preferable. .

Examples of the aryl group (aromatic hydrocarbon group) include groups obtained by removing one hydrogen from benzene, naphthalene, anthracene and the like.
The aromatic heterocyclic group includes a group obtained by removing one hydrogen atom from a thiophene ring, furan ring, pyran ring, pyrrole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, selenophene ring, imidazole ring, and the like. A group obtained by removing one hydrogen atom from a thiophene ring, a selenophene ring, or a pyrrole ring, more preferably a group obtained by removing one hydrogen atom from a thiophene ring or a furan ring, A group obtained by removing one hydrogen atom from the ring is more preferable.

When m is 1, at least one of R represents an aromatic hydrocarbon group or an aromatic heterocyclic group. When m is 1, unless at least one of R represents an aromatic hydrocarbon group or an aromatic heterocyclic group, sufficient mobility cannot be obtained because the π-conjugated system is small.
When m is 1, at least one of R is preferably an aromatic hydrocarbon group or an aromatic heterocyclic group, and from the viewpoint of mobility, at least two are preferably an aromatic hydrocarbon group or an aromatic heterocyclic group. .
When m is 1, examples of the aromatic hydrocarbon group represented by R include groups in which one hydrogen atom has been removed from a benzene ring, naphthalene ring, anthracene ring, or the like. Among these, a group in which one hydrogen atom is removed from a benzene ring or a naphthalene ring is preferable, and a group in which one hydrogen atom is removed from a benzene ring is particularly preferable.
As the aromatic heterocyclic group represented by R, one hydrogen atom is removed from a thiophene ring, furan ring, pyran ring, pyrrole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, selenophene ring, imidazole ring, etc. And is preferably a group obtained by removing one hydrogen atom from a thiophene ring, a selenophene ring, or a pyrrole ring, and more preferably a group obtained by removing one hydrogen atom from a thiophene ring or a furan ring. A group obtained by removing one hydrogen atom from a thiophene ring is more preferable.
The aromatic hydrocarbon group or aromatic heterocyclic group represented by R is particularly preferably a group obtained by removing one hydrogen atom from a benzene ring or thiophene ring.
Note that that at least one of R represents an aromatic hydrocarbon group or an aromatic heterocyclic group means that an aromatic hydrocarbon group or an aromatic heterocyclic group is directly bonded to a condensed polycyclic aromatic group containing ring A. Means that

When m is 4 or 5, three or more Rs do not become an aromatic hydrocarbon group or an aromatic heterocyclic group. When m is 4 or 5, when three or more Rs are aromatic hydrocarbon groups or aromatic heterocyclic groups, the solubility is very low because the π-conjugated system becomes too large, and the sublimation temperature is Become very expensive. Therefore, the performance is likely to deteriorate due to poor film quality during coating film formation, and the performance is likely to deteriorate because a thermal decomposition product is generated during vapor deposition film formation.
When m is 4 or 5, 0 to 2 R are aromatic hydrocarbon groups or aromatic heterocyclic groups, and 0 or 1 R is an aromatic hydrocarbon group or aromatic heterocyclic group Preferably, it does not have R representing an aromatic hydrocarbon group or an aromatic heterocyclic group.

  n represents an integer of 0 or more, and means the number of substitutions of R with respect to the condensed polycyclic aromatic group. In addition, when m is 1, n represents an integer of 1 or more, and when m is 2 to 5, n represents an integer of 0 or more. n is preferably 1 or more, and more preferably 2 or more. Although the upper limit of n is not particularly limited, it is preferably 8 or less, more preferably 6 or less, and still more preferably 4 or less from the viewpoint of mobility and film forming property.

  The specific organic semiconductor compound contains a condensed polycyclic aromatic group containing a ring A (condensed polycyclic aromatic structure), and this group is preferably contained as a main component. Here, the main component means that the molecular weight content of the condensed polycyclic aromatic group is 30% or more with respect to the total molecular weight of the specific organic semiconductor compound, and preferably 40% or more. The upper limit is not particularly limited, but is preferably 95% or less from the viewpoint of solubility.

  The specific organic semiconductor compound is more preferably a compound represented by the following formula 2.

In formula 2, T represents any structure selected from the group consisting of the following T-1 to T-35, R ′ each independently represents a substituent, n represents an integer of 0 to 6, When T is T-1 or T-2, at least one of R ′ represents an aromatic hydrocarbon group or an aromatic heterocyclic group, and when T is any of T-20 to T-35, three The above R ′ does not become an aromatic hydrocarbon group or an aromatic heterocyclic group.

In T-1 to T-35, X independently represents any of O, S, Se, and NR ′.

  In Formula 2, T is T-1, T-2, T-3, T-4, T-9, T-11, T-22, T-23, T-24, and T-25. T-3, T-4, T-9, T-11, and T-22 are more preferable, and T-9 and T-11 are even more preferable.

In Formula 2, R ′ has the same meaning as R in Formula 1.
In Formula 2, the preferred range of X is the same as the preferred range of X in Formula 1.
In Formula 2, R ′ is preferably represented by the following Formula 3.

In formula 3, each L is independently a divalent linking group represented by any of the following formulas L-1 to L-12, or any of two or more of the following formulas L-1 to L-12 Represents a divalent linking group in which two or more divalent linking groups are bonded, and Z is independently an oligooxyethylene group having 2 or more repeating hydrogen atoms, alkyl groups, and oxyethylene units. Represents an oligosiloxane group having 2 or more silicon atoms, or a trialkylsilyl group, wherein Z represents a trialkylsilyl group because L adjacent to Z is represented by the following formula L-3 Only when it is a group, a hydrogen atom is represented by the fact that L adjacent to Z is represented by the following formula L-1, L-2, L-3, L-10, L-11, or L-12. Only if it is a linking group.

In Formula L-1 to Formula L-12, * and a wavy line part represent a bonding position with another structure, and R ^L1 in Formula L-1, Formula L-2, and Formula L-10 to Formula L-12 is respectively Independently, it represents a hydrogen atom or a substituent.

In Formula L-1 to Formula L-12, the wavy line part represents the bonding position with any structure selected from the group consisting of T-1 to T-35, and * represents the bonding position with Z, or It is preferable to represent a bonding position with a divalent linking group selected from the group consisting of other L-1 to L-12.
In addition, when L represents a linking group to which a divalent linking group represented by any one of the above formulas L-1 to L-12 is bonded, it is represented by any one of the formulas L-1 to L-12. The number of bonds of the divalent linking group to be formed is preferably 2 to 4, more preferably 2 or 3.
In L-1, L-2, L-10, L-11 and L-12, a plurality of R ^L1 may be the same or different. In L-1 and L-2, RL1 may be bonded to each adjacent Z to form a ring structure, and the ring structure may form a condensed ring.
Examples of R ^L1 include a hydrogen atom or various substituents exemplified as R in Formula 1 above.

  The divalent linking group represented by the formula L-10 is a divalent linking group represented by the following formula L-10A, formula L-10B, or formula L-10C, and the formula L-10A or A divalent linking group represented by Formula L-10B is preferred, and a divalent linking group represented by Formula L-10B is more preferred.

  The divalent linking group represented by the formula L-12 is a divalent linking group represented by the following formula L-12A, L-12B or L-12C, and represented by the formula L-12A or L-12B: It is preferably a divalent linking group represented, and more preferably a divalent linking group represented by Formula L-12B.

  L is a divalent linking group represented by any one of formulas L-1 to L-6, L-10, L-11, and L-12, or two or more of these divalent linking groups are bonded. A divalent linking group is preferable, and the divalent linking group represented by any one of formulas L-1 to L-5, L-10, L-11, and L-12, or these divalent groups. Is more preferably a divalent linking group in which two or more linking groups are bonded, and from the viewpoint of obtaining chemical stability and high mobility, the formulas L-1, L-3, L-10, L-11 and More preferably, it is a divalent linking group represented by any one of L-12, or a divalent linking group in which two or more of these divalent linking groups are bonded. , L-10 and L-12, or a divalent linking group in which two or more of these divalent linking groups are bonded. It is particularly preferred divalent linking group represented by the formula L-1 or or L-3, or, most preferably these divalent divalent linking group linking groups bonded two or more.

When Z is an alkyl group, it is not particularly limited as long as it is an alkyl group having 1 or more carbon atoms. However, from the viewpoint of chemical stability and carrier transportability, the number of carbon atoms is preferably 2 to 18, and 3 to 12 Is more preferably 4 to 10, particularly preferably 4 to 8, and most preferably 4 to 6.
In the specific organic semiconductor compound, when an alkyl group is included in the above-LZ, the carrier mobility is increased when the alkyl group represented by Z is not less than the lower limit of the above range. When L includes Formula L-1 adjacent to Z, the number of carbon atoms of the alkyl group formed by combining the alkylene group represented by Formula L-1 and the alkyl group represented by Z is in the above range. When the value is equal to or greater than the lower limit value of the carrier mobility increases.
The alkyl group represented by Z may be linear, branched or cyclic, and is preferably a linear alkyl group from the viewpoint of increasing carrier mobility, and is a linear alkyl group having 1 to 12 carbon atoms. More preferably, it is a linear alkyl group having 3 to 12 carbon atoms, more preferably a linear alkyl group having 4 to 10 carbon atoms, and a linear alkyl group having 4 to 8 carbon atoms. The group is more particularly preferably a straight-chain alkyl group having 4 to 6 carbon atoms. When Z is an alkyl group having a substituent, examples of the substituent include a halogen atom, and a fluorine atom is preferable. In addition, when Z 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.

When Z represents an oligooxyethylene group having 2 or more repeating oxyethylene units, the oxyethylene unit represented by Z is a group represented by-(OCH ₂ CH ₂ ) _x OY in the present specification. (The repeating number x of the oxyethylene unit represents an integer of 2 or more, and Y at the terminal represents a hydrogen atom or a substituent). In addition, when Y at the terminal of the oligooxyethylene group is a hydrogen atom, it becomes a hydroxy group. The number of repeating oxyethylene units x is preferably 2 to 4, and more preferably 2 to 3. The terminal hydroxy group of the oligooxyethylene group is preferably 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 still more preferable.

When Z is an oligosiloxane group having 2 or more silicon atoms, the number of repeating siloxane units is preferably 2 to 4, more preferably 2 to 3. Further, it is preferable that a hydrogen atom or an alkyl group is bonded to the Si atom. When the alkyl group is bonded to the Si atom, the alkyl group preferably has 1 to 3 carbon atoms, and for example, a methyl group or an ethyl group is preferably bonded. The same alkyl group may be bonded to the Si atom, or different alkyl groups or hydrogen atoms may be bonded thereto. Moreover, although all the siloxane units which comprise an oligosiloxane group may be the same or different, it is preferable that all are the same.
Z can be a substituted or unsubstituted trialkylsilyl group only when L adjacent to Z is a divalent linking group represented by the above formula L-3. When Z is a substituted or unsubstituted trialkylsilyl group, the number of carbon atoms of the alkyl group bonded to the Si atom is preferably 1 to 3, for example, a methyl group, an ethyl group, or an isopropyl group is preferably bonded. .
The same alkyl group may be bonded to the Si atom, or different alkyl groups may be bonded thereto. There is no restriction | limiting in particular as a substituent in case Z is a trialkylsilyl group which has a substituent.

  In the present invention, the condensed polycyclic aromatic group (organic semiconductor mother nucleus) containing ring A in Formula 1 or the specific examples of T in Formula 2 include the condensed polycyclic aromatic groups (t-1 to t-1) shown below. t-35) is preferably exemplified, but the present invention is not limited to these examples.

  Among these, t-1, t-2, t-3, t-4, t-9, t-11, t-22, t-23, t-24, t-25 are preferable, t-3, t-4, t-9, t-11, and t-22 are more preferable, and t-9 and t-11 are still more preferable.

The molecular weight of the specific organic semiconductor compound is not particularly limited, but the molecular weight is preferably 1,500 or less, more preferably 1,000 or less, still more preferably 800 or less, and 700 or less. Is particularly preferred. By making molecular weight below the said upper limit, the solubility to a solvent can be improved. On the other hand, from the viewpoint of film quality stability of the thin film, the molecular weight is preferably 400 or more, more preferably 450 or more, and even more preferably 500 or more.
The organic semiconductor layer described later, the organic semiconductor film described later, or the composition for forming an organic semiconductor film includes two or more specific organic semiconductor compounds even if only one specific organic semiconductor compound is included. However, from the viewpoint of orientation, only one type is preferable.

  The method for synthesizing the specific organic semiconductor compound is not particularly limited, and can be synthesized with reference to known methods. As a synthesis method, an organic semiconductor mother nucleus having a halogen atom as a substituent is synthesized, and various coupling reactions such as Stille coupling reaction, Suzuki-Miyaura coupling reaction, Negishi coupling reaction, and Kumada coupling reaction are performed. Is mentioned.

  Although the preferable specific example of a specific organic-semiconductor compound is shown below, it cannot be overemphasized that it is not limited to these.

  The content of the specific organic semiconductor compound in the organic semiconductor layer of the organic semiconductor element of the present invention or the organic semiconductor film of the present invention described later is preferably 30 to 100% by mass, and preferably 50 to 100% by mass. More preferably, it is more preferably 70 to 100% by mass. Moreover, when not containing the binder polymer mentioned later, it is preferable that the said content is 90-100 mass%, and it is more preferable that it is 95-100 mass%.

<Binder polymer>
The organic semiconductor layer of the organic semiconductor element of the present invention preferably contains a binder polymer.
The organic semiconductor element of the present invention may be an organic semiconductor element having the organic semiconductor layer and a layer containing a binder polymer.
The kind in particular of a binder polymer is not restrict | limited, A well-known binder polymer can be used.
Examples of the binder polymer include polystyrene resin, acrylic resin, rubber, and thermoplastic elastomer.
Among these, as the binder polymer, a polymer compound having a benzene ring (a polymer having a monomer unit having a benzene ring group) is preferable. The content of the monomer 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 monomer units. The upper limit is not particularly limited, but 100 mol% can be mentioned.
Examples of the binder polymer include polystyrene, poly (α-methylstyrene), polyvinyl cinnamate, poly (4-vinylphenyl), poly (4-methylstyrene), and the like.

The weight average molecular weight of the binder polymer is not particularly limited, but is preferably 1,000 to 2,000,000, more preferably 3,000 to 1,000,000, and still more preferably 5,000 to 600,000.
Moreover, when using the solvent mentioned later, it is preferable that the solubility of the binder polymer in the solvent to be used is higher than that of the specific compound. It is excellent in the mobility and thermal stability of the organic semiconductor obtained as it is the said aspect.
The content of the binder polymer in the organic semiconductor layer of the organic semiconductor element of the present invention is preferably 1 to 200 parts by mass and more preferably 10 to 150 parts by mass with respect to 100 parts by mass of the specific compound. Preferably, it is 20-120 mass parts. It is excellent in the mobility and thermal stability of the organic semiconductor obtained as it is the said range.

<Other ingredients>
The organic semiconductor layer in the organic semiconductor element of the present invention may contain other components in addition to the specific organic semiconductor compound and the binder polymer.
As other components, known additives and the like can be used.
The content of components other than the specific compound and the binder polymer 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 content is particularly preferably 0.1% by mass or less. When it is in the above range, the film-forming property is excellent, and the mobility and thermal stability of the obtained organic semiconductor are excellent.

  The method for forming the organic semiconductor layer in the organic semiconductor element of the present invention is not particularly limited, and a composition for forming an organic semiconductor film of the present invention described later is applied on the source electrode, the drain electrode, and the gate insulating film, A desired organic semiconductor layer can be formed by performing a drying treatment as necessary.

The organic semiconductor element of the present invention is preferably manufactured using the composition for forming an organic semiconductor film of the present invention described later.
A method for producing an organic semiconductor film or an organic semiconductor element using the composition for forming an organic semiconductor film of the present invention is not particularly limited, and a known method can be adopted. For example, a method of producing an organic semiconductor film by applying the composition onto a predetermined substrate and subjecting it to a drying treatment as necessary can be mentioned.
The method for applying the composition on the substrate is not particularly limited, and a known method can be adopted, for example, an inkjet printing method, a flexographic printing method, a bar coating method, a spin coating method, a knife coating method, a doctor blade method, or the like. The inkjet printing method and the flexographic printing method are preferable.
In addition, as a flexographic printing method, the aspect using a photosensitive resin plate as a flexographic printing plate is mentioned suitably. In some embodiments, the composition can be printed on a substrate to easily form a pattern.
Especially, it is preferable that the manufacturing method of the organic-semiconductor element of this invention includes the application | coating process which apply | coats the composition for organic-semiconductor film formation of this invention on a board | substrate, The composition for organic-semiconductor film formation of this invention is a solvent. It is more preferable to include a coating step for coating the composition for forming an organic semiconductor film of the present invention on a substrate and a removing step for removing the solvent from the coated composition.

The composition for forming an organic semiconductor film of the present invention to be described later preferably contains a solvent, and more preferably contains an organic solvent.
A known solvent can be used as the solvent.
Specifically, for example, hydrocarbon solvents such as hexane, octane, decane, toluene, xylene, mesitylene, ethylbenzene, decalin, 1-methylnaphthalene, for example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Halogenated hydrocarbon solvents such as dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, chlorotoluene, ester solvents such as ethyl acetate, butyl acetate, amyl acetate, methanol, propanol, Alcohol solvents such as butanol, pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, ethylene glycol, dibutyl ether Ether solvents such as tetrahydrofuran, dioxane and anisole, amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide, imides such as 1-methyl-2-pyrrolidone and 1-methyl-2-imidazolidinone And nitrile solvents such as acetonitrile, sulfoxide solvents such as dimethyl sulfoxide, and acetonitrile.

A solvent may be used individually by 1 type and may be used in combination of multiple.
Among these, hydrocarbon solvents, halogenated hydrocarbon solvents and / or ether solvents are preferable, and toluene, xylene, mesitylene, tetralin, dichlorobenzene or anisole are more preferable.

It is preferable from a viewpoint of film forming property that the boiling point of a solvent is 100 degreeC or more. The boiling point of the solvent is more preferably 100 to 300 ° C, further preferably 125 to 250 ° C, and particularly preferably 150 to 225 ° C.
In addition, it is preferable that the boiling point of the solvent with most content is 100 degreeC or more, and it is more preferable that the boiling points of all the solvents are 100 degreeC or more.

  When the solvent is contained, the content of the specific compound in the composition for forming an organic semiconductor film of the present invention is preferably 0.05 to 50% by mass, more preferably 0.1 to 25% by mass. 0.25 to 15% by mass, more preferably 0.4 to 10% by mass, and the binder polymer content is preferably 0.01 to 50% by mass. 0.05 to 25 mass% is more preferable, and 0.1 to 10 mass% is still more preferable. Within the above range, the coating property is excellent and the organic semiconductor film can be easily formed.

  The drying process in the removal step is a process performed as necessary, and optimal conditions are appropriately selected depending on the type of the specific compound and the solvent used. Among them, the heating temperature is preferably 30 ° C. to 100 ° C., more preferably 40 ° C. to 80 ° C., and the heating time is excellent in terms of mobility and thermal stability of the obtained organic semiconductor and excellent productivity. 10 to 300 minutes are preferable, and 30 to 180 minutes are more preferable.

  The thickness of the formed organic semiconductor layer is not particularly limited, but is preferably 10 to 500 nm, and more preferably 30 to 200 nm, from the viewpoint of the mobility and thermal stability of the obtained organic semiconductor.

Although there is no restriction | limiting in particular as an organic semiconductor element, It is preferable that it is a 2-5 terminal organic semiconductor element, and it is more preferable that it is a 2 or 3 terminal organic semiconductor element.
The organic semiconductor element is preferably not a photoelectric conversion element.
Furthermore, the organic semiconductor element of the present invention is preferably a non-light emitting organic semiconductor element.
Examples of the two-terminal element include a rectifying diode, a constant voltage diode, a PIN diode, a Schottky barrier diode, a surge protection diode, a diac, a varistor, and a tunnel diode.
Examples of the three-terminal element include a bipolar transistor, a Darlington transistor, a field effect transistor, an insulated gate bipolar transistor, a unijunction transistor, a static induction transistor, a gate turn thyristor, a triac, and a static induction thyristor.
Among these, a rectifying diode and transistors are preferably exemplified, and a field effect transistor is more preferably exemplified.
As the field effect transistor, an organic thin film transistor is preferably exemplified.

One embodiment of the organic thin film transistor of the present invention will be described with reference to the drawings.
FIG. 1 is a schematic cross-sectional view of one embodiment of the organic semiconductor element (organic thin film transistor (organic TFT)) of the present invention.
In FIG. 1, an organic thin film transistor 100 includes a substrate 10, a gate electrode 20 disposed on the substrate 10, a gate insulating film 30 covering the gate electrode 20, and a side of the gate insulating film 30 opposite to the gate electrode 20 side. A source electrode 40 and a drain electrode 42 in contact with the surface, an organic semiconductor film 50 covering the surface of the gate insulating film 30 between the source electrode 40 and the drain electrode 42, and a sealing layer 60 covering each member are provided. The organic thin film transistor 100 is a bottom gate-bottom contact type organic thin film transistor.
In FIG. 1, the organic semiconductor film 50 corresponds to a film formed from the above-described composition.
Hereinafter, the substrate, the gate electrode, the gate insulating film, the source electrode, the drain electrode, the organic semiconductor film, the sealing layer, and the respective formation methods will be described in detail.

<Board>
The substrate plays a role of supporting a gate electrode, a source electrode, a drain electrode and the like which will be described later.
The kind of board | substrate is not restrict | limited in particular, For example, a plastic substrate, a glass substrate, a ceramic substrate etc. are mentioned. Among these, a glass substrate or a plastic substrate is preferable from the viewpoint of applicability to each device and cost.
The material of the plastic substrate may be a thermosetting resin (for example, epoxy resin, phenol resin, polyimide resin, polyester resin (for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN)) or thermoplastic resin (for example, phenoxy). Resin, polyether sulfone, polysulfone, polyphenylene sulfone, etc.).
Examples of the material for the ceramic substrate include alumina, aluminum nitride, zirconia, silicon, silicon nitride, silicon carbide, and the like.
Examples of the glass substrate material include soda glass, potash glass, borosilicate glass, quartz glass, aluminum silicate glass, and lead glass.

<Gate electrode, source electrode, drain electrode>
Examples of materials for the gate electrode, the source electrode, and the drain electrode include gold (Au), silver, aluminum (Al), copper, chromium, nickel, cobalt, titanium, platinum, tantalum, magnesium, calcium, barium, and sodium. Metal: conductive oxide such as InO ₂ , SnO ₂ , indium tin oxide (ITO); conductive polymer such as polyaniline, polypyrrole, polythiophene, polyacetylene, polydiacetylene; semiconductor such as silicon, germanium, gallium arsenide; fullerene And carbon materials such as carbon nanotubes and graphite. Among these, a metal is preferable, and silver or aluminum is more preferable.
The thickness of the gate electrode, source electrode, and drain electrode is not particularly limited, but is preferably 20 to 200 nm.

  The method for forming the gate electrode, the source electrode, and the drain electrode is not particularly limited, and examples thereof include a method of vacuum-depositing or sputtering an electrode material on a substrate, and a method of applying or printing an electrode-forming composition. In the case of patterning the electrode, examples of the patterning method include a photolithography method; a printing method such as ink jet printing, screen printing, offset printing, letterpress printing; and a mask vapor deposition method.

<Gate insulation film>
Materials for the gate insulating film include polymethyl methacrylate, polystyrene, polyvinylphenol, polyimide, polycarbonate, polyester, polyvinyl alcohol, polyvinyl acetate, polyurethane, polysulfone, polybenzoxazole, polysilsesquioxane, epoxy resin, phenol resin, etc. Examples thereof include oxides such as silicon dioxide, aluminum oxide, and titanium oxide; and nitrides such as silicon nitride. Of these materials, a polymer is preferable in view of compatibility with the organic semiconductor film.
When a polymer is used as the material for the gate insulating film, it is preferable to use a crosslinking agent (for example, melamine) in combination. By using a crosslinking agent in combination, the polymer is crosslinked and the durability of the formed gate insulating film is improved.
The thickness of the gate insulating film is not particularly limited, but is preferably 100 to 1,000 nm.

The method for forming the gate insulating film is not particularly limited, and examples thereof include a method of applying a composition for forming a gate insulating film on a substrate on which a gate electrode is formed, and a method of depositing or sputtering a gate insulating film material. It is done. The method for applying the gate insulating film forming composition is not particularly limited, and known methods (bar coating method, spin coating method, knife coating method, doctor blade method) can be used.
When a gate insulating film forming composition is applied to form a gate insulating film, it may be heated (baked) after application for the purpose of solvent removal, crosslinking, and the like.

<Binder polymer layer>
The organic semiconductor element of the present invention preferably has the binder polymer layer between the organic semiconductor layer and the insulating film, and more preferably has the binder polymer layer between the organic semiconductor layer and the gate insulating film. preferable. The thickness of the binder polymer layer is not particularly limited, but is preferably 20 to 500 nm. Although the said binder polymer layer should just be a layer containing the said polymer, it is preferable that it is a layer which consists of the said binder polymer.

The method for forming the binder polymer layer is not particularly limited, and a known method (bar coating method, spin coating method, knife coating method, doctor blade method, ink jet method) can be used.
When a binder polymer layer forming composition is applied to form a binder polymer layer, it may be heated (baked) after application for the purpose of solvent removal, crosslinking and the like.

<Sealing layer>
The organic semiconductor element of the present invention preferably includes a sealing layer as the outermost layer from the viewpoint of durability. A well-known sealing agent can be used for a sealing layer.
The thickness of the sealing layer is not particularly limited, but is preferably 0.2 to 10 μm.

  The method for forming the sealing layer is not particularly limited. For example, the composition for forming the sealing layer is applied onto the substrate on which the gate electrode, the gate insulating film, the source electrode, the drain electrode, and the organic semiconductor film are formed. The method etc. are mentioned. A specific example of the method of applying the sealing layer forming composition is the same as the method of applying the gate insulating film forming composition. When an organic semiconductor film is formed by applying the sealing layer forming composition, it may be heated (baked) after application for the purpose of solvent removal, crosslinking and the like.

FIG. 2 is a schematic cross-sectional view of another embodiment of the organic semiconductor element (organic thin film transistor) of the present invention.
2, the organic thin film transistor 200 includes a substrate 10, a gate electrode 20 disposed on the substrate 10, a gate insulating film 30 covering the gate electrode 20, and an organic semiconductor film 50 disposed on the gate insulating film 30. A source electrode 40 and a drain electrode 42 disposed on the organic semiconductor film 50 and a sealing layer 60 covering each member are provided. Here, the source electrode 40 and the drain electrode 42 are formed using the composition of the present invention described above. The organic thin film transistor 200 is a top contact type organic thin film transistor.
The substrate, gate electrode, gate insulating film, source electrode, drain electrode, organic semiconductor film, and sealing layer are as described above.

1 and 2, the embodiments of the bottom gate-bottom contact type organic thin film transistor and the bottom gate-top contact type organic thin film transistor have been described in detail. However, the organic semiconductor element of the present invention has a top gate-bottom type. It can also be suitably used for contact type organic thin film transistors and top gate-top contact type organic thin film transistors.
In addition, the organic thin-film transistor mentioned above can be used conveniently for electronic paper, a display device, etc.

(Composition for forming an organic semiconductor film)
The composition for forming an organic semiconductor film of the present invention is characterized by containing a specific organic semiconductor compound and a solvent.
Moreover, it is preferable that the composition for organic-semiconductor film formation of this invention contains a binder polymer.
The specific compound, binder polymer, and solvent in the composition for forming an organic semiconductor film of the present invention are synonymous with the specific compound, binder polymer, and solvent described above, and the preferred embodiments are also the same.

The composition for forming an organic semiconductor film of the present invention may contain other components in addition to the specific compound and the binder polymer.
As other components, known additives and the like can be used.
The content of the components other than the specific compound and the binder polymer in the composition for forming an organic semiconductor film of the present invention is preferably 10% by mass or less, more preferably 5% by mass or less based on the total solid content. The content is more preferably 1% by mass or less, and particularly preferably 0.1% by mass or less. When it is in the above range, the film-forming property is excellent, and the mobility and thermal stability of the obtained organic semiconductor are excellent. In addition, solid content is the quantity of the component except volatile components, such as a solvent.

The viscosity of the composition for forming an organic semiconductor film of the present invention is not particularly limited, but is preferably 3 to 100 mPa · s, more preferably 5 to 50 mPa · s, and more preferably 9 to 40 mPa · s in terms of more excellent coating properties. Further preferred. In addition, the viscosity in this invention is a viscosity in 25 degreeC.
As a measuring method of a viscosity, it is preferable that it is a measuring method based on JISZ8803.

  The manufacturing method of the composition for forming an organic semiconductor film of the present invention is not particularly limited, and a known method can be adopted. For example, a desired composition can be obtained by adding a predetermined amount of a specific compound in a solvent and appropriately stirring. Moreover, when using a binder polymer, a specific compound and a binder polymer can be added simultaneously or sequentially, and a composition can be produced suitably.

(Organic semiconductor film)
The organic semiconductor film of the present invention contains a specific organic semiconductor.
The organic semiconductor film of the present invention preferably contains a binder polymer.
The specific compound in the organic semiconductor film of the present invention, the polymer and oligomer obtained by polymerizing the specific compound, and the binder polymer are obtained by polymerizing the specific compound and the specific compound described above in the organic semiconductor element of the present invention. It is synonymous with the obtained polymer and oligomer, and a binder polymer, and its preferable aspect is also the same.

The composition for forming an organic semiconductor film of the present invention may contain other components in addition to the specific compound, the polymer and oligomer obtained by polymerizing the specific compound, and the binder polymer.
As other components, known additives and the like can be used.
The specific compound in the organic semiconductor film of the present invention, the polymer and oligomer obtained by polymerizing the specific compound, and the content of components other than the binder polymer are preferably 10% by mass or less, and preferably 5% by mass or less. More preferably, it is more preferably 1% by mass or less, and particularly preferably 0.1% by mass or less. When it is in the above range, the film-forming property is excellent, and the mobility and thermal stability of the obtained organic semiconductor are excellent. In addition, solid content is the quantity of the component except volatile components, such as a solvent.

Although the film thickness of the organic-semiconductor film of this invention is not restrict | limited in particular, 10-500 nm is preferable and 30-200 nm is more preferable from a viewpoint of the mobility and thermal stability of the organic semiconductor obtained.
The organic semiconductor film of the present invention can be suitably used for an organic semiconductor element, and can be particularly suitably used for an organic transistor (organic thin film transistor).
The organic semiconductor film of the present invention can be suitably produced using the composition for forming an organic semiconductor film of the present invention.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass.

(Organic semiconductor compound)
The structures of Compounds 1 to 15 and Comparative Compounds 1 to 6, which are organic semiconductor compounds used for the organic semiconductor layer, are shown below.

  Compound 1 was synthesized by the following synthesis scheme. Specifically, J. et al. Org. Chem. 1984, 49, 1027. Synthetic intermediate 1 was synthesized according to the method described, and synthetic intermediate 2 was synthesized according to the method described in JP-A-2009-200028, and compound 1 was obtained by a Stille coupling reaction.

  Compound 2 was synthesized by the following synthesis scheme. Specifically, Chem. Commun. 2013, 49, 5354. Synthesis intermediate 3 was synthesized according to the method described in J. Mater. Chem. S, 2014, 2, 3972. Synthesis Intermediate 4 was synthesized by the method described in 1. and Compound 2 was obtained by a Stille coupling reaction of both.

Compounds 3 to 15 were also synthesized according to the above method.
Comparative compound 1 is exemplary compound (II-5) described in JP-A-7-228865. Comparative compound 2 is exemplary compound (II-2) described in JP-A-5-158260. Comparative compound 3 and comparative compound 4 are exemplary compound 71 and exemplary compound 120 described in JP 2010-177643 A. Comparative compound 5 is exemplified compound 3 described in JP 2010-205984 A. Comparative compound 6 is described in J. Am. Am. Chem. Soc. 1998, 120, 664. Is the compound 7a.
In either case, it was confirmed by high performance liquid chromatography (manufactured by Tosoh Corporation, TSKgel ODS-100Z) that the purity (absorption intensity area ratio at 254 nm) was 99.8% or more.

<Starting materials used>
1,2,3,4-Tetramethylbenzene used for the synthesis of Compound 1 was purchased from Alpha Acer.
3,4-Dibromothiophene used for the synthesis of Compound 2 was purchased from Wako Pure Chemical Industries.

The compounds used in the schemes other than those described above are as follows.
Br ₂ : Bromine (manufactured by Wako Pure Chemical Industries, Ltd.)
Na ₂ S: Sodium sulfide (manufactured by Wako Pure Chemical Industries, Ltd.)
NaIO ₄ : Sodium periodate (manufactured by Wako Pure Chemical Industries, Ltd.)
Al ₂ O ₃ : Aluminum oxide (Wako Pure Chemical Industries, Ltd.)
NBS: N-bromosuccinimide (manufactured by Wako Pure Chemical Industries, Ltd.)
Pd (PPh ₃ ) ₄ : Tetrakis (triphenylphosphine) palladium (0) (manufactured by Tokyo Chemical Industry Co., Ltd.)
n-BuLi: n-butyllithium (manufactured by Tokyo Chemical Industry Co., Ltd.)
(PhSO ₂ ) ₂ S: bis (phenylsulfonyl) sulfide (prepared by the method described in Tetrahedron Lett., 2002, 43, 1553.)
Me ₃ SnSnMe ₃ : Hexamethyl distanan (manufactured by Tokyo Chemical Industry Co., Ltd.)
LDA: Lithium diisopropylamide (manufactured by Tokyo Chemical Industry Co., Ltd.)
TMSCl: Chlorotrimethylsilane (manufactured by Tokyo Chemical Industry Co., Ltd.)
ICl: Iodine monochloride (Wako Pure Chemical Industries, Ltd.)

<Binder polymer>
The polymer used as the binder is shown below.
PαMS: poly-α-methylstyrene, weight average molecular weight 437,000, manufactured by Sigma-Aldrich Corporation PTAA: poly [bis (4-phenyl) (2,4,6-trimethylphenyl) amine], number average molecular weight 7,000 to 10,000, Sigma-Aldrich PCPDTBT: Poly [2,6- (4,4-bis (2-ethylhexyl) -4Hcyclopenta [2,1-b; 3,4-b ′] dithiophene) -Alto-4 , 7- (2,1,3-benzothiadiazole)], weight average molecular weight 7,000 to 20,000, manufactured by Sigma-Aldrich

<Preparation of coating solution for organic semiconductor film formation>
The organic semiconductor compound (0.5% by mass) / binder polymer (concentration described in Table 1) / anisole (boiling point 154 ° C.) listed in Table 1 was weighed into a glass vial and mixed rotor (manufactured by ASONE Co., Ltd.). After stirring and mixing for 10 minutes, the coating solution for forming an organic semiconductor film (composition for forming an organic semiconductor film) was obtained by filtering with a 0.5 μm membrane filter. In Table 1, what is described as “-” in the column of the binder polymer indicates that no binder polymer is added.
In addition, the density | concentration of a binder polymer is the mass% in a coating liquid.

<TFT device fabrication>
Al serving as a gate electrode was deposited on a glass substrate (Eagle XG: Corning) (thickness: 50 nm). On top of that, a composition for forming a gate insulating film (polyvinylphenol / melamine = 1 part by weight / 1 part by weight (w / w) PGMEA (propylene glycol monomethyl ether acetate) solution (solid content concentration: 2% by weight)) is spun A gate insulating film having a thickness of 400 nm was formed by coating and baking at 150 ° C. for 60 minutes. On top of that, silver ink (H-1, manufactured by Mitsubishi Materials Corporation) is formed into a source electrode and a drain electrode (channel length: 40 μm, channel width: 200 μm) using an inkjet device DMP-2831 (manufactured by Fujifilm Dimatics). Drawn. Thereafter, baking was performed at 180 ° C. for 30 minutes in an oven, sintering was performed, and a source electrode and a drain electrode were formed to obtain an element substrate for TFT characteristic evaluation.
Each organic semiconductor film forming coating solution is spin-coated (500 rpm for 10 seconds and then 1,000 rpm for 30 seconds) on the TFT characteristic evaluation element substrate, and then dried on a hot plate at 50 ° C. for 10 minutes to form an organic semiconductor layer. Thus, a bottom gate-bottom contact type organic TFT element was obtained.

<Characteristic evaluation>
The following performance evaluation was performed under the atmosphere using a semiconductor characteristic evaluation apparatus B2900A (manufactured by Agilent Technologies).
(A) Carrier mobility, and (b) mobility variation A voltage of −60 V is applied between the source electrode and the drain electrode of each organic TFT element, and the gate voltage is changed in the range of +10 V to −60 V, and the drain The carrier mobility μ was calculated using the following formula representing the current I _d .
I _d = (w / 2L) μC _i (V _g −V _th ) ²
In the formula, L is the gate length, W is the gate width, C _i is the capacitance per unit area of the insulating layer, V _g is the gate voltage, and V _th is the threshold voltage.
The value of carrier mobility shown in Table 1 is an average value of 10 elements. The carrier mobility μ is preferably as high as possible, and is practically preferably 1 × 10 ⁻² cm ² / Vs or more, more preferably 1 × 10 ⁻¹ cm ² / Vs or more. In addition, about the thing whose mobility is less than 1 * 10 < ^-5 > cm < ² > / Vs, since a characteristic is too low, characteristic evaluation was not performed and "-" was described in the applicable column of Table 1. FIG.
In addition, the variation coefficient calculated by the following formula for the carrier mobility of 10 elements was evaluated in the following 5 stages and used as an index of mobility variation. The smaller this value, the smaller the mobility variation between elements. Practically, it is preferably A or B, more preferably A.
Variation coefficient = standard deviation ÷ average value x 100
A: Less than 15% B: 15% or more and less than 30% C: 30% or more and less than 50% D: 50% or more

(C) Heat resistance After heating each organic thin-film transistor element in a nitrogen glove box at 150 ° C. for 1 hour, the carrier mobility is measured by the same method as in (a), and after heating calculated by the following formula The carrier mobility maintenance rate was evaluated in the following four stages and used as an index of heat resistance. The larger this value, the higher the heat resistance, and it is preferable that it is A for practical use.
Carrier mobility retention rate after heating (%) = mobility (after heating) / mobility (before heating)
A: 80% or more B: 60% or more and less than 80% C: 40% or more and less than 60% D: Less than 40%

  10: substrate, 20: gate electrode, 30: gate insulating film, 40: source electrode, 42: drain electrode, 50: organic semiconductor film, 60: sealing layer, 100, 200: organic thin film transistor

Claims (17)

It has an organic semiconductor layer containing an organic semiconductor represented by the following formula 2,
Organic semiconductor element.

In Formula 2, T represents any structure selected from the following T-1, T-2, T-3, T-4, T-9, T-11, and T-2 3 I Li Cheng group , R ′ each independently represents a substituent represented by the following formula 3, n represents an integer of 0-6, and when T is T-1 or T-2, n represents an integer of 1-6. represents and, 'at least one of an aromatic hydrocarbon group or an aromatic heterocyclic group, when T is T -2 3, 3 or more R' of an aromatic hydrocarbon group or aromatic heterocyclic R It does not become a cyclic group.

In T-1, T-2, T-3, T-4, T-9, T-11 , and T- 23 , X independently represents any of O, S, Se, and NR ′. Represent.

In formula 3, each L is independently a divalent linking group represented by any of the following formulas L-1 to L-12, or any of two or more of the following formulas L-1 to L-12 Represents a divalent linking group in which two or more divalent linking groups are bonded to each other, and Z is independently an alkyl group, an oligooxyethylene group having 2 or more repeating oxyethylene units, or a silicon atom. An oligosiloxane group having a number of 2 or more, or a trialkylsilyl group, wherein Z represents a trialkylsilyl group is a linking group in which L adjacent to Z is represented by the following formula L-3 Limited to cases.

In Formula L-1 to Formula L-12, * and a wavy line part represent a bonding position with another structure, and R ^L1 in Formula L-1, Formula L-2, and Formula L-10 to Formula L-12 is respectively Independently, it represents a hydrogen atom or a substituent. Symmetry of the partial structure obtained by removing the R 'in the formula 2 _is, C _{2, C 2v, or} a _{C 2h,} the organic semiconductor device according to claim 1.   The organic-semiconductor element of Claim 1 or 2 in which X represents O or S each independently. A compound represented by the following formula 2.

In Formula 2, T is below t-1, t-2, t-3, t-4, t-9, t-11, and, any of the structures selected from t -2 3 by Li Cheng group R 'represents each independently a substituent represented by the following formula 3, n represents an integer of 0 to 6, and when T is t-1 or t-2, n is an integer of 1 to 6 And at least one of R ′ represents an aromatic hydrocarbon group or an aromatic heterocyclic group, and T is t −2 3 , three or more R ′ are an aromatic hydrocarbon group or an aromatic group It does not become a heterocyclic group.


In formula 3, each L is independently a divalent linking group represented by any of the following formulas L-1 to L-12, or any of two or more of the following formulas L-1 to L-12 Represents a divalent linking group in which two or more divalent linking groups are bonded to each other, and Z is independently an alkyl group, an oligooxyethylene group having 2 or more repeating oxyethylene units, or a silicon atom. An oligosiloxane group having a number of 2 or more, or a trialkylsilyl group, wherein Z represents a trialkylsilyl group is a linking group in which L adjacent to Z is represented by the following formula L-3 Limited to cases.

In Formula L-1 to Formula L-12, * and a wavy line part represent a bonding position with another structure, and R ^L1 in Formula L-1, Formula L-2, and Formula L-10 to Formula L-12 is respectively Independently, it represents a hydrogen atom or a substituent. The compound according to claim 4 , which is an organic semiconductor. A composition for forming an organic semiconductor film, comprising an organic semiconductor represented by Formula 2 and a solvent.

In Formula 2, T represents any structure selected from the following T-1, T-2, T-3, T-4, T-9, T-11, and T-2 3 I Li Cheng group , R ′ each independently represents a substituent represented by the following formula 3, n represents an integer of 0-6, and when T is T-1 or T-2, n represents an integer of 1-6. represents and, 'at least one of an aromatic hydrocarbon group or an aromatic heterocyclic group, when T is T -2 3, 3 or more R' of an aromatic hydrocarbon group or aromatic heterocyclic R It does not become a cyclic group.

In T-1, T-2, T-3, T-4, T-9, T-11 , and T- 23 , X independently represents any of O, S, Se, and NR ′. Represent.

In formula 3, each L is independently a divalent linking group represented by any of the following formulas L-1 to L-12, or any of two or more of the following formulas L-1 to L-12 Represents a divalent linking group in which two or more divalent linking groups are bonded to each other, and Z is independently an alkyl group, an oligooxyethylene group having 2 or more repeating oxyethylene units, or a silicon atom. An oligosiloxane group having a number of 2 or more, or a trialkylsilyl group, wherein Z represents a trialkylsilyl group is a linking group in which L adjacent to Z is represented by the following formula L-3 Limited to cases.

In Formula L-1 to Formula L-12, * and a wavy line part represent a bonding position with another structure, and R ^L1 in Formula L-1, Formula L-2, and Formula L-10 to Formula L-12 is respectively Independently, it represents a hydrogen atom or a substituent. Symmetry of the partial structure obtained by removing the R 'in the formula 2 _is, C _{2, C 2v, or} a _{C 2h,} the organic semiconductor film forming composition according to claim 6. The composition for forming an organic semiconductor film according to claim 6 or 7 , wherein each X independently represents O or S. The composition for organic-semiconductor film formation of any one of Claims 6-8 whose density | concentration of the organic semiconductor represented by Formula 2 is 0.1-15 mass% with respect to the whole composition. . The composition for organic-semiconductor film formation of any one of Claims 6-9 whose boiling point of a solvent is 100 degreeC or more. The composition for organic-semiconductor film formation of any one of Claims 6-10 which further contains a polymer binder. The composition for forming an organic semiconductor film according to any one of claims 6 to 11 , wherein the viscosity of the composition is 5 mPa · s to 50 mPa · s. The manufacturing method of an organic-semiconductor element including the application | coating process which apply | coats the composition for organic-semiconductor film formation of any one of Claims 6-12 on a board | substrate. An organic semiconductor film comprising an organic semiconductor represented by the following formula 2.

In Formula 2, T is below T-1, T-2, T-3, T-4, T-9, T-11, and, any of the structures selected from T-2 3 I Li Cheng group R 'represents each independently a substituent represented by the following formula 3, n represents an integer of 0 to 6, and when T is T-1 or T-2, n is an integer of 1 to 6 represents, and, 'at least one of an aromatic hydrocarbon group or an aromatic heterocyclic group, when T is T -2 3, 3 or more R' of an aromatic hydrocarbon group or an aromatic R It does not become a heterocyclic group.

In T-1, T-2, T-3, T-4, T-9, T-11, T -2 3, X independently represents O, S, Se, and either NR '.

In formula 3, each L is independently a divalent linking group represented by any of the following formulas L-1 to L-12, or any of two or more of the following formulas L-1 to L-12 Represents a divalent linking group in which two or more divalent linking groups are bonded to each other, and Z is independently an alkyl group, an oligooxyethylene group having 2 or more repeating oxyethylene units, or a silicon atom. An oligosiloxane group having a number of 2 or more, or a trialkylsilyl group, wherein Z represents a trialkylsilyl group is a linking group in which L adjacent to Z is represented by the following formula L-3 Limited to cases.

In Formula L-1 to Formula L-12, * and a wavy line part represent a bonding position with another structure, and R ^L1 in Formula L-1, Formula L-2, and Formula L-10 to Formula L-12 is respectively Independently, it represents a hydrogen atom or a substituent. Symmetry of the partial structure obtained by removing the R 'in the formula 2 _is, C _{2, C 2v, or} a _{C 2h,} the organic semiconductor film according to claim 14. The organic semiconductor film according to claim 14 or 15 , wherein each X independently represents O or S. The organic semiconductor film according to any one of claims 14 to 16 , which is formed by a solution coating method.