JP6573840B2 - ORGANIC SEMICONDUCTOR DEVICE AND ORGANIC SEMICONDUCTOR FILM, COMPOUND AND ORGANIC SEMICONDUCTOR COMPOSITION USED FOR THE SAME - Google Patents

Description

  The present invention relates to an organic semiconductor element, and an organic semiconductor film, a compound, and an organic semiconductor composition used therefor.

A semiconductor element is used in a device using a logic circuit such as a liquid crystal display, an organic electroluminescence display, an RFID (radio frequency identifier: RF tag) or a memory, or a solar cell. Among these, an organic semiconductor element having an organic semiconductor film is superior to an inorganic semiconductor element having an inorganic semiconductor film because it can be reduced in weight or cost and is excellent in flexibility. Examples of such an organic semiconductor element include an organic thin film transistor element that controls the amount of current or voltage, an organic photoelectric conversion device that converts light energy into electric power, or an organic thermoelectric conversion device that converts heat energy into electric power. .
In these organic semiconductor elements, research on organic semiconductor films containing organic compounds is underway. Examples of such an organic compound include an organic polymer or a low molecular weight organic compound. As an example of a low molecular weight organic compound, there is dithienofluorene having two octyl groups at the 9-position of the fluorene skeleton (Non-patent Document 1).

Organic Letters, 2014, 16, 936-939.

  In recent years, the performance of liquid crystal displays and the like equipped with organic semiconductor elements has been rapidly advanced. In addition, the applications are diversified, and the opportunity for use in an environment such as a high-temperature and high-humidity environment is increasing as compared with the conventional case. Examples of the high temperature and high humidity environment include an environment having a temperature of 50 to 85 ° C. and a humidity of 50 to 85 RH%. Therefore, in addition to high initial performance, the organic semiconductor element is required to have durability (also referred to as high temperature and high humidity resistance) that can be maintained even in a high temperature and high humidity environment. It is also important to exhibit excellent hysteresis characteristics (voltage controllability) in terms of operational stability.

  It is an object of the present invention to provide an organic semiconductor element that exhibits high carrier mobility, high temperature and high humidity resistance, and excellent hysteresis characteristics. Moreover, this invention makes it a subject to provide the organic-semiconductor film | membrane, organic-semiconductor composition, and compound used for the organic-semiconductor element which has the said characteristic.

  As a result of intensive studies, the present inventors have found that a compound in which an aromatic heterocycle is further condensed to each benzene ring of a fluorene skeleton and a specific substituent is introduced into at least one of the two aromatic heterocycles is an organic semiconductor. It can be used for an organic semiconductor film of an element, and further, when an organic semiconductor film containing this compound is used for an organic semiconductor element, it can provide high carrier mobility, high temperature and high humidity resistance, and excellent hysteresis characteristics. I found. The present invention has been further studied and completed based on these findings.

式（２−２）中、
Ｘは各々独立に酸素原子、硫黄原子又はセレン原子を示す。
Ｙ^１は、ＣＲ^Ｙ１Ｒ^Ｙ２又はＳｉＲ^Ｙ１Ｒ^Ｙ２を示し、Ｒ^Ｙ１及びＲ^Ｙ２は各々独立に水素原子又は置換基を示す。
Ｒ^１及びＲ^２は各々独立に下記式（Ｚ）で表される基を示す。ｐ及びｑは各々独立に０〜２の整数である。ただし、ｐ＋ｑは１以上の整数である。
Ｒ^３及びＲ^４は各々独立に置換基を示す。ｒ及びｓは各々独立に０〜２の整数である。
−Ｌ−Ｒ^Ｚ （Ｚ）
式（Ｚ）中、Ｌは、単結合、下記式（Ｌ−１）〜式（Ｌ−１２）のいずれかで表される連結基、又は、下記式（Ｌ−１）〜式（Ｌ−１２）のいずれかで表される連結基が２つ以上結合した連結基を示す。
Ｒ^Ｚは、アルキル基、ハロアルキル基、シアノ基、ビニル基、エチニル基、アリール基、ヘテロアリール基、シロキサン基、ケイ素原子数が２以上のオリゴシロキサン基、又は、トリアルキルシリル基を示す。 The above-described problems of the present invention have been solved by the following means.
<1> An organic semiconductor element comprising an organic semiconductor film containing a compound represented by the following formula (2-2) .

In formula (2-2) ,
X each independently represents an oxygen atom, a sulfur atom or a selenium atom.
Y ¹ represents CR ^Y1 R ^Y2 or SiR ^Y1 R ^Y2 , and R ^Y1 and R ^Y2 each independently represent a hydrogen atom or a substituent .
R ¹ and R ² each independently represent a group represented by the following formula (Z). p and q are each independently an integer of 0 to 2. However, p + q is an integer of 1 or more.
R ³ and R ⁴ each independently represent a substituent. r and s are each independently an integer of 0 to 2.
^-L-R Z (Z)
In formula (Z), L represents a single bond, a linking group represented by any of the following formulas (L-1) to (L-12), or the following formulas (L-1) to (L- 12) A linking group in which two or more linking groups represented by any one are bonded.
R ^Z is an alkyl group, a haloalkyl group, a cyano group, a vinyl group, an ethynyl group, an aryl group, a heteroaryl group, a siloxane group, the number of silicon atoms is more than one oligosiloxane groups, or show a trialkylsilyl group.

式（Ｌ−１）〜式（Ｌ−１２）中、
＊＊は、式（２−２）中のＸを環構成原子とする芳香族複素環との連結部位、又は式（Ｌ−１）〜式（Ｌ−１２）のいずれかで表される他の連結基との結合部位を示し、＊はＲ^Ｚ、又は式（Ｌ−１）〜式（Ｌ−１２）のいずれかで表される他の連結基との結合部位を示す。
ｍ１は０〜４の整数であり、ｍ２は各々独立に０〜２の整数である。
Ｒ^Ｚ１は各々独立に水素原子又は置換基を示す。
Ｒ^Ｚ２は各々独立に置換基を示す。

In formula (L-1) to formula (L-12),
** represents a linking site with an aromatic heterocycle having X as a ring-constituting atom in formula (2-2) , or any one of formula (L-1) to formula (L-12) The coupling | bonding site | part with a coupling group of * shows a coupling | bonding site | part with the other coupling group represented by either R ^<Z > or Formula (L-1)-Formula (L-12).
m1 is an integer of 0-4, and m2 is an integer of 0-2 each independently.
R ^Z1 each independently represents a hydrogen atom or a substituent.
R ^Z2 each independently represents a substituent.

< 2> The organic semiconductor element according to <1 >, wherein r and s are both 0.
< 3> The organic semiconductor element according to <1> or <2>, wherein p and q are both 1.
<4> ^{Y 1} is a ^CR Y1 ^{R Y2} <1> ~ organic semiconductor device according to any one of <3>.
< 5> The organic semiconductor element according to any one of < 1 > to < 4 >, wherein X is an oxygen atom or a sulfur atom.

式（３−２）中、Ｒ^３１及びＲ^３２は各々独立に水素原子又は置換基を示す。
Ｘは各々独立に酸素原子又は硫黄原子を示す。
Ｒ^１及びＲ^２は、それぞれ、式（２−２）のＲ^１及びＲ^２と同義である。 The organic semiconductor device according to any one of <1> to <5> represented by the following following formula is a compound represented by <6> formula (2-2) (3-2).

In formula (3-2) , R ³¹ and R ³² each independently represent a hydrogen atom or a substituent.
X represents an oxygen atom or a sulfur atom each independently.
R ¹ and R ² have the same meanings as R ¹ and R ² in Formula (2-2) , respectively.

<7> R ^Y1 and R ^Y2 in formula (2-2) or R ³¹ and R ^{32 in} formula (3-2) are each independently an alkyl group having 1 to 6 carbon atoms. The organic semiconductor element according to any one of 6>.
< 8> R ¹ and R ² in formula (2-2) or formula (3-2) are the same as those in formula (L-1), formula (L-9), formula (L-10), and formula (L -11) or a linking group represented by any of formula (L-1), formula (L-4), formula (L-5), or formula (L-7). Is a linking group in which two or more are bonded, and R ^Z represents a group that is an alkyl group. The organic semiconductor element according to any one of <1> to < 7 >.
< 9 > The organic semiconductor element according to any one of <1> to < 8 >, wherein the organic semiconductor element is an organic thin film transistor element.

式（２−２）中、Ｘは各々独立に酸素原子、硫黄原子又はセレン原子を示す。
Ｙ^１は、ＣＲ^Ｙ１Ｒ^Ｙ２又はＳｉＲ^Ｙ１Ｒ^Ｙ２を示し、Ｒ^Ｙ１及びＲ^Ｙ２は各々独立に水素原子又は置換基を示す。
Ｒ^１及びＲ^２は各々独立に下記式（Ｚ）で表される基を示す。ｐ及びｑは各々独立に０〜２の整数である。ただし、ｐ＋ｑは１以上の整数である。
Ｒ^３及びＲ^４は各々独立に置換基を示す。ｒ及びｓは各々独立に０〜２の整数である。
−Ｌ−Ｒ^Ｚ （Ｚ）
式（Ｚ）中、Ｌは、単結合、下記式（Ｌ−１）〜式（Ｌ−１２）のいずれかで表される連結基、又は、下記式（Ｌ−１）〜式（Ｌ−１２）のいずれかで表される連結基が２つ以上結合した連結基を示す。
Ｒ^Ｚは、アルキル基、ハロアルキル基、シアノ基、ビニル基、エチニル基、アリール基、ヘテロアリール基、シロキサン基、ケイ素原子数が２以上のオリゴシロキサン基、又は、トリアルキルシリル基を示す。

式（Ｌ−１）〜式（Ｌ−１２）中、
＊＊は、式（２−２）中のＸを環構成原子とする芳香族複素環との連結部位、又は式（Ｌ−１）〜式（Ｌ−１２）のいずれかで表される他の連結基との結合部位を示し、＊はＲ^Ｚ、又は式（Ｌ−１）〜式（Ｌ−１２）のいずれかで表される他の連結基との結合部位を示す。
ｍ１は０〜４の整数であり、ｍ２は各々独立に０〜２の整数である。
Ｒ^Ｚ１は各々独立に水素原子又は置換基を示す。
Ｒ^Ｚ２は各々独立に置換基を示す。 < 10 > A compound represented by the following formula (2-2) .

In formula (2-2) , each X independently represents an oxygen atom, a sulfur atom or a selenium atom.
Y ¹ represents CR ^Y1 R ^Y2 or SiR ^Y1 R ^Y2 , and R ^Y1 and R ^Y2 each independently represent a hydrogen atom or a substituent.
R ¹ and R ² each independently represent a group represented by the following formula (Z). p and q are each independently an integer of 0 to 2. However, p + q is an integer of 1 or more.
R ³ and R ⁴ each independently represent a substituent. r and s are each independently an integer of 0 to 2.
^-L-R Z (Z)
In formula (Z), L represents a single bond, a linking group represented by any of the following formulas (L-1) to (L-12), or the following formulas (L-1) to (L- 12) A linking group in which two or more linking groups represented by any one are bonded.
R ^Z represents an alkyl group, a haloalkyl group, a cyano group, a vinyl group, an ethynyl group, an aryl group, a heteroaryl group, a siloxane group, an oligosiloxane group having 2 or more silicon atoms, or a trialkylsilyl group.

In formula (L-1) to formula (L-12),
** represents a linking site with an aromatic heterocycle having X as a ring-constituting atom in formula (2-2) , or any one of formula (L-1) to formula (L-12) The coupling | bonding site | part with a coupling group of * shows a coupling | bonding site | part with the other coupling group represented by either R ^<Z > or Formula (L-1)-Formula (L-12).
m1 is an integer of 0-4, and m2 is an integer of 0-2 each independently.
R ^Z1 each independently represents a hydrogen atom or a substituent.
R ^Z2 each independently represents a substituent.

< 11> The compound according to < 10 >, wherein r and s are both 0.
< 12> The compound according to < 10> or <11> , wherein both p and q are 1.
<13> ^{Y 1} is a CR ^Y1 R ^Y2 <10> ~ The compound according to any one of <12>.
< 14> The compound according to any one of < 10 > to < 13 >, wherein X is an oxygen atom or a sulfur atom.

式（３−２）中、Ｒ^３１及びＲ^３２は各々独立に水素原子又は置換基を示す。
Ｘは各々独立に酸素原子又は硫黄原子を示す。
Ｒ^１及びＲ^２は、それぞれ、式（２−２）のＲ^１及びＲ^２と同義である。 <15> formula (2-2) <10> a compound represented is represented by the following formula (3-2) in ~ The compound according to any one of <14>.

In formula (3-2) , R ³¹ and R ³² each independently represent a hydrogen atom or a substituent.
X represents an oxygen atom or a sulfur atom each independently.
R ¹ and R ² have the same meanings as R ¹ and R ² in Formula (2-2) , respectively.

<16> R ^Y1 and R ^Y2 of formula (2-2) or R ³¹ and R ³² of formula (3-2) are each independently an alkyl group having 1 to 6 carbon atoms. 15. The compound according to any one of 15>.
< 17> R ¹ and R ² in formula (2-2) or formula (3-2) are the same as those in formula (L-1), formula (L-9), formula (L-10), and formula (L -11) or a linking group represented by any of formula (L-1), formula (L-4), formula (L-5), or formula (L-7). There are two or more bonded linking groups, a group R ^Z is an alkyl group <10> - the compound according to any one of <16>.
< 18 > An organic semiconductor composition containing the compound according to any one of the above < 10 > to < 17 > and a solvent.
< 19 > An organic semiconductor film containing the compound according to any one of the above < 10 > to < 17 >.

  ADVANTAGE OF THE INVENTION According to this invention, the organic-semiconductor element which shows high carrier mobility, high temperature, high humidity tolerance, and the outstanding hysteresis characteristic can be provided. Moreover, according to this invention, the organic-semiconductor film which can provide said outstanding characteristic to an organic-semiconductor element, and the organic-semiconductor composition and compound used for this can be provided.

It is a cross-sectional schematic diagram which shows the bottom gate-bottom contact type organic thin-film transistor element which is an example of the semiconductor element of this invention. It is a cross-sectional schematic diagram which shows the bottom gate-top contact type organic thin-film transistor element which is an example of the semiconductor element of this invention.

In this specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the present specification, when “(meth) acrylate” is described, it means acrylate, metaacrylate, or both.

In this specification, the indication of a compound includes its salt and its ion in addition to the compound itself. Moreover, what changed the structure in part within the range which does not impair the target effect is included.
Moreover, about the compound which does not specify substituted or unsubstituted, the thing which has arbitrary substituents is included in the range which does not impair the target effect. The same applies to substituents and linking groups (hereinafter referred to as substituents and the like).

In this specification, when there are a plurality of substituents indicated by a specific symbol, or when a plurality of substituents are specified at the same time, the respective substituents may be the same unless otherwise specified. May be different. The same applies to the definition of the number of substituents and the like. Further, when a plurality of substituents and the like are adjacent (particularly adjacent), they may be connected to each other to form a ring unless otherwise specified.
Further, when the number of carbon atoms of the group is limited, the number of carbon atoms of this group means the total number of carbon atoms including substituents unless otherwise specified.
In the present invention, when a group can form a non-cyclic skeleton and a cyclic skeleton, this group includes a non-cyclic skeleton group and a cyclic skeleton group unless otherwise specified. For example, the alkyl group includes a linear alkyl group, a branched alkyl group, and a cyclic (cyclo) alkyl group. 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, and preferably 5 or more, regardless of the lower limit of the number of atoms specifically described for the group.

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

[Compound represented by Formula (1)]
First, the compound represented by formula (1) of the present invention (hereinafter sometimes referred to as the compound of the present invention) will be described.
The organic semiconductor film containing the compound of the present invention can impart high carrier mobility, high temperature and high humidity resistance, and excellent hysteresis characteristics to the organic semiconductor element. The reason is not clear in detail, but can be considered as follows. As will be described later, the compound of the present invention has at least one group represented by the formula (Z) in a specific condensed ring structure. By having this group, when it is set as the organic-semiconductor composition mentioned later, the solubility (solubility) with respect to a solvent improves, and the productivity of an organic-semiconductor film improves. In addition, in the formed organic semiconductor film, the compound of the present invention is in a predetermined direction with respect to the substrate to which the organic semiconductor composition is applied (the above-mentioned specific condensed ring structure is in an upright state with respect to the substrate to be applied). Arrange closely. Furthermore, the order of the arrangement is maintained near the electrodes. Therefore, film quality stability is improved. As a result, the organic semiconductor film is considered to exhibit high carrier mobility, high temperature and high humidity resistance, and excellent hysteresis characteristics when used in an organic semiconductor element.

In Formula (1), Y ¹ represents CR ^Y1 R ^Y2 or SiR ^Y1 R ^Y2 , and CR ^Y1 R ^Y2 is preferable.
R ^Y1 and R ^Y2 each represent a hydrogen atom or a substituent. The substituent that can be adopted as R ^Y1 and R ^Y2 is not particularly limited. Preferred substituents are alkyl groups (C1 is preferably 1-6, more preferably 1-5, and still more preferably 1-3), and alkenyl groups (C2 is preferably 2-6, 4 is more preferable), an alkynyl group (the carbon number is preferably 2-6, more preferably 2-4), and an alkoxy group (the carbon number is preferably 1-6, more preferably 1-3). , An aromatic hydrocarbon group (the number of carbon atoms is preferably 6 to 18, more preferably 6 to 10), an aromatic heterocyclic group (a 5 to 7-membered ring is preferable. The ring-constituting hetero atom is not particularly limited. Is preferably an oxygen atom, a nitrogen atom, a sulfur atom, a selenium atom, or a silicon atom, preferably having 4 to 18 carbon atoms, more preferably 6 to 10 carbon atoms). R ^Y1 and R ^Y2 are preferably both alkyl groups.

Ring A and ring B each represent an aromatic heterocyclic ring and are condensed with an adjacent benzene ring.
The aromatic heterocyclic ring that can be used as ring A and ring B is not particularly limited, and may be a single ring or a condensed ring in which two or more rings are condensed. This aromatic heterocycle is preferably a monocycle.

  The ring-constituting hetero atom of the aromatic heterocycle is not particularly limited, but is preferably an oxygen atom, a nitrogen atom, a sulfur atom, a selenium atom or a silicon atom, more preferably an oxygen atom, a nitrogen atom, a sulfur atom or a selenium atom, An oxygen atom or a sulfur atom is more preferable, and a sulfur atom is particularly preferable. Examples of the number of ring hetero atoms include 1 to 3, preferably 1 or 2, and more preferably 1.

  The monocyclic aromatic heterocycle is not particularly limited as long as it contains the above-described ring-constituting heteroatoms. The number of single-ring members is not particularly limited, but a 5- to 7-membered ring is preferable. Examples of such monocyclic aromatic heterocycle include, for example, thiophene ring, furan ring, pyrrole ring, selenophene ring, thiazole ring, oxazole ring, isothiazole ring, isoxazole ring, imidazole ring, pyrazole ring, thiadiazole ring, Examples thereof include a 5-membered aromatic heterocycle such as an oxadiazole ring or a silole ring, or a 6-membered aromatic heterocycle such as a pyridine ring, a pyrazine ring, a pyrimidine ring, or a pyridazine ring.

The condensed aromatic heterocycle includes a ring formed by condensing a plurality of the above monocyclic aromatic heterocycles and a mixture of the above monocyclic aromatic heterocycle and a hydrocarbon ring. A ring etc. are mentioned. The hydrocarbon ring only needs to be a ring formed of only carbon atoms as ring-constituting atoms, and examples thereof include a benzene ring and a cyclopentadiene ring. Here, the number of rings to be condensed is not particularly limited, and is preferably 2 to 4, for example, and more preferably 2 or 3.
Examples of the condensed aromatic heterocycle include benzofuran ring, benzothiophene ring, benzopyrrole ring, indole ring, benzoselenophene ring, indazole ring, isoindole ring, quinoline ring, thienopyridine ring, cyclopentadifuran ring, Examples include a cyclopentadithiophene ring, a thieno [3,2-b] thiophene ring, a thieno [2,3-b] thiophene ring, a thieno [3,4-b] thiophene ring, a trithiophene ring, and the like.

As the aromatic heterocyclic ring, the following rings are preferable, and among them, a thiophene ring, a furan ring, a selenophene ring, a pyrrole ring, or a thieno [2,3-b] thiophene ring is more preferable, and a thiophene ring, a furan ring, and a selenophene ring. Alternatively, a pyrrole ring is more preferable, a thiophene ring or a furan ring is particularly preferable, and a thiophene ring is most preferable.
In the following aromatic heterocycle, R ²¹ has the same meaning as R ^{21 of} NR ^{21 which} can be taken as X described later, and preferred ones are also the same.

  The two aromatic heterocycles in the formula (1) may be the same or different from each other, and are preferably the same.

  In the condensed aromatic heterocycle, the ring condensed with the benzene ring in formula (1) may be either an aromatic heterocycle or a hydrocarbon ring. Moreover, the bond position of the ring condensed with the benzene ring is not particularly limited. For example, when the ring condensed with the benzene ring is a 5-membered ring, ring-constituting atoms at the 2nd and 3rd positions are exemplified. In addition to this, the bonding positions in the exemplary compounds described later are mentioned.

R ¹ and R ² in the formula (1) each represent a group represented by the following formula (Z).

^-L-R Z (Z)

In the formula (Z), L is a single bond, a linking group (divalent) represented by any one of the following formulas (L-1) to (L-12), or the following formula (L-1) to A linking group in which two or more linking groups represented by formula (L-12) are bonded is shown.

In the formula (L-1) to the formula (L-12), ** is represented by any one of the connection site with the A ring or the B ring, or the formula (L-1) to the formula (L-12). A bonding site with another linking group is shown, and * represents a bonding site with R ^Z or another linking group represented by any one of formulas (L-1) to (L-12).

R ^Z1 represents a hydrogen atom or a substituent, respectively.
R ^Z2 represents a substituent.
The substituents can take as R ^Z1 and R ^Z2, but are not limited to, include groups selected from the following substituent group G ^Z. Among these, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, or an aromatic hydrocarbon group is preferable, and a fluorine atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group is more preferable.

<Substituent group G ^Z >
A halogen atom (a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), an alkyl group (including a cycloalkyl group, a bicycloalkyl group and a tricycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), Alkynyl group, aromatic hydrocarbon group (also called aryl group), aromatic heterocyclic group (also called heteroaryl group), cyano group, hydroxy group, nitro group, carboxy group, alkoxy group, aryloxy group, silyloxy group, Heteroaryloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxy Cal Nylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heteroarylthio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group , Aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heteroarylazo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, phosphono group, silyl group, hydrazino group, Ureido group, boronic acid group (—B (OH) ₂ ), phosphato group (—OPO (OH) ₂ ) or sulfato group (—OSO ₃ H)

Specifically, as R ^Z1 in formula (L-1) and formula (L-2), a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms is preferable, respectively, and a hydrogen atom or carbon number A 1-6 unsubstituted alkyl group is more preferable, a hydrogen atom or a C1-C3 unsubstituted alkyl group is still more preferable, and a hydrogen atom is especially preferable. Of the two ^RZ1s contained in the linking group represented by the formula (L-1), the number of substituents is preferably 0 or 1, particularly preferably 0.

R ^Z1 in formula (L-6) is preferably a hydrogen atom or a substituted or unsubstituted alkyl group, more preferably a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and 1 to 4 carbon atoms. The substituted or unsubstituted alkyl group is more preferable.

R ^Z2 in formula (L-9) to formula (L-12) is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, substituted or unsubstituted, respectively. An alkoxy group is preferred, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 12 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 12 carbon atoms, or carbon A substituted or unsubstituted alkoxy group of formula 1 to 12 is more preferred.
In Formula (L-9) to Formula (L-12), the position at which R ^Z2 is bonded is not particularly limited.

m1 is an integer of 0 to 4, an integer of 0 to 1 is preferable, and 0 is preferable.
m2 is an integer of 0-2, respectively, 0 or 1 is preferable and 0 is preferable.

  When L is a linking group represented by any one of formulas (L-1) to (L-12), L represents formula (L-1), formula (L-2), formula (L-3). ), The formula (L-9), the formula (L-10), and the formula (L-11) are preferable, and the linking group represented by the formula (L-1), the formula (L-9), the formula (L L-10) and a linking group represented by formula (L-11) are more preferred, and a linking group represented by any of formula (L-1) and formula (L-11) is more preferred.

  When L is a linking group in which two or more linking groups represented by any of formulas (L-1) to (L-12) are bonded, any of formulas (L-1) to (L-12) The number of bonds of the linking group represented by the formula is not particularly limited as long as it is 2 or more, preferably 2 to 10, more preferably 2 to 8, and particularly preferably 2 to 6. .

The linking group in which two or more linking groups represented by the above formulas are bonded is not particularly limited, and examples thereof include the linking groups of the exemplified compounds or the compounds used in the examples described later. Among them, a linking group in which two or more linking groups represented by any one of formula (L-1), formula (L-4), formula (L-5) and formula (L-7) are bonded is preferable. A linking group in which two or more linking groups represented by any one of (L-1), formula (L-4), and formula (L-5) are bonded is more preferred. Formula (L-1) and formula (L -4) is particularly preferably a linking group in which two or more linking groups represented by any one are bonded.
For example, as a linking group in which one linking group represented by the formula (L-4) and one linking group represented by the formula (L-7) are bonded, **-C (= O) -O- *, Or **-OC (= O)-* is mentioned. In addition, as a linking group in which one linking group represented by the formula (L-6) and one linking group represented by the formula (L-7) are bonded, **-C (═O) —NR ^Z1 — * Or **- ^NRZ1- C (= O)-*. Here, *, ** and R ^Z1 are as described above.
Moreover, the thing (alkylene group) which has two or more (for example, 2-5 pieces) the coupling groups represented by Formula (L-1) couple | bonded with the said A ring or B ring is also preferable.

  L is a linking group represented by any one of formulas (L-1) to (L-12) or a linking group represented by any of formulas (L-1) to (L-12). A linking group in which two or more groups are bonded is preferred.

In the above formula (Z), R ^Z represents an alkyl group, a haloalkyl group, a cyano group, a vinyl group, an ethynyl group, an aryl group, a heteroaryl group, a siloxane group, an oligosiloxane group having 2 or more silicon atoms, or tri An alkylsilyl group is shown. Among these, ^RZ is preferably an alkyl group.

The alkyl group that can be used as R ^Z may be linear, branched, or cyclic, and is preferably a linear alkyl group.
In the present invention, when only a substituted or unsubstituted alkyl group (n carbon atoms) is present as the group represented by the above formula (Z), the group represented by the formula (L-1) (corresponding to L) ) and one, alkyl group (corresponding to R ^Z) and are bonded group of carbon number (n-1), to interpret. Specifically, in the case of an n-octyl group, a group in which one methylene group in which R ^{Z1 in} formula (L-1) is a hydrogen atom as L and an n-heptyl group as R ^Z are bonded to each other; Interpret.

When the group represented by the formula (Z) includes an alkyl group, the carrier mobility is increased when the total number of carbon atoms of the alkyl group in L and R ^Z is 4 or more. The total maximum number of carbon atoms of the alkyl group in L and R ^Z is not particularly limited and may be, for example, twenty.

The preferred number of carbon atoms of the alkyl group that can be taken as R ^Z is determined as follows depending on the linking group represented by the above formulas.

When L is a linking group represented by the formula (L-1), the alkyl group that can be taken as R ^Z may be a substituted alkyl group or an unsubstituted alkyl group, and preferably has 2 or more carbon atoms, The number is preferably 2 to 15, and more preferably 3 to 10 from the viewpoint of increasing the carrier mobility.

When L is a linking group represented by formula (L-2) or formula (L-3), the alkyl group that can be taken as R ^Z may be a substituted alkyl group or an unsubstituted alkyl group, and the number of carbon atoms is 2 or more. The number of carbon atoms is preferably 2 to 12, more preferably 2 to 12, and further preferably 3 to 10 carbon atoms, and particularly preferably 4 to 9 carbon atoms from the viewpoint of increasing carrier mobility.

When L is a linking group represented by the formula (L-4) to the formula (L-12), the alkyl group that can be taken as R ^Z may be a substituted alkyl group or an unsubstituted alkyl group, and the number of carbon atoms is 1 to 1. 15 is preferable, 1 to 10 carbon atoms are more preferable, and 1 to 7 carbon atoms are further preferable from the viewpoint of increasing carrier mobility.

When showing the L 2 or of the formula (L-1) ~ 2 divalent linking group linking group is attached, which is represented by any one of (L-12), it can take as above R ^Z, a substituted or unsubstituted the preferred range of number of carbon atoms in the alkyl group is, depending on the type of expression which is adjacent to ^{R Z (L-1) ~} (L-12), determined as described above.

The haloalkyl group that can be taken as R ^Z is an alkyl group in which the hydrogen atom of the alkyl group that can be taken as R ^Z is substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and a fluorine atom is preferable.
In the haloalkyl group, the number of hydrogen atoms substituted with a halogen atom is not particularly limited. For example, a perfluoroalkyl group in which all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms can be mentioned.

The aryl group can take as R ^Z, but are not limited to, include aromatic hydrocarbon groups having 6 to 18 carbon atoms, preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, 6 aromatic carbon A hydrocarbon group is more preferred. The aryl group may be a monocyclic group or a condensed group of two or more rings.
As the aryl group, a benzene ring group, a naphthalene ring group, or a group obtained by removing one hydrogen atom from an aromatic hydrocarbon (for example, a fluorene ring) in which three or more rings are condensed is more preferable. In the aromatic hydrocarbon in which 3 or more rings are condensed, the number of condensed rings is not particularly limited as long as it is 3 or more, but for example, 3 to 6 is preferable. Examples of the group obtained by removing one hydrogen atom from an aromatic hydrocarbon in which three or more rings are condensed include a group obtained by removing one hydrogen atom from a fluorene ring, anthracene ring, phenanthrene ring, chrysene ring or pyrene ring. Can be mentioned.
The aryl group is preferably a benzene ring group or a naphthalene ring group, and more preferably a benzene ring group, from the viewpoint of better carrier mobility.

Examples of the heteroaryl group that can be adopted as R ^Z include a ring group having at least one nitrogen atom, oxygen atom, sulfur atom, or selenium atom as a ring-constituting atom. This heteroaryl group may be a monocyclic group or a condensed group of two or more rings. When it is a monocyclic group, the number of ring members is preferably 5 to 7 members.
Examples of the aromatic heterocyclic ring forming the heteroaryl group include a pyrrole ring, a furan ring, a thiophene ring, a selenophene ring, an oxazole ring, a thiazole ring, an imidazole ring, a triazole ring, a thiadiazole ring, a pyridine ring or a triazine ring. A ring is mentioned. Moreover, the condensed ring which combined at least 2 single ring among these single rings, or the condensed ring of at least 1 said single ring and at least 1 benzene ring or a cyclopentadiene ring etc. are mentioned. In the condensed ring, the number of rings to be combined is not particularly limited as long as it is 2 or more, but for example, 2 to 6 is preferable.
As the heteroaryl group, among them, a thiophene ring group and a furan ring group are preferable.

Examples of the siloxane group that can be used as R ^Z include (R ^Si ) ₃ Si—O— group. R ^Si is a hydrogen atom or a substituent, and the substituent is preferably an alkyl group (preferably having 1 to 3 carbon atoms). The number of substituents among the three R ^Si is not particularly limited and may be 0 to 3, but it is preferable that all three are substituents. Three R ^Si may be the same as or different from each other.

Examples of the oligosiloxane group having 2 or more silicon atoms that can be adopted as R ^Z include groups in which two or more siloxane units having one silicon atom are bonded. The oligosiloxane group preferably has 2 to 4 repeating siloxane units, and more preferably 2 or 3. In addition, a hydrogen atom or an alkyl group is preferably bonded to the silicon atom. When an alkyl group is bonded to a silicon 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 silicon atom, or a different alkyl group or a hydrogen atom may be bonded thereto. Further, among the siloxane units constituting the oligosiloxane group, all but the terminal siloxane unit may be the same or different, but it is preferable that they are all the same.

Examples of the trialkylsilyl group that can be adopted as R ^Z include a group in which three substituted or unsubstituted alkyl groups are bonded to a silicon atom. It is preferable that carbon number of the alkyl group couple | bonded with a silicon atom is 1-3, for example, a methyl group, an ethyl group, or an isopropyl group is mentioned. The alkyl groups bonded to the silicon atom may be the same alkyl group or different alkyl groups.

R ^Z may have a substituent. In this case, the substituent is not particularly limited, and examples thereof include groups selected from the substituent group G ^Z.

In the present invention, as R ¹ and R ² , L is a linking group represented by any one of formula (L-1), formula (L-9), formula (L-10), and formula (L-11). Or a linking group in which two or more linking groups represented by any one of formula (L-1), formula (L-4), formula (L-5) and formula (L-7) are bonded, and R ^A group in which ^Z is an alkyl group is preferred.

When ring A or ring B has R ¹ or R ² , the position (ring member atom) to which R ¹ or R ² is bonded in each ring is not particularly limited. For example, when the ring A and the ring B are monocyclic aromatic heterocycles, the 2-position or the 3-position may be mentioned with respect to the ring-constituting hetero atom (1-position) of each ring, and the 2-position is preferred. In the case where Ring A and Ring B are condensed aromatic heterocycles, in the adjacent ring that is not condensed with the benzene ring in Formula (1), position 2 with respect to the ring-constituting heteroatom (position 1) Or the 3rd position is mentioned and the 2nd position is preferred.

  In the formula (1), p and q are each an integer of 0 to 2, preferably 0 or 1, more preferably 1, and particularly preferably 1. However, the sum (p + q) of p and q is an integer of 1 or more, preferably 1 to 2, and more preferably 2.

In the formula (1), R ³ and R ⁴ each represent a substituent. The substituents can take as R ³ and R ^4, but are not limited to, groups selected from the aforementioned substituent group G ^Z. Especially, a halogen atom, an alkyl group, or an aryl group is preferable, and a fluorine atom, a C1-C3 alkyl group, or a phenyl group is more preferable.

  r and s are each an integer of 0 to 2, preferably 0 or 1, more preferably 0, and particularly preferably 0.

  The compound represented by the formula (1) is preferably a compound represented by the following formula (2-1) or the formula (2-2).

In formula (2-1) or formula (2-2), X represents an oxygen atom, a sulfur atom, a selenium atom or NR ²¹ , respectively, preferably an oxygen atom or a sulfur atom, and more preferably a sulfur atom. Here, R ²¹ represents a hydrogen atom or a substituent. The substituent that can be employed as R ²¹ is not particularly limited, and is the same as the substituent that can be ^employed as R ^Y1 and R ^Y2 , and the preferred range is also the same. R ²¹ is preferably a hydrogen atom or an alkyl group.
Formula (2-1) or ^{Y 1,} R 1 ^{~R 4} and p~s in Formula (2-2), respectively, ^Y 1 in the formula ^(1), R 1 to R ⁴ and p~s synonymous The preferred range is also the same.

  The compounds represented by the formula (2-1) and the formula (2-2) are preferably compounds represented by the following formula (3-1) and the formula (3-2), respectively.

In formula (3-1) and formula (3-2), R ³¹ and R ³² each represent a hydrogen atom or a substituent. The substituent that can be employed as R ³¹ and R ³² is not particularly limited, and is the same as the substituent that can be ^employed as R ^Y1 and R ^Y2 , and the preferred range is also the same. R ³¹ and R ³² are preferably both alkyl groups.
X represents an oxygen atom or a sulfur atom, respectively, and a sulfur atom is preferable.
^{R 1} and ^{R 2} in the formula (3-1) and (3-2), respectively, have the same meanings as ^{R 1} and ^{R 2} in the formula (1), and the preferred range is also the same.

The compound represented by the formula (1) preferably has a molecular weight of 3000 or less, more preferably 2000 or less, still more preferably 1000 or less, and particularly preferably 850 or less. It is preferable to make the molecular weight not more than the above upper limit value because the solubility in a solvent can be increased.
On the other hand, from the viewpoint of film quality stability of the organic semiconductor film, the molecular weight is preferably 300 or more, and more preferably 400 or more.

A method for synthesizing the compound represented by the formula (1) is not particularly limited, and the compound can be synthesized with reference to a usual method. For example, a substituent (R ¹ and R ² ) is obtained by a coupling reaction using a transition metal catalyst on a condensed polycyclic aromatic ring compound (a ring obtained by further condensing an aromatic heterocycle with each benzene ring of the fluorene skeleton). ) And the like.

  Specific examples of the compound represented by the above formula (1) are shown below and in the Examples, but the present invention is not limited thereto. In the compounds shown below, the alkyl group is a linear alkyl group or a branched alkyl group, and a linear alkyl group is preferred.

[Organic semiconductor composition]
Next, the organic semiconductor composition of the present invention will be described.
This organic semiconductor composition contains the compound represented by the above formula (1) and a solvent, and is preferably used for forming the organic semiconductor film of the present invention.

<Compound represented by Formula (1)>
The compound represented by Formula (1) is as above-mentioned, may be used individually by 1 type, and may be used together 2 or more types.
The compound content of the organic semiconductor composition is not particularly limited, and can be represented, for example, by the content in a solid content excluding the solvent described below. As a content rate in solid content, it is preferable to set it as the same range as the content rate of the compound in the organic-semiconductor film mentioned later, for example.

<Solvent>
A solvent will not be specifically limited if the above-mentioned compound is dissolved or disperse | distributed, An inorganic solvent or an organic solvent is mentioned. Among these, an organic solvent is preferable. A solvent may be used individually by 1 type and may use 2 or more types together.

  The organic solvent is not particularly limited, but is a hydrocarbon solvent such as hexane, octane or decane, an aromatic hydrocarbon solvent such as toluene, xylene, mesitylene, ethylbenzene, decalin, 1-methylnaphthalene, tetralin or anisole, acetone, methyl ethyl ketone. Ketone solvents such as methyl isobutyl ketone or cyclohexanone, halogenated hydrocarbon solvents such as dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene or chlorotoluene, ethyl acetate, butyl acetate, amyl acetate or Ester solvent such as ethyl lactate, methanol, propanol, butanol, pentanol, hexanol, cyclohexanol, methyl celloso Alcohol solvent such as butyl, ethyl cellosolve or ethylene glycol, ether solvent such as butoxybenzene, dibutyl ether, tetrahydrofuran or dioxane, amide solvent such as N, N-dimethylformamide or N, N-dimethylacetamide, 1-methyl-2- Examples thereof include imide solvents such as pyrrolidone and 1-methyl-2-imidazolidinone, sulfoxide solvents such as dimethyl sulfoxide, and nitrile solvents such as acetonitrile.

  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 96 to 99.95% by mass. Is more preferable.

<Other ingredients>
The organic semiconductor composition of the present invention may contain components other than the compound of the present invention and a solvent.
Examples of such a component include a binder polymer or various additives.
(Binder polymer)
The organic semiconductor composition of the present invention may contain a binder polymer. The kind of binder polymer can use the binder polymer normally used for the organic-semiconductor composition, without being restrict | limited especially.
Examples of such a binder polymer include polystyrene, poly (α-methylstyrene), polyvinyl cinnamate, poly (4-divinylbenzene), poly (4-vinylphenol), poly (4-methylstyrene), polycarbonate, Insulating polymers such as polyarylate, polyester, polyamide, polyimide, polyurethane, polysiloxane, polysulfone, polymethyl methacrylate, polymethyl acrylate, cellulose, polyethylene or polypropylene, and copolymers thereof, polysilane, polycarbazole, poly Semiconductor polymers such as arylamine, polyfluorene, polythiophene, polypyrrole, polyaniline, polyparaphenylene vinylene, polyacene or polyheteroacene, and these Copolymers, rubbers, or, may be mentioned thermoplastic elastomers.
Among these, as the binder polymer, a polymer compound having a benzene ring (a polymer having a repeating unit having a benzene ring group) is preferable. Although content in particular of the repeating unit which has a benzene ring group is not restrict | limited, 50 mol% or more is preferable in all the repeating units, 70 mol% or more is more preferable, 90 mol% or more is still more preferable. The upper limit is not particularly limited, but 100 mol% can be mentioned.
Although the weight average molecular weight of a binder polymer is not specifically limited, 1,000-10,000,000 are preferable, 3,000-5 million are more preferable, 5,000-3 million are still more preferable.
The content of the binder polymer in the organic semiconductor composition is not particularly limited. For example, the content in the solid content is preferably in the same range as the content of the binder polymer in the organic semiconductor film described later. . When an organic semiconductor film of an organic thin film transistor element is formed using an organic semiconductor composition having a binder polymer content within the above range, the carrier mobility and heat resistance of the organic thin film transistor element are further improved.

(Additive)
As an additive, what is normally used for an organic-semiconductor composition can be used, without being restrict | limited especially.
The content of the additive in the organic semiconductor composition is not particularly limited. For example, the content in the solid content is preferably in the same range as the content of the additive in the organic semiconductor film described later. . It is excellent in film forming property as it is the said range. For example, when an organic semiconductor film of an organic thin film transistor element is formed using an organic semiconductor composition having an additive content within the above range, the film forming property is excellent, and the carrier mobility and heat resistance of the organic thin film transistor element are further improved. To do.

<Preparation method>
The method for preparing the organic semiconductor composition is not particularly limited, and a normal preparation method can be adopted. For example, the organic semiconductor composition of the present invention can be prepared by adding a predetermined amount of each component to a solvent and appropriately stirring.

[Organic semiconductor film]
The organic semiconductor film of the present invention will be described.
The organic semiconductor film of the present invention contains the above-described compound of the present invention, and may contain the above binder polymer or additive. The compound, binder polymer and additive of the present invention are as described above.

The compound of the present invention contained in the organic semiconductor film of the present invention may be one kind or two or more kinds.
The content of the compound in the organic semiconductor film is not particularly limited and can be set as appropriate. For example, it is preferably 10% by mass or more, more preferably 30% by mass or more, and further preferably 50% by mass or more. The upper limit can be 100 mass%, for example, it is preferable that it is 90 mass% or less, and it is still more preferable that it is 80 mass% or less.

The binder polymer may contain 1 type, and may contain 2 or more types.
The content rate of the binder polymer in the organic semiconductor film is not particularly limited and can be appropriately set. For example, 90 mass% or less is preferable, 75 mass% or less is more preferable, and 50 mass% or less is still more preferable. The lower limit can be set to 0% by mass or more, for example, preferably 1% by mass or more, more preferably 10% by mass or more, and further preferably 20% by mass or more.
The additive may contain 1 type, and may contain 2 or more types.
The content of the additive in the organic semiconductor film is preferably 10% by mass or less, preferably 5% by mass or less, and more preferably 1% by mass or less.

  The film thickness of the organic semiconductor film cannot be uniquely determined according to the applied organic semiconductor element. For example, when applied to an organic thin film transistor element, the thickness of the organic semiconductor film is preferably 10 to 500 nm, and more preferably 20 to 200 nm.

This organic semiconductor film is preferably formed by the method described later using the above-described organic semiconductor composition of the present invention.
The organic semiconductor film of the present invention is preferably applied to an organic semiconductor element, and more preferably applied to an organic thin film transistor element.

[Organic semiconductor devices]
The organic semiconductor element of the present invention includes the organic semiconductor film of the present invention.
Although it does not specifically limit as an organic-semiconductor element of this invention, It uses preferably as a nonluminous organic-semiconductor device. The non-light-emitting organic semiconductor device may be any device that does not aim to emit light. For example, an organic thin film transistor element, an organic photoelectric conversion element (an individual imaging element for photosensor use or a solar cell for energy conversion use). , Gas sensors, organic rectifying elements, organic inverters, information recording elements and the like. In a non-light-emitting organic semiconductor device, it is preferable that an organic semiconductor film functions as an electronic element.

<Organic thin-film transistor element>
As one preferred application mode of the organic semiconductor film of the present invention, an embodiment applied to an organic thin film transistor element will be described, but the semiconductor element of the present invention is not limited to this.

The organic thin film transistor element (also referred to as organic TFT element) of the present invention has the above-described organic semiconductor film (organic semiconductor layer) of the present invention, and further includes a source electrode, a drain electrode, and a gate electrode. it can.
The organic TFT element of the present invention is provided on a substrate in contact with an organic semiconductor layer, a gate electrode, an organic semiconductor layer, a gate insulating layer provided between the gate electrode and the organic semiconductor layer, and an organic semiconductor layer. And a source electrode and a drain electrode which are connected via each other. In this organic TFT element, an organic semiconductor layer and a gate insulating layer are provided adjacent to each other.
If the organic thin-film transistor element of this invention is provided with said each layer, it will not specifically limit about the structure. For example, it has any structure such as bottom contact type (bottom gate-bottom contact type and top gate-bottom contact type) or top contact type (bottom gate-top contact type and top gate-top contact type). May be.
Hereinafter, an example of the organic thin film transistor element 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 type organic thin film transistor element 100 as an example of the semiconductor element of the present invention.
As shown in FIG. 1, the organic thin film transistor element 100 includes a substrate (base material) 10, a gate electrode 20, a gate insulating film 30, a source electrode 40 and a drain electrode 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 (organic semiconductor layer) and the sealing layer, and the respective production methods will be described in detail.

(substrate)
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 silicon substrate, a glass substrate, or 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.
Although the thickness of a board | substrate is not specifically limited, For example, it is preferable that it is 10 mm or less, it is still more preferable that it is 2 mm or less, and it is especially preferable that it is 1.5 mm or less. On the other hand, it is preferably 0.01 mm or more, and more preferably 0.05 mm or more.

(Gate electrode)
As the gate electrode, a normal electrode used as the gate electrode of the organic TFT element can be applied without particular limitation.
The material (electrode material) for forming the gate electrode is not particularly limited. For example, gold, silver, aluminum, copper, chromium, nickel, cobalt, titanium, platinum, magnesium, calcium, barium, sodium, or a metal such as InO ₂ , conductive oxide such as SnO ₂ or indium tin oxide (ITO), conductive polymer such as polyaniline, polypyrrole, polythiophene, polyacetylene or polydiacetylene, semiconductor such as silicon, germanium or gallium arsenide, or fullerene And carbon materials such as carbon nanotubes or graphite. Especially, the said metal is preferable and silver or aluminum is more preferable.
Although the thickness of a gate electrode is not specifically limited, It is preferable that it is 20-200 nm.
The gate electrode may function as the substrate, and in this case, the substrate may not be provided.

  A method for forming the gate electrode is not particularly limited. For example, a method for vacuum deposition (hereinafter also simply referred to as vapor deposition) or sputtering of the above electrode material on a substrate, or a composition for forming an electrode containing the above electrode material. Examples thereof include a method for applying or printing an object. In the case of patterning the electrode, examples of the patterning method include printing methods such as inkjet printing, screen printing, offset printing or relief printing (flexographic printing), photolithography methods, mask vapor deposition methods, and the like.

(Gate insulation film)
The gate insulating layer is not particularly limited as long as it is an insulating layer, and may be a single layer or a multilayer.
The material for forming the gate insulating film is not particularly limited. For example, polymethyl methacrylate, polystyrene, polyvinyl phenol, melamine resin, polyimide, polycarbonate, polyester, polyvinyl alcohol, polyvinyl acetate, polyurethane, polysulfone, polybenzoxa Examples thereof include polymers such as sol, polysilsesquioxane, epoxy resin or phenol resin, oxides such as silicon dioxide, aluminum oxide or titanium oxide, or nitrides such as silicon nitride. Among these, the polymer is preferable in view of compatibility with the organic semiconductor film.
These materials may be used alone or in combination of two or more.
Although the film thickness of a gate insulating film is not specifically limited, It is preferable that it is 100-1000 nm.

  A method for forming the gate insulating film is not particularly limited. For example, a method of applying a composition for forming a gate insulating film containing the above material onto a substrate on which a gate electrode is formed, or vapor deposition or sputtering of the above material. Methods and the like.

(Source electrode and drain electrode)
In the organic TFT element of the present invention, the source electrode is an electrode through which current flows from the outside through wiring. The drain electrode is an electrode that sends current to the outside through wiring.
The material for forming the source electrode and the drain electrode can be the same as the electrode material for forming the gate electrode described above. Among these, metals are preferable, and silver is more preferable.
Although the thickness of a source electrode and a drain electrode is not specifically limited, 1 nm or more is preferable respectively and 10 nm or more is especially preferable. Moreover, 500 nm or less is preferable and 300 nm or less is especially preferable.
Although the space | interval (gate length) between a source electrode and a drain electrode can be determined suitably, for example, 200 micrometers or less are preferable and 100 micrometers or less are especially preferable. The gate width can be determined as appropriate, but is preferably 5000 μm or less, and particularly preferably 1000 μm or less.
A method for forming the source electrode and the drain electrode is not particularly limited. For example, a method of vacuum-depositing or sputtering an electrode material on a substrate on which a gate electrode and a gate insulating film are formed, and applying an electrode forming composition. Or the method of printing etc. are mentioned. In the case of patterning, the patterning method is the same as the gate electrode method described above.

(Organic semiconductor film)
In the organic TFT element, the organic semiconductor film of the present invention described above is used as the organic semiconductor film.
This organic semiconductor film can be formed by applying the organic semiconductor composition described above. Specifically, an organic semiconductor film can be formed by applying the organic semiconductor composition described above onto a substrate and drying it.
In the present invention, the application of the organic semiconductor composition on the substrate means not only an embodiment in which the organic semiconductor composition is directly applied to the substrate, but also the organic semiconductor composition above the substrate via another layer provided on the substrate. A mode of applying the object is also included. As another layer, a gate insulating film, a source electrode, or a drain electrode is mentioned, for example.
As a coating method of the organic semiconductor composition, a normal method can be used, for example, 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, or a screen. The printing method is mentioned. Furthermore, as a coating method of the organic semiconductor composition, a method for forming an organic semiconductor film (so-called gap casting method) described in JP2013-207085A, and a method for manufacturing an organic semiconductor thin film described in International Publication No. 2014/175351 A method (so-called edge casting method or continuous edge casting method) or the like is also preferably used.
Drying (drying process) can select suitable conditions according to the kind of each component contained in an organic-semiconductor composition. Although natural drying may be used, heat treatment is preferable from the viewpoint of improving productivity. Although the heat treatment conditions cannot be uniquely determined, for example, the heating temperature is preferably 30 to 250 ° C, more preferably 40 to 200 ° C, still more preferably 50 to 150 ° C, and the heating time is 10 to 300 minutes. Preferably, 20 to 180 minutes is more preferable.

(Sealing layer)
The organic thin film transistor element of the present invention preferably includes a sealing layer as the outermost layer from the viewpoint of durability. For the sealing layer, a sealing agent (composition for forming a sealing layer) usually used for organic TFT elements can be used.
Although the film thickness of a sealing layer is not specifically limited, It is preferable that it is 0.2-10 micrometers.

− Bottom gate − Top contact type organic thin film transistor device −
FIG. 2 is a schematic cross-sectional view showing a bottom gate-top contact type organic thin film transistor element 200 which is an example of the semiconductor element 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, a source electrode 40 and a drain electrode 42, an organic semiconductor film 50, and a sealing layer 60. Have in this order.
The organic thin film transistor element 200 is the same as the organic thin film transistor element 100 except that the layer configuration (stacking mode) is different. Therefore, the substrate, gate electrode, gate insulating film, source electrode, drain electrode, organic semiconductor film, and sealing layer are the same as those in the above-described bottom gate-bottom contact type organic thin film transistor element. Omitted.

  The present invention will be described in more detail based on examples, but the present invention is not limited to the following examples.

  Compounds 1 to 19 used in each example are shown below. In the following compounds, the alkyl group is a linear alkyl group.

[Synthesis example]
<Synthesis Example 1: Synthesis of Compound 1>
Compound 1 was synthesized according to the following scheme. 3,6-Dibromo-9,9-dimethylfluorene is described in Journal of Material Chemistry, 2012, 22, p. Synthesis was performed according to the method described in 4383-4390, and Intermediate 1 was synthesized with reference to the method described in Non-Patent Document 1.

-Synthesis of Intermediate 2-
Under a nitrogen atmosphere, Intermediate 1 (2 g, 6.53 mmol) and tetrahydrofuran (THF, 65 mL) were mixed and cooled to -90 ° C. To this, 14 mL of a tetrahydrofuran solution of lithium tetramethylpiperidine (TMPLi, 14.0 mmol) was added dropwise, followed by stirring at −90 ° C. for 1 hour. Next, a solution of dibromotetrachloroethane (6.37 g, 19.6 mmol) dissolved in 20 mL of tetrahydrofuran was added dropwise to the obtained liquid, and the mixture was further stirred for 30 minutes. The temperature of the reaction solution was raised to room temperature (about 20 ° C.), water was added to quench the reaction, and the reaction product was extracted with chloroform. The organic phase was dried over sodium sulfate, filtered and concentrated. The obtained crude product was recrystallized twice with toluene / methanol to obtain Intermediate 2 (1.97 g, yield 65%).

-Synthesis of Compound 1-
Under a nitrogen atmosphere, Intermediate 2 (300 mg, 0.65 mmol), 0.5 M (mol / L) of butyl zinc bromide in tetrahydrofuran (7.8 mL, 3.9 mmol) and [1,1′-bis (diphenyl) Phosphino) ferrocene] dichloropalladium (II) dichloromethane adduct (53 mg, 0.06 mmol) was mixed and heated to reflux for 3 hours. The reaction solution was cooled to room temperature, methanol was added to deactivate the alkyl metal reagent, and the reaction product was extracted with chloroform. The organic phase was washed with water, dried over sodium sulfate, filtered and concentrated. The resulting crude product was purified by preparative purification gel permeation chromatography (GPC (Gel Permeation Chromatography), eluent: tetrahydrofuran) to obtain Compound 1 (122 mg, yield: 45%).

<Synthesis Example 2: Synthesis of Compound 10>
Compound 10 was synthesized according to the following scheme.

  Under nitrogen atmosphere, intermediate 2 (300 mg, 0.65 mmol), (5-hexylthiophen-2-yl) trimethyltin (535 mg, 1.62 mmol), N, N-dimethylformamide (DMF, 6.5 mL), 0 A tetrahydrofuran solution (3.3 mL, 1.65 mmol) of 5 M lithium chloride and tetrakistriphenylphosphine palladium (0) (37 mg, 32,3 μmol) were mixed, and the mixture was heated and stirred at 100 ° C. for 5 hours. The reaction solution was concentrated to dryness and then purified by silica gel column chromatography (eluent: chloroform). The resulting crude product was further purified by preparative gel permeation chromatography (GPC, eluent: tetrahydrofuran) to obtain Compound 10 (223 mg, 54% yield).

<Synthesis Example 3: Synthesis of Compound 12>
Compound 12 was synthesized according to the following scheme.

Under a nitrogen atmosphere, a magnesium ribbon (165 mg, 6.79 mmol) and tetrahydrofuran (1.5 mL) were mixed. A solution of 1-bromo-3-methoxypropane (989 mg, 6.46 mmol) diluted in tetrahydrofuran (4 mL) was added dropwise thereto, and the mixture was further stirred for 1 hour to prepare a Grignard reagent. did.
A 0.5 M solution of zinc chloride in tetrahydrofuran (12.9 mL, 6.46 mmol) was cooled to 0 ° C., and the Grignard reagent prepared above was added dropwise. After the temperature of the reaction solution was increased to room temperature, intermediate 2 (300 mg, 0.65 mmol) and [1,1′-bis (diphenylphosphino) ferrocene] dichloropalladium (II) dichloromethane adduct (53 mg, 0.06 mmol) ) And heated to reflux for 3 hours. The reaction solution was cooled to room temperature, methanol was added to deactivate the alkyl metal reagent, and the reaction product was extracted with chloroform. The organic phase was washed with water, dried over sodium sulfate, filtered and concentrated. The resulting crude product was purified by preparative gel permeation chromatography (GPC, eluent: tetrahydrofuran) to obtain Compound 15 (125 mg, 43% yield).

<Synthesis Example 4: Synthesis of Compounds 2-9, 11 and 13-19>
Compounds 2-9, 11 and 13-19 were synthesized in the same manner as in Synthesis Examples 1, 2, or 3.

<Compound for comparison>
Comparative compounds 1 to 3 shown below were prepared.
Comparative compound 1 and comparative compound 2 are both compounds described in Non-Patent Document 1, and were synthesized according to the synthesis method described in Non-Patent Document 1.
Comparative compound 3 was synthesized according to the synthesis method described in Non-Patent Document 1.

[Preparation Example of Organic Semiconductor Composition]
1 mL of toluene and 1 mg of the compound shown in Table 1 were put into a glass vial, and stirred and mixed at 60 ° C. for 1 hour with a mix rotor (manufactured by ASONE). Subsequently, the obtained liquid was filtered through a 0.5 μm membrane filter, and the organic semiconductor compositions 1 to 17 of the present invention, the organic semiconductor compositions 18 and 19 for reference, and the organic semiconductor composition for comparison were used. c1-c3 were prepared.
The content rate of the compound in each obtained composition was all 0.11 mass%.

[Example 1]
A bottom gate-bottom contact type organic thin film transistor element 100 shown in FIG. 1 was manufactured and its characteristics were evaluated.
<Manufacture of organic thin-film transistor elements>
Aluminum was vapor-deposited on a glass substrate (Eagle XG: manufactured by Corning, thickness 1.1 mm) to form a gate electrode (thickness 50 nm). On top of that, a composition for forming a gate insulating film (polyvinylphenol / melamine resin = 1 mass part / 1 mass part of PGMEA (propylene glycol monomethyl ether acetate) solution (solid content concentration 2 mass%)) is spin-coated, 150 A gate insulating film having a film thickness of 400 nm was formed by baking (heat drying) at 60 ° C. for 60 minutes.
Next, a silver ink (silver nanocolloid H-1 (trade name), manufactured by Mitsubishi Materials Corporation) is used thereon, and an ink jet apparatus: DMP-2831 (trade name, manufactured by Fuji Film Dimatics) is used as a source electrode. And a drain electrode (thickness: about 100 nm, gate length: 100 μm, gate width: 200 μm). Thereafter, the substrate was baked at 180 ° C. for 30 minutes and sintered to form a source electrode and a drain electrode. Thus, a device precursor was obtained.
In a nitrogen glove box, 300 μL of each organic semiconductor composition shown in Table 1 was cast on the device precursor, and then dried on a hot plate at 60 ° C. for 1 hour to obtain an organic semiconductor layer (film thickness 200 nm). Formed. In this way, organic thin film transistor elements 1 to 17 of the present invention, organic thin film transistors 18 and 19 for reference, and organic thin film transistor elements C1 to C3 for comparison were manufactured, respectively.
The compound content in the organic semiconductor layer was 100% by mass.

<Evaluation of organic thin film transistor element>
About each manufactured organic thin-film transistor element, the following performance evaluation was carried out in air | atmosphere using semiconductor characteristic evaluation apparatus: B2900A (brand name, product made by Agilent Technologies). The results are shown in Table 1.

(Measurement of carrier mobility μ)
A voltage of −60 V is applied between the source electrode and the drain electrode of each organic thin film transistor element, the gate voltage is changed in the range of +20 V to −80 V, and the carrier mobility μ (cm ₎ is expressed using the following formula representing the drain current I _d. ² / Vs) was calculated and evaluated. The carrier mobility mu, preferably higher, in this study, is preferably 0.05 cm ² / Vs or more, more preferably 0.1 cm ² / Vs or more, is 0.2 cm ² / Vs or more It is particularly preferred.

I _d = (w / 2L) μC _i (V _g −V _th ) ²
In the formula, L is the gate length, w is the gate width, μ is the carrier mobility, C _i is the capacitance per unit area of the gate insulating layer, V _g is the gate voltage, and V _th is the threshold voltage.

(High temperature and high humidity resistance (Stability over time in high temperature and high humidity environment))
In the “measurement of carrier mobility μ” test, organic thin film transistor elements having a carrier mobility μ of 0.01 cm ² / Vs or more were stored for 24 hours in an environment of 50 ° C. and a relative humidity of 80%, respectively. The carrier mobility μ was measured by the same method as “measurement of carrier mobility μ”.
In each organic thin film transistor element, the carrier mobility maintenance rate (%) is calculated based on the following formula using the carrier mobility μ ^Be before storage and the carrier mobility μ ^Af after storage. It was used as an indicator of stability over time in a wet environment. The obtained carrier mobility maintenance rate was evaluated according to the following evaluation criteria. The larger the carrier mobility retention rate, the higher the temporal stability in a high temperature and high humidity environment. In this test, it is preferably “B” or more, and more preferably “A”.

Carrier mobility maintenance ratio (%) = (carrier mobility μ ^Af / carrier mobility μ ^Be ) × 100

Carrier mobility maintenance rate (%)
“A”: 90% or more “B”: 75% or more and less than 90% “C”: 50% or more and less than 75% “D”: 25% or more and less than 50%

(Evaluation of hysteresis characteristics)
The voltage applied between the source electrode and the drain electrode was fixed at −60 V, the gate voltage was changed in the range of +20 V to −80 V, and the threshold voltage V _th ⁺ was obtained. Similarly, the threshold voltage V _th ⁻ when the voltage applied between the source electrode and the drain electrode was fixed at −60 V and the gate voltage was changed from −80 V to +20 V was obtained. The absolute value of the difference between V _th ⁺ and V _th ⁻ was used as an index of hysteresis characteristics. The closer the absolute value is to 0, the better the hysteresis characteristics. When the hysteresis characteristic is excellent, the organic thin film transistor element can be stably operated.
The absolute value of the difference between V _th ⁺ and V _th ⁻ is
“A”: 0 V or more and less than 3 V “B”: 3 V or more and less than 7 V “C”: 7 V or more

From the results in Table 1, the following can be understood.
Each of the organic thin film transistor elements C1 to C3 includes an organic semiconductor layer containing the above-described comparative compound that does not have the group represented by the formula (Z), and has carrier mobility μ or high temperature and high humidity resistance, and hysteresis. Both properties were not sufficient. That is, the organic thin film transistor elements C1 and C2 provided with the organic semiconductor film containing the comparative compounds 1 and 2 have a carrier mobility μ that is too small and has a low hysteresis characteristic, and do not function sufficiently as an organic thin film transistor. Moreover, the organic thin film transistor element C3 provided with the organic semiconductor film containing the comparative compound 3 was inferior in all of carrier mobility μ, high temperature and high humidity resistance, and hysteresis characteristics.

On the other hand, the organic thin film transistor elements 1 to 19 using the compounds 1 to 19 having the group represented by the formula (Z) all exhibit high carrier mobility μ and high temperature and high humidity resistance, and further have hysteresis characteristics. It was also found to be excellent.
In particular, the L of formula (Z) is a linking group represented by the formula (L-1) or Formula (L-11), when R ^Z is further coupled to the linking groups of these is an alkyl group, 0 A carrier mobility μ of 20 cm ² / Vs or higher was exhibited, and the carrier mobility μ, high temperature and high humidity resistance, and hysteresis characteristics could be combined at a higher level (element Nos. 1 to 5, 10 and 16 to 19). .

DESCRIPTION OF SYMBOLS 10 Substrate 20 Gate electrode 30 Gate insulating film 40 Source electrode 42 Drain electrode 50 Organic semiconductor film (semiconductor active layer)
60 Sealing layer 100, 200 Organic thin film transistor element

Claims (19)

The organic-semiconductor element provided with the organic-semiconductor film containing the compound represented by a following formula (2-2) .

In formula (2-2) ,
X each independently represents an oxygen atom, a sulfur atom or a selenium atom.
Y ¹ represents CR ^Y1 R ^Y2 or SiR ^Y1 R ^Y2 , and R ^Y1 and R ^Y2 each independently represent a hydrogen atom or a substituent .
R ¹ and R ² each independently represent a group represented by the following formula (Z). p and q are each independently an integer of 0 to 2. However, p + q is an integer of 1 or more.
R ³ and R ⁴ each independently represent a substituent. r and s are each independently an integer of 0 to 2.
^-L-R Z (Z)
In formula (Z),
L is a single bond, a linking group represented by any of the following formulas (L-1) to (L-12), or any one of the following formulas (L-1) to (L-12). A linking group in which two or more of the represented linking groups are bonded is shown.
R ^Z represents an alkyl group, a haloalkyl group, a cyano group, a vinyl group, an ethynyl group, an aryl group, a heteroaryl group, a siloxane group, an oligosiloxane group having 2 or more silicon atoms, or a trialkylsilyl group.

In formula (L-1) to formula (L-12),
** represents a linking site with an aromatic heterocycle having X as a ring-constituting atom in formula (2-2) , or any one of formula (L-1) to formula (L-12) The coupling | bonding site | part with a coupling group of * shows the coupling | bonding site | part with the other coupling group represented by either said R ^<Z > or Formula (L-1)-Formula (L-12).
m1 is an integer of 0-4, and m2 is an integer of 0-2 each independently.
R ^Z1 each independently represents a hydrogen atom or a substituent.
R ^Z2 each independently represents a substituent. The organic semiconductor element according to claim 1, wherein both r and s are 0. The organic semiconductor element according to claim 1, wherein both p and q are 1. 3. Y ¹ But CR ^Y1 R ^Y2 The organic semiconductor element according to any one of claims 1 to 3. The organic semiconductor element according to claim 1, wherein X is an oxygen atom or a sulfur atom. The organic semiconductor element according to claim 1, wherein the compound represented by the formula (2-2) is represented by the following formula (3-2).

In formula (3-2),
R ³¹ And R ³² Each independently represents a hydrogen atom or a substituent.
X represents an oxygen atom or a sulfur atom each independently.
R ¹ And R ² Are R in the formula (2-2), respectively. ¹ And R ² It is synonymous with. R in the formula (2-2) ^Y1 And R ^Y2 Or R in the formula (3-2) ³¹ And R ³² Are each independently a C1-C6 alkyl group, The organic-semiconductor element of any one of Claims 1-6. R in the formula (2-2) or the formula (3-2) ¹ And R ² L is a linking group represented by any one of formula (L-1), formula (L-9), formula (L-10) and formula (L-11), or formula (L -1), a linking group in which two or more linking groups represented by any one of the formula (L-4), the formula (L-5) and the formula (L-7) are bonded, and R ^Z The organic-semiconductor element of any one of Claims 1-7 which shows group which is an alkyl group. The organic semiconductor element according to claim 1, wherein the organic semiconductor element is an organic thin film transistor element. A compound represented by the following formula (2-2).

In formula (2-2),
X each independently represents an oxygen atom, a sulfur atom or a selenium atom.
Y ¹ Is CR ^Y1 R ^Y2 Or SiR ^Y1 R ^Y2 R ^Y1 And R ^Y2 Each independently represents a hydrogen atom or a substituent.
R ¹ And R ² Each independently represents a group represented by the following formula (Z). p and q are each independently an integer of 0 to 2. However, p + q is an integer of 1 or more.
R ³ And R ⁴ Each independently represents a substituent. r and s are each independently an integer of 0 to 2.
                          -LR ^Z       (Z)
In formula (Z),
L is a single bond, a linking group represented by any of the following formulas (L-1) to (L-12), or any one of the following formulas (L-1) to (L-12). A linking group in which two or more of the represented linking groups are bonded is shown.
R ^Z Represents an alkyl group, a haloalkyl group, a cyano group, a vinyl group, an ethynyl group, an aryl group, a heteroaryl group, a siloxane group, an oligosiloxane group having 2 or more silicon atoms, or a trialkylsilyl group.

In formula (L-1) to formula (L-12),
** represents a linking site with an aromatic heterocycle having X as a ring-constituting atom in formula (2-2), or any one of formula (L-1) to formula (L-12) Represents a bonding site with a linking group of ^Z Or a binding site with another linking group represented by any one of formula (L-1) to formula (L-12).
m1 is an integer of 0-4, and m2 is an integer of 0-2 each independently.
R ^Z1 Each independently represents a hydrogen atom or a substituent.
R ^Z2 Each independently represents a substituent. The compound according to claim 10, wherein both r and s are 0. The compound according to claim 10 or 11, wherein both of p and q are 1. Formula Y ¹ But CR ^Y1 R ^Y2 The compound according to any one of claims 10 to 12. Said X is an oxygen atom or a sulfur atom, The compound of any one of Claims 10-13. The compound according to any one of claims 10 to 14, wherein the compound represented by the formula (2-2) is represented by the following formula (3-2).

In formula (3-2) ,
R ³¹ and R ³² each independently represent a hydrogen atom or a substituent.
X represents an oxygen atom or a sulfur atom each independently.
R ¹ and R ² have the same meanings as R ¹ and R ^{2 in} the formula (2-2), respectively . R in the formula (2-2) ^Y1 And R ^Y2 Or R in the formula (3-2) ³¹ And R ³² Is a C1-C6 alkyl group, respectively, The compound of any one of Claims 10-15. R in the formula (2-2) or the formula (3-2) ¹ And R ² L is a linking group represented by any one of formula (L-1), formula (L-9), formula (L-10) and formula (L-11), or formula (L -1), a linking group in which two or more linking groups represented by any one of the formula (L-4), the formula (L-5) and the formula (L-7) are bonded, and R ^Z The compound of any one of Claims 10-16 which shows group which is an alkyl group. The organic-semiconductor composition containing the compound and solvent of any one of Claims 10-17. The organic-semiconductor film containing the compound of any one of Claims 10-17.

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