JP5972234B2 - Organic thin film transistor, organic semiconductor thin film and organic semiconductor material - Google Patents

Description

  The present invention relates to an organic thin film transistor, an organic semiconductor thin film, an organic semiconductor material, and the like. Specifically, the present invention relates to a compound having a chrysenodipyrrole structure, an organic thin film transistor containing the compound, an organic semiconductor material for a non-luminescent organic semiconductor device containing the compound, a material for an organic thin film transistor containing the compound, It is related with the coating solution for nonluminous organic-semiconductor devices characterized by containing this compound, and the organic-semiconductor film for nonluminous organic-semiconductor devices containing this compound.

  Devices using organic semiconductor materials are attracting a great deal of interest because they are expected to have various advantages over conventional devices using inorganic semiconductor materials such as silicon. Examples of a device using an organic semiconductor material include a photoelectric conversion element such as an organic thin film solar cell or a solid-state imaging device using the organic semiconductor material as a photoelectric conversion material, and a non-light emitting organic transistor. A device using an organic semiconductor material may be capable of manufacturing a large-area element at a lower temperature and lower cost than a device using an inorganic semiconductor material. Furthermore, since the material characteristics can be easily changed by changing the molecular structure, there are a wide variety of materials, and it is possible to realize functions and elements that could not be achieved with inorganic semiconductor materials.

For example, Patent Document 1 describes a compound obtained by condensing a benzene ring or a heterocycle (thiophene ring, furan ring, pyrrole ring) at both ends of chrysene, and in particular, a carbon atom on a nitrogen atom at both ends of chrysene. The general formula of the structure which has a pyrrole ring which has a substituent of several 1-30 is described. Patent Document 1 describes that by using this compound for an organic thin film transistor, an organic thin film transistor having a high mobility, a high driving speed, and a large on / off ratio can be obtained. However, Patent Document 1 lists only compounds having a methyl group on the nitrogen atom of the pyrrole ring as specific examples of compounds in which pyrrole rings are introduced at both ends of chrysene. In the example of Patent Document 1, dibenzochrysene is listed. Only dithienochrysene has been studied, and the solubility was about 0.5% by mass with respect to chloroform.
On the other hand, Patent Document 2 describes a compound having a pyrrole ring on both ends or one end of a condensed ring of 3 to 7 aromatic rings, particularly on both ends of chrysene on a nitrogen atom. The general formula of the structure which has a pyrrole ring which has a C1-C40 alkyl group is described. Patent Document 2 describes that by using this compound for an organic thin film transistor, an organic thin film transistor having a high charge transport rate, a low threshold voltage, and a large on / off ratio was obtained. However, in the example of Patent Document 2, the organic thin film transistor characteristics are examined only for a compound having a pyrrole ring having a branched alkyl group having 5 carbon atoms on a nitrogen atom at one end of chrysene, and field effect transfer The voltage was as low as about 0.003 cm ² / Vs, and the drive voltage was still a high value of about −40 V as a threshold voltage in the bottom gate / top contact element of the gold electrode.

International Publication WO2010 / 024388 International Publication WO2013 / 078407

  Under such circumstances, the present inventors examined organic thin film transistors using the compounds described in Examples of Patent Document 1 or 2, and many of the compounds described in Examples of these documents are carriers. The mobility was low, the driving voltage was high, and the solubility in organic solvents was low.

  Therefore, the present inventors proceeded with studies in order to solve such problems of the prior art. The problem to be solved by the present invention is to use a compound having high carrier mobility, low driving voltage and high solubility in an organic solvent when used in a semiconductor active layer of an organic thin film transistor. An organic thin film transistor is provided.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that, among the structures represented by the general formulas of Patent Documents 1 and 2, chrysenodipyrrole that has not been disclosed in these documents By introducing a specific substituent at the 2-position of the pyrrole ring of the structure and having an unsubstituted NH, the carrier mobility is high when used in a semiconductor active layer of an organic thin film transistor, and driving The inventors have found that a compound having a low voltage and high solubility in an organic solvent can be obtained, leading to the present invention.
The present invention, which is a specific means for solving the above problems, has the following configuration.

（一般式（１）において、Ｒ¹〜Ｒ¹⁰はそれぞれ独立に水素原子またはハロゲン原子を表す。
Ｒ²³およびＲ²⁴はそれぞれ独立に水素原子または置換基を表し、Ｒ²³およびＲ²⁴のうち少なくとも１つは下記一般式（Ｗ）で表される置換基である。）
−Ｓ−Ｌ−Ｔ 一般式（Ｗ）
（一般式（Ｗ）においてＳは−(ＣＲ^S ₂)_n−を表す（Ｒ^Sはそれぞれ独立に水素原子またはハロゲン原子を表し、ｎは０〜１７の整数を表す）。Ｌは下記一般式（Ｌ−１）〜（Ｌ−１５）のいずれかで表される２価の連結基または下記一般式（Ｌ−１）〜（Ｌ−１５）のいずれかで表される２価の連結基が２つ以上結合した２価の連結基を表す。Ｔは置換または無置換のアルキル基、オキシエチレン単位の繰り返し数ｖが１以上のオリゴオキシエチレン基、ケイ素原子数が１以上のオリゴシロキサン基、あるいは、置換または無置換のシリル基を表す。ただし、Ｔが置換または無置換のシリル基を表すのは、Ｔに隣接するＬが下記一般式（Ｌ−３）で表される２価の連結基である場合に限る。）

（一般式（Ｌ−１）〜（Ｌ−１５）において、波線部分はＳとの結合位置を示す。一般式（Ｌ−１０）におけるｍは４を表し、一般式（Ｌ−１１）〜（Ｌ−１３）におけるｍは２を表す。一般式（Ｌ−１）、（Ｌ−２）および（Ｌ−１０）〜（Ｌ−１４）におけるＲ’はそれぞれ独立に水素原子または置換基を表す。Ｒⁿは水素原子またはメチル基を表す。Ｒ^siはそれぞれ独立に水素原子、アルキル基、アルケニル基またはアルキニル基を表す。）
［２］ ［１］に記載の有機薄膜トランジスタは、前記一般式（１）で表される化合物が、下記一般式（２）で表される化合物であることが好ましい。
一般式（２）

（一般式（２）において、Ｒ²³およびＲ²⁴はそれぞれ独立に水素原子または置換基を表し、Ｒ²³およびＲ²⁴のうち少なくとも１つは前記一般式（Ｗ）で表される基である。）
［３］ ［１］または［２］に記載の有機薄膜トランジスタは、前記一般式（１）において、Ｓ、ＬおよびＴに含まれる炭素数の合計が５〜１８であることが好ましい。
［４］ ［１］〜［３］のいずれか１項に記載の有機薄膜トランジスタは、前記一般式（１）において、Ｌが前記一般式（Ｌ−１）〜（Ｌ−６）および（Ｌ−１０）〜（Ｌ−１５）のいずれかで表される２価の連結基、または前記一般式（Ｌ−１）〜（Ｌ−６）および（Ｌ−１０）〜（Ｌ−１５）のいずれかで表される２価の連結基が２つ以上結合した２価の連結基であることが好ましい。
［５］ ［１］〜［４］のいずれか一項に記載の有機薄膜トランジスタは、前記一般式（１）において、Ｌが前記一般式（Ｌ−１）で表される２価の連結基を含む２価の連結基であることが好ましい。
［６］ ［１］〜［５］のいずれか一項に記載の有機薄膜トランジスタは、前記一般式（１）において、Ｌが前記一般式（Ｌ−１）で表される２価の連結基であり、Ｔが置換または無置換のアルキル基であることが好ましい。
［７］ ［１］〜［５］のいずれか一項に記載の有機薄膜トランジスタは、前記一般式（１）において、Ｌが前記一般式（Ｌ−６）で表される２価の連結基を含む２価の連結基であることが好ましい。
［８］ ［１］〜［７］のいずれか一項に記載の有機薄膜トランジスタは、前記一般式（１）において、Ｔが直鎖アルキル基であることが好ましい。
［９］ ［１］〜［７］のいずれか一項に記載の有機薄膜トランジスタは、前記一般式（１）において、Ｔが分枝アルキル基であることが好ましい。
［１０］ 下記一般式（１）で表される化合物。
一般式（１）

（一般式（１）において、Ｒ¹〜Ｒ¹⁰はそれぞれ独立に水素原子またはハロゲン原子を表す。
Ｒ²³およびＲ²⁴はそれぞれ独立に水素原子または置換基を表し、Ｒ²³およびＲ²⁴のうち少なくとも１つは下記一般式（Ｗ）で表される置換基である。）
−Ｓ−Ｌ−Ｔ 一般式（Ｗ）
（一般式（Ｗ）においてＳは−(ＣＲ^S ₂)_n−を表す（Ｒ^Sはそれぞれ独立に水素原子またはハロゲン原子を表し、ｎは０〜１７の整数を表す）。Ｌは下記一般式（Ｌ−１）〜（Ｌ−１５）のいずれかで表される２価の連結基または下記一般式（Ｌ−１）〜（Ｌ−１５）のいずれかで表される２価の連結基が２つ以上結合した２価の連結基を表す。Ｔは置換または無置換のアルキル基、オキシエチレン単位の繰り返し数ｖが１以上のオリゴオキシエチレン基、ケイ素原子数が１以上のオリゴシロキサン基、あるいは、置換または無置換のシリル基を表す。ただし、Ｔが置換または無置換のシリル基を表すのは、Ｔに隣接するＬが下記一般式（Ｌ−３）で表される２価の連結基である場合に限る。）

（一般式（Ｌ−１）〜（Ｌ−１５）において、波線部分はＳとの結合位置を示す。一般式（Ｌ−１０）におけるｍは４を表し、一般式（Ｌ−１１）〜（Ｌ−１３）におけるｍは２を表す。一般式（Ｌ−１）、（Ｌ−２）および（Ｌ−１０）〜（Ｌ−１４）におけるＲ’はそれぞれ独立に水素原子または置換基を表す。Ｒⁿは水素原子またはメチル基を表す。Ｒ^siはそれぞれ独立に水素原子、アルキル基、アルケニル基またはアルキニル基を表す。）
［１１］ ［１０］に記載の化合物は、前記一般式（１）で表される化合物が、下記一般式（２）で表される化合物であることが好ましい。
一般式（２）

（一般式（２）において、Ｒ²³およびＲ²⁴はそれぞれ独立に水素原子または置換基を表し、Ｒ²³およびＲ²⁴のうち少なくとも１つは前記一般式（Ｗ）で表される基である。）
［１２］ ［１０］または［１１］に記載の化合物は、前記一般式（１）において、Ｓ、ＬおよびＴに含まれる炭素数の合計が５〜１８であることが好ましい。
［１３］ ［１０］〜［１２］のいずれか１項に記載の化合物は、前記一般式（１）において、Ｌが前記一般式（Ｌ−１）〜（Ｌ−６）および（Ｌ−１０）〜（Ｌ−１５）のいずれかで表される２価の連結基、または前記一般式（Ｌ−１）〜（Ｌ−６）および（Ｌ−１０）〜（Ｌ−１５）のいずれかで表される２価の連結基が２つ以上結合した２価の連結基であることが好ましい。
［１４］ ［１０］〜［１３］のいずれか一項に記載の化合物は、前記一般式（１）において、Ｌが前記一般式（Ｌ−１）で表される２価の連結基を含む２価の連結基であることが好ましい。
［１５］ ［１０］〜［１４］のいずれか一項に記載の化合物は、前記一般式（１）において、Ｌが前記一般式（Ｌ−１）で表される２価の連結基であり、Ｔが置換または無置換のアルキル基であることが好ましい。
［１６］ ［１０］〜［１４］のいずれか一項に記載の化合物は、前記一般式（１）において、Ｌが前記一般式（Ｌ−６）で表される２価の連結基を含む２価の連結基であることが好ましい。
［１７］ ［１０］〜［１６］のいずれか一項に記載の化合物は、前記一般式（１）において、Ｔが直鎖アルキル基であることが好ましい。
［１８］ ［１０］〜［１６］のいずれか一項に記載の化合物は、前記一般式（１）において、Ｔが分枝アルキル基であることが好ましい。
［１９］ ［１０］〜［１８］のいずれか一項に記載の化合物を含有することを特徴とする非発光性有機半導体デバイス用有機半導体材料。
［２０］ ［１０］〜［１８］のいずれか一項に記載の化合物を含有することを特徴とする有機薄膜トランジスタ用材料。
［２１］ ［１０］〜［１８］のいずれか一項に記載の化合物を含有することを特徴とする非発光性有機半導体デバイス用塗布溶液。
［２２］ ［１０］〜［１８］のいずれか一項に記載の化合物とポリマーバインダーを含有することを特徴とする非発光性有機半導体デバイス用塗布溶液。
［２３］ ［１０］〜［１８］のいずれか一項に記載の化合物を含有することを特徴とする非発光性有機半導体デバイス用有機半導体薄膜。
［２４］ ［１０］〜［１８］のいずれか一項に記載の化合物とポリマーバインダーを含有することを特徴とする非発光性有機半導体デバイス用有機半導体薄膜。
［２５］ 溶液塗布法により作製されたことを特徴とする［２３］または［２４］に記載の非発光性有機半導体デバイス用有機半導体薄膜。 [1] An organic thin film transistor comprising a compound represented by the following general formula (1) in a semiconductor active layer.
General formula (1)

(In General formula (1), R < ¹ > -R < ¹⁰ > represents a hydrogen atom or a halogen atom each independently.
R ²³ and R ²⁴ each independently represent a hydrogen atom or a substituent, and at least one of R ²³ and R ²⁴ is a substituent represented by the following general formula (W). )
-SLT General Formula (W)
(In the general formula (W), S represents — (CR ^S ₂ ) _n — (R ^S independently represents a hydrogen atom or a halogen atom, and n represents an integer of 0 to 17.) L represents the following general formula. A divalent linking group represented by any one of (L-1) to (L-15) or a divalent linking group represented by any one of the following general formulas (L-1) to (L-15) Represents a divalent linking group in which two or more are bonded, T is a substituted or unsubstituted alkyl group, an oligooxyethylene group having a repeating number v of oxyethylene units of 1 or more, and an oligosiloxane group having 1 or more silicon atoms Or a substituted or unsubstituted silyl group, wherein T represents a substituted or unsubstituted silyl group because L adjacent to T is represented by the following general formula (L-3) (Only when it is a linking group.)

(In the general formulas (L-1) to (L-15), the wavy line part represents the bonding position with S. In the general formula (L-10), m represents 4, and the general formulas (L-11) to (L-11) M in L-13) represents 2. R ′ in formulas (L-1), (L-2) and (L-10) to (L-14) each independently represents a hydrogen atom or a substituent. R ⁿ represents a hydrogen atom or a methyl group, and R ^si each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group.)
[2] In the organic thin film transistor according to [1], the compound represented by the general formula (1) is preferably a compound represented by the following general formula (2).
General formula (2)

(In General Formula (2), R ²³ and R ²⁴ each independently represent a hydrogen atom or a substituent, and at least one of R ²³ and R ²⁴ is a group represented by General Formula (W). )
[3] In the organic thin film transistor according to [1] or [2], the total number of carbon atoms contained in S, L and T in the general formula (1) is preferably 5 to 18.
[4] In the organic thin film transistor according to any one of [1] to [3], in the general formula (1), L represents the general formulas (L-1) to (L-6) and (L- 10) to (L-15), or any one of the general formulas (L-1) to (L-6) and (L-10) to (L-15) It is preferable that it is a bivalent coupling group which two or more bivalent coupling groups represented by these couple | bonded.
[5] In the organic thin film transistor according to any one of [1] to [4], in the general formula (1), L represents a divalent linking group represented by the general formula (L-1). The divalent linking group is preferably included.
[6] The organic thin film transistor according to any one of [1] to [5] is a divalent linking group in which L is represented by the general formula (L-1) in the general formula (1). And T is preferably a substituted or unsubstituted alkyl group.
[7] In the organic thin film transistor according to any one of [1] to [5], in the general formula (1), L represents a divalent linking group represented by the general formula (L-6). The divalent linking group is preferably included.
[8] In the organic thin film transistor according to any one of [1] to [7], in the general formula (1), T is preferably a linear alkyl group.
[9] In the organic thin film transistor according to any one of [1] to [7], in the general formula (1), T is preferably a branched alkyl group.
[10] A compound represented by the following general formula (1).
General formula (1)

(In General formula (1), R < ¹ > -R < ¹⁰ > represents a hydrogen atom or a halogen atom each independently.
R ²³ and R ²⁴ each independently represent a hydrogen atom or a substituent, and at least one of R ²³ and R ²⁴ is a substituent represented by the following general formula (W). )
-SLT General Formula (W)
(In the general formula (W), S represents — (CR ^S ₂ ) _n — (R ^S independently represents a hydrogen atom or a halogen atom, and n represents an integer of 0 to 17.) L represents the following general formula. A divalent linking group represented by any one of (L-1) to (L-15) or a divalent linking group represented by any one of the following general formulas (L-1) to (L-15) Represents a divalent linking group in which two or more are bonded, T is a substituted or unsubstituted alkyl group, an oligooxyethylene group having a repeating number v of oxyethylene units of 1 or more, and an oligosiloxane group having 1 or more silicon atoms Or a substituted or unsubstituted silyl group, wherein T represents a substituted or unsubstituted silyl group because L adjacent to T is represented by the following general formula (L-3) (Only when it is a linking group.)

(In the general formulas (L-1) to (L-15), the wavy line part represents the bonding position with S. In the general formula (L-10), m represents 4, and the general formulas (L-11) to (L-11) M in L-13) represents 2. R ′ in formulas (L-1), (L-2) and (L-10) to (L-14) each independently represents a hydrogen atom or a substituent. R ⁿ represents a hydrogen atom or a methyl group, and R ^si each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group.)
[11] In the compound according to [10], the compound represented by the general formula (1) is preferably a compound represented by the following general formula (2).
General formula (2)

(In General Formula (2), R ²³ and R ²⁴ each independently represent a hydrogen atom or a substituent, and at least one of R ²³ and R ²⁴ is a group represented by General Formula (W). )
[12] In the compound according to [10] or [11], the total number of carbon atoms contained in S, L and T in the general formula (1) is preferably 5 to 18.
[13] In the compound according to any one of [10] to [12], in the general formula (1), L represents the general formulas (L-1) to (L-6) and (L-10). ) To (L-15), or any one of the general formulas (L-1) to (L-6) and (L-10) to (L-15). It is preferable that it is a bivalent coupling group which two or more bivalent coupling groups represented by these couple | bonded.
[14] The compound according to any one of [10] to [13] includes a divalent linking group in which L is represented by the general formula (L-1) in the general formula (1). A divalent linking group is preferred.
[15] The compound according to any one of [10] to [14], in the general formula (1), L is a divalent linking group represented by the general formula (L-1). , T is preferably a substituted or unsubstituted alkyl group.
[16] The compound according to any one of [10] to [14] includes a divalent linking group in which L is represented by the general formula (L-6) in the general formula (1). A divalent linking group is preferred.
[17] In the compound according to any one of [10] to [16], T in the general formula (1) is preferably a linear alkyl group.
[18] In the compound according to any one of [10] to [16], T in the general formula (1) is preferably a branched alkyl group.
[19] An organic semiconductor material for non-light-emitting organic semiconductor devices, comprising the compound according to any one of [10] to [18].
[20] A material for an organic thin film transistor, comprising the compound according to any one of [10] to [18].
[21] A coating solution for non-light-emitting organic semiconductor devices, comprising the compound according to any one of [10] to [18].
[22] A coating solution for non-light-emitting organic semiconductor devices, comprising the compound according to any one of [10] to [18] and a polymer binder.
[23] An organic semiconductor thin film for a non-light-emitting organic semiconductor device comprising the compound according to any one of [10] to [18].
[24] An organic semiconductor thin film for a non-light-emitting organic semiconductor device, comprising the compound according to any one of [10] to [18] and a polymer binder.
[25] The organic semiconductor thin film for non-light-emitting organic semiconductor devices according to [23] or [24], which is produced by a solution coating method.

  According to the present invention, a compound having high carrier mobility and low driving voltage when used in a semiconductor active layer of an organic thin film transistor and having high solubility in an organic solvent, and an organic thin film transistor using the compound are provided. Can be provided.

FIG. 1 is a schematic view showing a cross section of an example of the structure of the organic thin film transistor of the present invention. FIG. 2 is a schematic view showing a cross section of the structure of an organic thin film transistor manufactured as a substrate for measuring FET characteristics in an example of the present invention.

Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be made based on representative embodiments and specific examples, but the present invention is not limited to such embodiments. In the present 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 invention, a hydrogen atom when used without being particularly distinguished in the description of each general formula represents that it also contains an isotope (such as a deuterium atom). Furthermore, the atom which comprises a substituent represents that the isotope is also included.

（一般式（１）において、Ｒ¹〜Ｒ¹⁰はそれぞれ独立に水素原子またはハロゲン原子を表す。
Ｒ²³およびＲ²⁴はそれぞれ独立に水素原子または置換基を表し、Ｒ²³およびＲ²⁴のうち少なくとも１つは下記一般式（Ｗ）で表される置換基である。）
−Ｓ−Ｌ−Ｔ 一般式（Ｗ）
（一般式（Ｗ）においてＳは−(ＣＲ^S ₂)_n−を表す（Ｒ^Sはそれぞれ独立に水素原子またはハロゲン原子を表し、ｎは０〜１７の整数を表す）。Ｌは下記一般式（Ｌ−１）〜（Ｌ−１５）のいずれかで表される２価の連結基または下記一般式（Ｌ−１）〜（Ｌ−１５）のいずれかで表される２価の連結基が２つ以上結合した２価の連結基を表す。Ｔは置換または無置換のアルキル基、オキシエチレン単位の繰り返し数ｖが１以上のオリゴオキシエチレン基、ケイ素原子数が１以上のオリゴシロキサン基、あるいは、置換または無置換のシリル基を表す。ただし、Ｔが置換または無置換のシリル基を表すのは、Ｔに隣接するＬが下記一般式（Ｌ−３）で表される２価の連結基である場合に限る。）

（一般式（Ｌ−１）〜（Ｌ−１５）において、波線部分はＳとの結合位置を示す。一般式（Ｌ−１０）におけるｍは４を表し、一般式（Ｌ−１１）〜（Ｌ−１３）におけるｍは２を表す。一般式（Ｌ−１）、（Ｌ−２）および（Ｌ−１０）〜（Ｌ−１４）におけるＲ’はそれぞれ独立に水素原子または置換基を表す。Ｒⁿは水素原子またはメチル基を表す。Ｒ^siはそれぞれ独立に水素原子、アルキル基、アルケニル基またはアルキニル基を表す。） [Organic thin film transistor]
The organic thin film transistor of the present invention includes a compound represented by the following general formula (1) in a semiconductor active layer.
General formula (1)

(In General formula (1), R < ¹ > -R < ¹⁰ > represents a hydrogen atom or a halogen atom each independently.
R ²³ and R ²⁴ each independently represent a hydrogen atom or a substituent, and at least one of R ²³ and R ²⁴ is a substituent represented by the following general formula (W). )
-SLT General Formula (W)
(In the general formula (W), S represents — (CR ^S ₂ ) _n — (R ^S independently represents a hydrogen atom or a halogen atom, and n represents an integer of 0 to 17.) L represents the following general formula. A divalent linking group represented by any one of (L-1) to (L-15) or a divalent linking group represented by any one of the following general formulas (L-1) to (L-15) Represents a divalent linking group in which two or more are bonded, T is a substituted or unsubstituted alkyl group, an oligooxyethylene group having a repeating number v of oxyethylene units of 1 or more, and an oligosiloxane group having 1 or more silicon atoms Or a substituted or unsubstituted silyl group, wherein T represents a substituted or unsubstituted silyl group because L adjacent to T is represented by the following general formula (L-3) (Only when it is a linking group.)

(In the general formulas (L-1) to (L-15), the wavy line part represents the bonding position with S. In the general formula (L-10), m represents 4, and the general formulas (L-11) to (L-11) M in L-13) represents 2. R ′ in formulas (L-1), (L-2) and (L-10) to (L-14) each independently represents a hydrogen atom or a substituent. R ⁿ represents a hydrogen atom or a methyl group, and R ^si each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group.)

The compound represented by the general formula (1) having such a structure has high solubility in an organic solvent, and the compound represented by the general formula (1) is contained in the semiconductor active layer, whereby the organic compound of the present invention is used. Thin film transistors have high carrier mobility and low driving voltage.
Here, in Patent Document 1, the main focus is on dibenzochrysene and chrysenodithiophene, and the chrysenodipyrrole compound having the same skeleton as that of the present invention is only described in the exemplified compounds, and is described in the examples. There is no. In addition, the exemplified compounds described are only compounds having a methyl group on the nitrogen atom of the pyrrole ring and having an alkyl group introduced into the 2-position of the pyrrole ring. Since the obstacle is large, the intermolecular distance is widened, and sufficient HOMO orbital overlap cannot be obtained. In Patent Document 1, there is no example in which these are used in an organic transistor, and even if used, it is difficult to achieve both carrier mobility and solubility. Furthermore, dibenzochrysene and chrysenodithiophene described in the examples have a deep HOMO compared to the work function of the electrode, and a driving voltage as high as 50 V or more despite being a top contact element using an Au electrode.
The compounds described in Examples of Patent Document 2 are asymmetric skeletons not included in the general formula (1), and have low field effect mobility.
On the other hand, the compound represented by the general formula (1) has an unsubstituted NH structure, and a predetermined group is introduced at the 2-position, so that high carrier mobility and low driving voltage are obtained. And the solubility in general organic solvents. In this compound, unlike an organic semiconductor material having active hydrogen in particular, having an unsubstituted NH structure is advantageous in increasing carrier mobility. Here, an organic semiconductor material having active hydrogen such as an unsubstituted NH structure is generally difficult to use in a transistor because it is chemically weak and easily oxidized to become a conductor. For example, in Synthetic Metals 82, 167-173 (1996), p-toluenesulfonic acid is added to poly (N-methylpyrrole) or poly (N-ethylpyrrole) rather than a film obtained by doping p-toluenesulfonic acid into polypyrrole. It has been shown that doped films have higher mobility and lower threshold voltages. On the other hand, the compound represented by the general formula (1) acts such that the unsubstituted NH structure of the pyrrole ring stabilizes the crystal structure, and obtains high carrier mobility by this previously unknown mechanism. Can do.

In addition, it cannot be immediately said that what is useful as an organic EL element material is useful as a semiconductor material for organic thin film transistors. This is because organic EL elements and organic thin film transistors have different characteristics required for organic compounds. In the organic EL element, it is usually necessary to transport charges in the film thickness direction (usually several nm to several hundred nm), whereas in the organic thin film transistor, the long distance between the electrodes in the thin film surface direction (usually several μm to several hundred μm). It is necessary to transport charges (carriers). For this reason, the required carrier mobility is remarkably high. Therefore, as a semiconductor material for an organic thin film transistor, an organic compound having high molecular order and high crystallinity is required. In order to develop high carrier mobility, the π conjugate plane is preferably upright with respect to the substrate. On the other hand, in order to increase the light emission efficiency, an organic EL element is required to have a high light emission efficiency and uniform light emission in the surface. In general, organic compounds with high crystallinity cause light emission defects such as in-plane electric field strength non-uniformity, light emission non-uniformity, and light emission quenching, so organic EL device materials have low crystallinity and are amorphous. High material is desired. For this reason, even if the organic compound constituting the organic EL element material is directly transferred to the organic semiconductor material, good transistor characteristics cannot be obtained immediately.
Hereinafter, preferred embodiments of the compound of the present invention and the organic thin film transistor of the present invention will be described.

（一般式（１）において、Ｒ¹〜Ｒ¹⁰はそれぞれ独立に水素原子またはハロゲン原子を表す。
Ｒ²³およびＲ²⁴はそれぞれ独立に水素原子または置換基を表し、Ｒ²³およびＲ²⁴のうち少なくとも１つは下記一般式（Ｗ）で表される置換基である。）
−Ｓ−Ｌ−Ｔ 一般式（Ｗ）
（一般式（Ｗ）においてＳは−(ＣＲ^S ₂)_n−を表す（Ｒ^Sはそれぞれ独立に水素原子またはハロゲン原子を表し、ｎは０〜１７の整数を表す）。Ｌは下記一般式（Ｌ−１）〜（Ｌ−１５）のいずれかで表される２価の連結基または下記一般式（Ｌ−１）〜（Ｌ−１５）のいずれかで表される２価の連結基が２つ以上結合した２価の連結基を表す。Ｔは置換または無置換のアルキル基、オキシエチレン単位の繰り返し数ｖが１以上のオリゴオキシエチレン基、ケイ素原子数が１以上のオリゴシロキサン基、あるいは、置換または無置換のシリル基を表す。ただし、Ｔが置換または無置換のシリル基を表すのは、Ｔに隣接するＬが下記一般式（Ｌ−３）で表される２価の連結基である場合に限る。）

（一般式（Ｌ−１）〜（Ｌ−１５）において、波線部分はＳとの結合位置を示す。一般式（Ｌ−１０）におけるｍは４を表し、一般式（Ｌ−１１）〜（Ｌ−１３）におけるｍは２を表す。一般式（Ｌ−１）、（Ｌ−２）および（Ｌ−１０）〜（Ｌ−１４）におけるＲ’はそれぞれ独立に水素原子または置換基を表す。Ｒⁿは水素原子またはメチル基を表す。Ｒ^siはそれぞれ独立に水素原子、アルキル基、アルケニル基またはアルキニル基を表す。） <Compound represented by the general formula (1)>
The compound of the present invention is represented by the following general formula (1). The compound of this invention is contained in the below-mentioned semiconductor active layer in the organic thin-film transistor of this invention. That is, the compound of the present invention can be used as a material for an organic thin film transistor.
General formula (1)

(In General formula (1), R < ¹ > -R < ¹⁰ > represents a hydrogen atom or a halogen atom each independently.
R ²³ and R ²⁴ each independently represent a hydrogen atom or a substituent, and at least one of R ²³ and R ²⁴ is a substituent represented by the following general formula (W). )
-SLT General Formula (W)
(In the general formula (W), S represents — (CR ^S ₂ ) _n — (R ^S independently represents a hydrogen atom or a halogen atom, and n represents an integer of 0 to 17.) L represents the following general formula. A divalent linking group represented by any one of (L-1) to (L-15) or a divalent linking group represented by any one of the following general formulas (L-1) to (L-15) Represents a divalent linking group in which two or more are bonded, T is a substituted or unsubstituted alkyl group, an oligooxyethylene group having a repeating number v of oxyethylene units of 1 or more, and an oligosiloxane group having 1 or more silicon atoms Or a substituted or unsubstituted silyl group, wherein T represents a substituted or unsubstituted silyl group because L adjacent to T is represented by the following general formula (L-3) (Only when it is a linking group.)

(In the general formulas (L-1) to (L-15), the wavy line part represents the bonding position with S. In the general formula (L-10), m represents 4, and the general formulas (L-11) to (L-11) M in L-13) represents 2. R ′ in formulas (L-1), (L-2) and (L-10) to (L-14) each independently represents a hydrogen atom or a substituent. R ⁿ represents a hydrogen atom or a methyl group, and R ^si each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group.)

In General formula (1), R < ¹ > -R < ¹⁰ > represents a hydrogen atom or a halogen atom each independently.
Examples of the halogen atom that R ^{1 to} R ¹⁰ can take include a fluorine atom, a chlorine atom, and a bromine atom, and a fluorine atom is preferable.
R ^{1 to} R ¹⁰ each independently represent a hydrogen atom from the viewpoint of increasing carrier mobility and reducing driving voltage.

In the general formula (1), R ²³ and R ²⁴ each independently represent a hydrogen atom or a substituent, and at least one represents a group represented by the general formula (W).
As substituents that R ²³ and R ^{24 in} the general formula (1) can independently take, a halogen atom, an alkyl group (methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, C1-C40 alkyl groups such as nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc., provided that 2,6-dimethyloctyl group, 2-decyltetradecyl group, 2- Hexyldecyl group, 2-ethyloctyl group, 2-decyltetradecyl group, 2-butyldecyl group, 1-octylnonyl group, 2-ethyloctyl group, 2-octyltetradecyl group, 2-ethylhexyl group, cycloalkyl group, Bicycloalkyl group, tricycloalkyl group and the like), alkenyl group (1-pentenyl group, cycloalkene) Alkynyl group (including 1-pentynyl group, trimethylsilylethynyl group, triethylsilylethynyl group, tri-i-propylsilylethynyl group, 2-p-propylphenylethynyl group, etc.), Aryl group (phenyl group, naphthyl group, p-pentylphenyl group, 3,4-dipentylphenyl group, p-heptoxyphenyl group, 3,4-diheptoxyphenyl group aryl group having 6 to 20 carbon atoms, etc.) Including), heterocyclic groups (may be referred to as heterocyclic groups, including 2-hexylfuranyl group, etc.), cyano groups, hydroxyl groups, nitro groups, acyl groups (including hexanoyl groups, benzoyl groups, etc.), alkoxy Group (including butoxy group), aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoy Oxy group, amino group (including anilino group), acylamino group, aminocarbonylamino group (including ureido group), alkoxy and aryloxycarbonylamino group, alkyl and arylsulfonylamino group, mercapto group, alkyl and arylthio group (methylthio group) , Octylthio group, etc.), heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, alkyl and aryloxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imido group , Phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, phosphono group, silyl group (ditrimethylsiloxymethylbutoxy group etc.), hydrazino group, ureido group, boronic acid group (-B (OH) _2), phosphato group (-OPO (OH) _2), a sulfato group (-OSO ₃ H), and other known substituents.
Moreover, these substituents may further have the above substituents. Moreover, when the compound represented by the general formula (1) is a polymer compound having a repeating structure, R ²³ and R ²⁴ may have a group derived from a polymerizable group.

In the compound represented by the general formula (1), both R ²³ and R ²⁴ are groups represented by the general formula (W), which increases carrier mobility and decreases driving voltage, It is preferable from the viewpoint of increasing the solubility in an organic solvent.

（一般式（Ｌ−１）〜（Ｌ−１５）において、波線部分はＳとの結合位置を示す。一般式（Ｌ−１０）におけるｍは４を表し、一般式（Ｌ−１１）〜（Ｌ−１３）におけるｍは２を表す。一般式（Ｌ−１）、（Ｌ−２）および（Ｌ−１０）〜（Ｌ−１４）におけるＲ’はそれぞれ独立に水素原子または置換基を表す。Ｒⁿは水素原子またはメチル基を表す。Ｒ^siはそれぞれ独立に水素原子、アルキル基、アルケニル基またはアルキニル基を表す。） In the general formula (1), the group represented by the general formula (W) having at least one of R ²³ and R ²⁴ will be described.
-SLT General Formula (W)
(In the general formula (W), S represents — (CR ^S ₂ ) _n — (R ^S independently represents a hydrogen atom or a halogen atom, and n represents an integer of 0 to 17.) L represents the following general formula. A divalent linking group represented by any one of (L-1) to (L-15) or a divalent linking group represented by any one of the following general formulas (L-1) to (L-15) Represents a divalent linking group in which two or more are bonded, T is a substituted or unsubstituted alkyl group, an oligooxyethylene group having a repeating number v of oxyethylene units of 1 or more, and an oligosiloxane group having 1 or more silicon atoms Or a substituted or unsubstituted silyl group, wherein T represents a substituted or unsubstituted silyl group because L adjacent to T is represented by the following general formula (L-3) (Only when it is a linking group.)

(In the general formulas (L-1) to (L-15), the wavy line part represents the bonding position with S. m in the general formula (L-10) represents 4, and the general formulas (L-11) to (L M in L-13) represents 2. R ′ in formulas (L-1), (L-2) and (L-10) to (L-14) each independently represents a hydrogen atom or a substituent. R ⁿ represents a hydrogen atom or a methyl group, and R ^si each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group.)

In the general formula (W), S represents — (CR ^S ₂ ) _n —.
R ^S independently represents a hydrogen atom or a halogen atom, and the range and preferred range of the halogen atom that R ^S can take are the same as the range and preferred range of the halogen atom that R ^{1 to} R ¹⁰ can take. R ^S is preferably a hydrogen atom.
In general formula (W), n represents an integer of 0 to 17, preferably 0 to 3, more preferably 0 or 1, and particularly preferably 0. When n is 0, S represents a single bond.

In the general formula (W), L is a divalent linking group represented by any one of the following general formulas (L-1) to (L-15) or the following general formulas (L-1) to (L-15). It represents a divalent linking group in which two or more divalent linking groups represented by any of the above are bonded. However, T represents a substituted or unsubstituted silyl group only when L adjacent to T is a divalent linking group represented by the following general formula (L-3). )

In the general formulas (L-1) to (L-15), the wavy line indicates the bonding position with S, and * is a divalent linking group represented by the general formulas (L-1) to (L-15). And the binding position with any of T. M in the general formula (L-10) represents 4, and m in the general formulas (L-11) to (L-13) represents 2. R ′ in general formulas (L-1), (L-2) and (L-10) to (L-14) each independently represents a hydrogen atom or a substituent. R ⁿ represents a hydrogen atom or a methyl group. R ^si each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group. R ′ in general formulas (L-1) and (L-2) may be bonded to T adjacent to L to form a condensed ring.

  When the L forms a linking group to which a divalent linking group represented by any one of the general formulas (L-1) to (L-15) is bonded, the general formulas (L-1) to (L-15) ) Is preferably 2 to 4 and more preferably 2 or 3.

As the substituent R ′ in the general formulas (L-1), (L-2) and (L-10) to (L-14), R ²³ and R ^{24 in} the above general formula (1) can be adopted. What was illustrated as a substituent can be mentioned. Among them, the substituent R ′ in the general formula (L-14) is preferably an alkyl group. When R ′ in the (L-14) is an alkyl group, the alkyl group has 1 to 1 carbon atoms. 9 is preferable, 4-9 is more preferable from the viewpoint of chemical stability and carrier transportability, and 5-9 is still more preferable. When R ′ in (L-14) is an alkyl group, the alkyl group is preferably a linear alkyl group from the viewpoint of increasing carrier mobility.
R ⁿ represents a hydrogen atom or a methyl group, and is preferably a methyl group.
R ^si each independently represents a hydrogen atom, an alkyl group or an alkenyl group, preferably an alkyl group. The alkyl group that R ^si can take is not particularly limited, but the preferred range of the alkyl group that R ^si can take is the same as the preferred range of the alkyl group that the silyl group can take when T is a silyl group. The alkenyl group that R ^si can take is not particularly limited, but is preferably a substituted or unsubstituted alkenyl group, more preferably a branched alkenyl group, and the alkenyl group has 2 to 3 carbon atoms. preferable. The alkynyl group that R ^si can take is not particularly limited, but a substituted or unsubstituted alkynyl group is preferable, a branched alkynyl group is more preferable, and the alkynyl group has 2 to 3 carbon atoms. preferable.
M in the general formula (L-10) represents 4, and m in the general formulas (L-11) to (L-13) represents 2.

L is a divalent linking group represented by any one of the general formulas (L-1) to (L-6) and (L-10) to (L-15), or the general formula (L-1) ~ (L-6) and (L-10) ~ (L-15) are preferably a divalent linking group in which two or more divalent linking groups are bonded to each other. It is more preferable that the divalent linking group represented by any one of -1) and (L-6) or a divalent linking group in which two or more of these divalent linking groups are bonded.
From the viewpoints of chemical stability and carrier transportability, a divalent linking group including a divalent linking group represented by the general formula (L-1) is particularly preferable, and represented by the general formula (L-1). The divalent linking group is more preferably, L is a divalent linking group represented by the general formula (L-1), and T is a substituted or unsubstituted alkyl group. Even more particularly preferred.
On the other hand, from the viewpoint of relaxing local dipoles, stabilizing the structure by intramolecular hydrogen bonding, and increasing carrier mobility, L is a divalent group containing a divalent linking group represented by the general formula (L-6). And particularly preferably a divalent linking group represented by the general formula (L-6). In addition, when L is a divalent linking group containing a divalent linking group represented by the general formula (L-6), a divalent linking group represented by the general formula (L-1) in L When n is not further included, n in S is preferably 1 or more, preferably 1 to 3, and more preferably 1.

In the general formula (W), T represents a substituted or unsubstituted alkyl group, an oligooxyethylene group having 1 or more repeating oxyethylene units, an oligosiloxane group having 1 or more silicon atoms, or a substituted or unsubstituted group. Represents a silyl group. However, T represents a substituted or unsubstituted silyl group only when L adjacent to T is a divalent linking group represented by the following general formula (L-3).
In the general formula (W), when L adjacent to T is a divalent linking group represented by the general formula (L-1), T represents a substituted or unsubstituted alkyl group or an oxyethylene unit. It is preferably an oligooxyethylene group having 1 or more repeats and an oligosiloxane group having 1 or more silicon atoms, more preferably a substituted or unsubstituted alkyl group.
In the general formula (W), when L adjacent to T is a divalent linking group represented by the general formulas (L-2) and (L-4) to (L-15), T is It is more preferably a substituted or unsubstituted alkyl group.
In the general formula (W), when L adjacent to T is a divalent linking group represented by the general formula (L-3), T is a substituted or unsubstituted alkyl group, substituted or unsubstituted. The silyl group is preferable.

When T is a substituted or unsubstituted alkyl group, the number of carbon atoms is preferably 4-18, more preferably 4-15, more preferably from the viewpoint of chemical stability and carrier transportability, and 7-15. Is particularly preferable, and 7 to 13 is particularly preferable. It is preferable that T is a long-chain alkyl group in the above range, particularly a long-chain linear alkyl group, from the viewpoint of improving the linearity of the molecule and increasing the carrier mobility.
When T represents an alkyl group, it may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group, but the linear alkyl group increases the linearity of the molecule and increases the carrier mobility. From the viewpoint of being able to.
On the other hand, from the viewpoint of increasing the solubility in an organic solvent, it is preferable that T is a branched alkyl group.
In the compound represented by the general formula (1), when the alkyl group is contained in the -SLT, the carrier mobility is increased when the alkyl group represented by T is not less than the lower limit of the above range. In addition, when L includes the general formula (L-1) adjacent to T or when n in -S- is 1 or more, an alkylene group represented by the general formula (L-1), -S- Carrier mobility becomes high when the carbon number of the alkyl group formed by combining the alkylene group contained therein and the alkyl group represented by T is not less than the lower limit of the above range.
Examples of the substituent when T is an alkyl group having a substituent include a halogen atom, and a fluorine atom is preferable. In addition, when T is an alkyl group having a fluorine atom, all hydrogen atoms of the alkyl group may be substituted with a fluorine atom to form a perfluoroalkyl group. However, T is preferably an unsubstituted alkyl group.

When T is an oligoethyleneoxy group having a repeating number of oxyethylene groups of 1 or more, the “oxyethylene group” represented by T is a group represented by — (OCH ₂ CH ₂ ) _v OY in the present specification. (The repeating number v of the oxyethylene unit represents an integer of 1 or more, and the terminal Y 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 repeating number v of oxyethylene units 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 particularly preferable.

  When the T is an oligosiloxane group having 1 or more silicon atoms, the number of repeating siloxane units is preferably 2 to 4, and 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 to it. 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.

  Only when L adjacent to T is a divalent linking group represented by the general formula (L-3), T may be a substituted or unsubstituted silyl group. Among them, when T is a substituted or unsubstituted silyl group, it is preferable that T is a substituted silyl group. Although there is no restriction | limiting in particular as a substituent of a silyl group, A substituted or unsubstituted alkyl group is preferable and it is more preferable that it is a branched alkyl group. When T is a trialkylsilyl group, the alkyl group bonded to the Si atom preferably has 1 to 3 carbon atoms. 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. When T is a trialkylsilyl group further having a substituent on the alkyl group, the substituent is not particularly limited.

In the general formula (W), when the total number of carbon atoms contained in S, L and T is 5 or more when used in the semiconductor active layer of the organic thin film transistor, the carrier mobility becomes high, and the driving voltage becomes low. It is preferable because the film quality is good and the solubility in an organic solvent is high.
On the other hand, in the general formula (W), the total number of carbon atoms contained in S, L and T is preferably 30 or less from the viewpoint of increasing the solubility in organic solvents, and 18 or less is a semiconductor of the organic thin film transistor. When used in the active layer, the carrier mobility is increased, the driving voltage is decreased, and the solubility in an organic solvent is more preferable.
The total number of carbon atoms contained in S, L and T is more preferably 5 to 14, more preferably 6 to 14, particularly preferably 8 to 14, and more preferably 8 to 12. More particularly preferred.

The compound represented by the general formula (1) is preferably a compound represented by the following general formula (2).
General formula (2)

In the general formula (2), R ²³ and R ²⁴ each independently represent a hydrogen atom or a substituent, and at least one of R ²³ and R ²⁴ is a group represented by the general formula (W).
A preferred range of R ²³ and R ²⁴ in the general formula (2) are the same as the preferred ranges of R ²³ and R ²⁴ in the general formula (1).

  Specific examples of the compound represented by the above general formula (1) are shown below, but the compound represented by the general formula (1) that can be used in the present invention is limitedly interpreted by these specific examples. Should not be done.

The compound represented by the general formula (1) may have a repeating structure, and may be a low molecule or a polymer. When the compound represented by the general formula (1) is a low molecular compound, the molecular weight is preferably 3000 or less, more preferably 2000 or less, further preferably 1000 or less, and 850 or less. It is particularly preferred. 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 thin film, the molecular weight is preferably 400 or more, more preferably 450 or more, and further preferably 500 or more.
In the case where the compound represented by the general formula (1) is a polymer compound having a repeating structure, the weight average molecular weight is preferably 30,000 or more, more preferably 50,000 or more, and 100,000 More preferably, it is the above. When the compound represented by the general formula (1) is a polymer compound having a repeating structure, the intermolecular interaction can be increased by setting the weight average molecular weight to be equal to or higher than the above lower limit, and high mobility. Is preferable.
Examples of the polymer compound having a repeating structure include a π-conjugated polymer in which the compound represented by the general formula (1) represents at least one arylene group or heteroarylene group (thiophene, bithiophene) and exhibits a repeating structure, A pendant polymer in which a compound represented by the formula (1) is bonded to a polymer main chain through a side chain is exemplified. As the polymer main chain, polyacrylate, polyvinyl, polysiloxane, and the like are preferable. Is preferably an alkylene group or a polyethylene oxide group.

The compound represented by the general formula (1) is disclosed in WO2010 / 024388, WO2013 / 078407, Angew. Chem. Int. Ed. 2000, 39, 2488, etc. can be used as a reference for synthesis.
Any reaction conditions may be used in the synthesis of the compounds of the invention. Any solvent may be used as the reaction solvent. In order to promote the ring formation reaction, it is preferable to use an acid or a base, and it is particularly preferable to use a base. Optimum reaction conditions vary depending on the structure of the target chrysenodipyrrole derivative, but can be set with reference to specific reaction conditions described in the above-mentioned documents.

  Synthetic intermediates having various substituents can be synthesized by combining known reactions. Each substituent may be introduced at any intermediate stage. After the synthesis of the intermediate, it is preferable to purify by sublimation purification after purification by column chromatography, recrystallization or the like. By sublimation purification, not only can organic impurities be separated, but inorganic salts and residual solvents can be effectively removed.

<Structure of organic thin film transistor>
The organic thin-film transistor of this invention has a semiconductor active layer containing the compound represented by the said General formula (1).
The organic thin film transistor of the present invention may further include other layers in addition to the semiconductor active layer.
The organic thin film transistor of the present invention is preferably used as an organic field effect transistor (FET), and more preferably as an insulated gate FET in which a gate-channel is insulated.
Hereinafter, although the aspect of the preferable structure of the organic thin-film transistor of this invention is demonstrated in detail using drawing, this invention is not limited to these aspects.

(Laminated structure)
There is no restriction | limiting in particular as a laminated structure of an organic field effect transistor, It can be set as the thing of various well-known structures.
As an example of the structure of the organic thin film transistor of the present invention, a structure in which an electrode, an insulator layer, a semiconductor active layer (organic semiconductor layer), and two electrodes are sequentially arranged on the upper surface of the lowermost substrate (bottom gate / top contact type) ). In this structure, the electrode on the upper surface of the lowermost substrate is provided on a part of the substrate, and the insulator layer is disposed so as to be in contact with the substrate at a portion other than the electrode. Further, the two electrodes provided on the upper surface of the semiconductor active layer are arranged separately from each other.
The structure of the bottom gate / top contact type element is shown in FIG. FIG. 1 is a schematic view showing a cross section of an example of the structure of the organic thin film transistor of the present invention. The organic thin film transistor of FIG. 1 has a substrate 11 disposed in the lowermost layer, an electrode 12 is provided on a part of the upper surface thereof, further covers the electrode 12 and is in contact with the substrate 11 at a portion other than the electrode 12. 13 is provided. Further, the semiconductor active layer 14 is provided on the upper surface of the insulator layer 13, and the two electrodes 15a and 15b are disposed separately on a part of the upper surface.
In the organic thin film transistor shown in FIG. 1, the electrode 12 is a gate, and the electrodes 15a and 15b are drains or sources, respectively. The organic thin film transistor shown in FIG. 1 is an insulated gate FET in which a channel that is a current path between a drain and a source is insulated from a gate.

An example of the structure of the organic thin film transistor of the present invention is a bottom gate / bottom contact type element.
The structure of the bottom gate / bottom contact type element is shown in FIG. FIG. 2 is a schematic view showing a cross section of the structure of an organic thin film transistor manufactured as a substrate for measuring FET characteristics in an example of the present invention. In the organic thin film transistor of FIG. 2, the substrate 31 is disposed in the lowermost layer, the electrode 32 is provided on a part of the upper surface thereof, and the insulator layer is further covered with the electrode 32 and in contact with the substrate 31 at a portion other than the electrode 32. 33 is provided. Further, the semiconductor active layer 35 is provided on the upper surface of the insulator layer 33, and the electrodes 34 a and 34 b are below the semiconductor active layer 35.
In the organic thin film transistor shown in FIG. 2, the electrode 32 is a gate, and the electrode 34a and the electrode 34b are a drain or a source, respectively. The organic thin film transistor shown in FIG. 2 is an insulated gate FET in which a channel that is a current path between a drain and a source is insulated from a gate.

  As the structure of the organic thin film transistor of the present invention, a top gate / top contact type element having an insulator and a gate electrode above the semiconductor active layer, and a top gate / bottom contact type element can also be preferably used.

(thickness)
When the organic thin film transistor of the present invention needs to be a thinner transistor, for example, the thickness of the entire transistor is preferably 0.1 to 0.5 μm.

(Sealing)
In order to shield the organic thin film transistor element from the air and moisture and improve the storage stability of the organic thin film transistor element, the entire organic thin film transistor element is made of a metal sealing can, glass, an inorganic material such as silicon nitride, a polymer material such as parylene, It may be sealed with a low molecular material or the like.
Hereinafter, although the preferable aspect of each layer of the organic thin-film transistor of this invention is demonstrated, this invention is not limited to these aspects.

<Board>
(material)
The organic thin film transistor of the present invention preferably includes a substrate.
There is no restriction | limiting in particular as a material of the said board | substrate, For example, a well-known material can be used, For example, polyester films, such as a polyethylene naphthoate (PEN) and a polyethylene terephthalate (PET), a cycloolefin polymer film, a polycarbonate film, a triacetyl cellulose (TAC) film, polyimide film, and those obtained by bonding these polymer films to ultrathin glass, ceramic, silicon, quartz, glass, and the like can be mentioned, and silicon is preferred.

<Electrode>
(material)
The organic thin film transistor of the present invention preferably includes an electrode.
Examples of the constituent material of the electrode include metal materials such as Cr, Al, Ta, Mo, Nb, Cu, Ag, Au, Pt, Pd, In, Ni, and Nd, alloy materials thereof, carbon materials, and conductive materials. Any known conductive material such as a conductive polymer can be used without particular limitation.

(thickness)
The thickness of the electrode is not particularly limited, but is preferably 10 to 50 nm.
There is no particular limitation on the gate width (or channel width) W and the gate length (or channel length) L, but the ratio W / L is preferably 10 or more, more preferably 20 or more.

<Insulating layer>
(material)
The material constituting the insulating layer is not particularly limited as long as the necessary insulating effect can be obtained. For example, fluorine polymer insulating materials such as silicon dioxide, silicon nitride, PTFE, CYTOP, polyester insulating materials, polycarbonate insulating materials, acrylic polymers Insulating material, epoxy resin insulating material, polyimide insulating material, polyvinylphenol resin insulating material, polyparaxylylene resin insulating material, and the like.
The upper surface of the insulating layer may be surface-treated. For example, an insulating layer whose surface is treated by applying hexamethyldisilazane (HMDS) or octadecyltrichlorosilane (OTS) to the silicon dioxide surface can be preferably used.

(thickness)
The thickness of the insulating layer is not particularly limited, but when thinning is required, the thickness is preferably 10 to 400 nm, more preferably 20 to 200 nm, and particularly preferably 50 to 200 nm. .

<Semiconductor active layer>
(material)
The organic thin film transistor of the present invention is characterized in that the semiconductor active layer contains the compound represented by the general formula (1), that is, the compound of the present invention.
The semiconductor active layer may be a layer made of the compound of the present invention, or may be a layer further containing a polymer binder described later in addition to the compound of the present invention. Moreover, the residual solvent at the time of film-forming may be contained.
The content of the polymer binder in the semiconductor active layer is not particularly limited, but is preferably used in the range of 0 to 95% by mass, more preferably in the range of 10 to 90% by mass, Preferably it is used within the range of 20 to 80% by mass, and particularly preferably within the range of 30 to 70% by mass.

(thickness)
Although there is no restriction | limiting in particular in the thickness of a semiconductor active layer, When thinning is calculated | required, it is preferable to set thickness to 10-400 nm, It is more preferable to set it as 10-200 nm, It is especially preferable to set it as 10-100 nm. preferable.

[Organic semiconductor materials for non-luminescent organic semiconductor devices]
The present invention also relates to an organic semiconductor material for a non-light-emitting organic semiconductor device containing the compound represented by the general formula (1), that is, the compound of the present invention.

(Non-luminescent organic semiconductor devices)
In the present specification, the “non-light emitting organic semiconductor device” means a device not intended to emit light. The non-light-emitting organic semiconductor device is preferably a non-light-emitting organic semiconductor device using an electronic element having a thin film layer structure. Non-light-emitting organic semiconductor devices include organic thin film transistors, organic photoelectric conversion elements (solid-state imaging elements for optical sensors, solar cells for energy conversion, etc.), gas sensors, organic rectifying elements, organic inverters, information recording elements, etc. The The organic photoelectric conversion element can be used for both optical sensor applications (solid-state imaging elements) and energy conversion applications (solar cells). An organic photoelectric conversion element and an organic thin film transistor are preferable, and an organic thin film transistor is more preferable. That is, the organic semiconductor material for a non-light-emitting organic semiconductor device of the present invention is preferably an organic thin film transistor material as described above.

(Organic semiconductor materials)
In the present specification, the “organic semiconductor material” is an organic material exhibiting semiconductor characteristics. Similar to semiconductors made of inorganic materials, there are p-type (hole-transporting) organic semiconductors that conduct holes as carriers, and n-type (electron-transporting) organic semiconductors that conduct electrons as carriers.
The compound of the present invention may be used as either a p-type organic semiconductor material or an n-type organic semiconductor material, but is more preferably used as a p-type. The ease of carrier flow in the organic semiconductor is represented by carrier mobility μ. The carrier mobility μ is preferably high, preferably 1 × 10 ⁻³ cm ² / Vs or more, more preferably 5 × 10 ⁻³ cm ² / Vs or more, and 1 × 10 ⁻² cm ^2. / Vs or higher is particularly preferable, 1 × 10 ⁻¹ cm ² / Vs or higher is more preferable, and 1 cm ² / Vs or higher is even more preferable. The carrier mobility μ can be obtained by characteristics when a field effect transistor (FET) element is manufactured or by a time-of-flight measurement (TOF) method.

[Organic semiconductor thin film for non-luminescent organic semiconductor devices]
(material)
The present invention also relates to a compound represented by the above general formula (1), that is, an organic semiconductor thin film for a non-light-emitting organic semiconductor device containing the compound of the present invention.
The aspect in which the organic semiconductor thin film for a non-luminescent organic semiconductor device of the present invention contains the compound represented by the general formula (1), that is, the compound of the present invention and does not contain a polymer binder is also preferable.
Moreover, the organic-semiconductor thin film for nonluminous organic-semiconductor devices of this invention may contain the compound represented by the said General formula (1), ie, the compound of this invention, and a polymer binder.

Examples of the polymer binder include insulating polymers such as polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyimide, polyurethane, polysiloxane, polysulfone, polymethyl methacrylate, polymethyl acrylate, cellulose, polyethylene, and polypropylene, and co-polymers thereof. Examples thereof include a polymer, a photoconductive polymer such as polyvinyl carbazole and polysilane, a conductive polymer such as polythiophene, polypyrrole, polyaniline, and polyparaphenylene vinylene, and a semiconductor polymer.
The polymer binders may be used alone or in combination.
In addition, the organic semiconductor material and the polymer binder may be uniformly mixed, or a part or all of them may be phase-separated, but from the viewpoint of charge mobility, A structure in which the binder and the binder are phase-separated is most preferable because the binder does not hinder the charge transfer of the organic semiconductor.
In consideration of the mechanical strength of the thin film, a polymer binder having a high glass transition temperature is preferable, and in consideration of charge mobility, a polymer binder, a photoconductive polymer, or a conductive polymer having a structure containing no polar group is preferable.
Although there is no restriction | limiting in particular in the usage-amount of a polymer binder, Preferably it uses in the range of 0-95 mass% in the organic-semiconductor thin film for nonluminous organic-semiconductor devices of this invention, More preferably, it is 10-90 mass% Is more preferably used within a range of 20 to 80% by mass, and particularly preferably within a range of 30 to 70% by mass.

  Furthermore, in the present invention, an organic thin film with good film quality can be obtained by the compound having the structure described above. Specifically, since the compound obtained by the present invention has good crystallinity, a sufficient film thickness can be obtained, and the obtained organic semiconductor thin film for a non-luminescent organic semiconductor device of the present invention has a good quality. Become.

(Film formation method)
Any method may be used for forming the compound of the present invention on the substrate.
During film formation, the substrate may be heated or cooled, and the film quality and molecular packing in the film can be controlled by changing the temperature of the substrate. Although there is no restriction | limiting in particular as temperature of a board | substrate, It is preferable that it is between 0 degreeC and 200 degreeC, It is more preferable that it is between 15 degreeC-100 degreeC, It is especially between 20 degreeC-95 degreeC. preferable.
When the compound of the present invention is formed on a substrate, it can be formed by a vacuum process or a solution process, both of which are preferable.

  Specific examples of film formation by a vacuum process include physical vapor deposition methods such as vacuum deposition, sputtering, ion plating, molecular beam epitaxy (MBE), and chemical vapor deposition (CVD) such as plasma polymerization. ) Method, and it is particularly preferable to use a vacuum deposition method.

Here, film formation by a solution process refers to a method in which an organic compound is dissolved in a solvent that can be dissolved and a film is formed using the solution. Specifically, coating methods such as casting method, dip coating method, die coater method, roll coater method, bar coater method, spin coating method, ink jet method, screen printing method, gravure printing method, flexographic printing method, offset printing Various printing methods such as micro contact printing, micro contact printing, and ordinary methods such as Langmuir-Blodgett (LB) can be used. Casting, spin coating, ink jet, gravure printing, flexographic printing, offset It is particularly preferable to use a printing method or a microcontact printing method.
The organic semiconductor thin film for a non-luminescent organic semiconductor device of the present invention is preferably produced by a solution coating method. Further, when the organic semiconductor thin film for a non-light-emitting organic semiconductor device of the present invention contains a polymer binder, the material for forming the layer and the polymer binder are dissolved or dispersed in an appropriate solvent to form a coating solution. It is preferably formed by a coating method.
Hereinafter, the coating solution for non-light-emitting organic semiconductor devices of the present invention that can be used for film formation by a solution process will be described.

[Coating solution for non-luminescent organic semiconductor devices]
The present invention also relates to a coating solution for a non-light-emitting organic semiconductor device containing the compound represented by the general formula (1), that is, the compound of the present invention.
When a film is formed on a substrate using a solution process, a material for forming the layer is selected from hydrocarbons such as hexane, octane, decane, toluene, xylene, mesitylene, ethylbenzene, decalin, and 1-methylnaphthalene. Solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketone solvents such as dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, chlorotoluene and the like Solvent, for example, ester solvent such as ethyl acetate, butyl acetate, amyl acetate, for example, methanol, propanol, butanol, pentanol, hexanol, cyclohexanol, methyl Alcohol solvents such as rosolve, ethyl cellosolve, ethylene glycol, for example, ether solvents such as dibutyl ether, tetrahydrofuran, dioxane, anisole, such as N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2- An amide / imide solvent such as pyrrolidone, 1-methyl-2-imidazolidinone, a sulfoxide solvent such as dimethyl sulfoxide, a nitrile solvent such as acetonitrile) and / or water is dissolved or dispersed into a coating solution. A thin film can be formed by various coating methods. A solvent may be used independently and may be used in combination of multiple. Among these, the solvent for the compound having an unsubstituted NH structure of the present invention includes polar solvents such as ketone solvents, alcohol solvents, amide / imide solvents, sulfoxide solvents, nitrile solvents, or hydrocarbons. Solvents, halogenated hydrocarbon solvents or ether solvents are preferred, hydrocarbon solvents, halogenated hydrocarbon solvents or ether solvents are more preferred, hydrocarbon solvents are particularly preferred, toluene, xylene, mesitylene, tetralin Dichlorobenzene or anisole is more particularly preferred, and toluene, xylene, tetralin and anisole are even more particularly preferred. The concentration of the compound represented by the general formula (1) in the coating solution is preferably 0.1 to 80% by weight, more preferably 0.1 to 10% by weight, and particularly preferably 0.5 to 10% by weight. By setting the ratio to%, a film having an arbitrary thickness can be formed.

  In order to form a film by a solution process, it is necessary that the material is dissolved in the above-described solvent or the like, but it is not sufficient to simply dissolve the material. Usually, even a material for forming a film by a vacuum process can be dissolved in a solvent to some extent. However, in the solution process, there is a process in which after the material is dissolved in a solvent and applied, the solvent evaporates to form a thin film, and many materials that are not suitable for solution process film formation have high crystallinity. It is difficult to form a good thin film due to inappropriate crystallization (aggregation) in the process. The compound represented by the general formula (1) is excellent in that crystallization (aggregation) hardly occurs.

The coating solution for a non-light-emitting organic semiconductor device of the present invention is also preferably an embodiment containing the compound represented by the general formula (1), that is, the compound of the present invention and not containing a polymer binder.
Moreover, the coating solution for non-luminous organic semiconductor devices of this invention may contain the compound represented by the said General formula (1), ie, the compound of this invention, and a polymer binder. In this case, the material for forming the layer and the polymer binder can be dissolved or dispersed in the aforementioned appropriate solvent to form a coating solution, and a thin film can be formed by various coating methods. The polymer binder can be selected from those described above.

  The features of the present invention will be described more specifically with reference to examples and comparative 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 should not be construed as being limited by the specific examples shown below.

[Examples 1 to 5 and Comparative Examples 1 to 3]
<Synthesis Example 1> Synthesis of Compound 4 According to a specific synthesis procedure shown in the following scheme, Compound 4, which is a compound represented by the general formula (1), was synthesized.

(Synthesis of 2,8-diaminochrysene M1)
2,8-Diaminochrysene M1 was synthesized by the method described in Tetrahedron Letters 2004, 45, 4737-4739.
(Synthesis of Intermediate M2)
Diaminochrysene M1 (2.3 g) was dissolved in chloroform (90 ml), and bromine (0.96 ml) was added dropwise over 5 minutes at room temperature while stirring. After completion of the dropwise addition, stirring was continued at room temperature for 2 hours. After quenching by adding 25 ml of an aqueous sodium hydrogen sulfite solution dropwise to the reaction solution, the pH of the aqueous layer was adjusted to 9 with 2N potassium carbonate. The precipitate was collected by suction filtration and dried at 100 ° C. to obtain Intermediate M2 (3.5 g, yield 93%).
(Synthesis of Intermediate M3)
Intermediate M2 (3.5 g) was dissolved in 30 ml of dehydrated viridine, and tosyl chloride (4.9 g) was added in portions over 10 minutes while cooling to 0 ° C. with an ice bath. The ice bath was removed after the addition, and the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into water, and the precipitate was collected by filtration and ultrasonically washed in methanol to obtain Intermediate M3 (6.1 g, yield 100%). Ts represents a tosyl group (paratoluenesulfonyl group).
(Synthesis of Intermediate M4)
Intermediate M3 (6.1 g), bis (triphenylphosphine) palladium (II) dichloride (1.0 g), copper iodide (0.54 g), 1-decyne (6.1 ml), diisopropylamine (12 ml), After mixing and degassing 30 ml of dehydrated DMF, the mixture was stirred at an external temperature of 110 ° C. for 4 hours. After confirming the completion of the reaction by TLC, the reaction solution was filtered through Celite, and the filtrate was extracted with ethyl acetate and 5% dilute hydrochloric acid. The organic layer was dried over anhydrous magnesium sulfate and filtered, and ethyl acetate was distilled off under reduced pressure. The residue was ultrasonically washed with methanol to obtain Intermediate M4 (4.6 g, yield 65%).
(Synthesis of Compound 4)
40 ml of tetrabutylammonium fluoride (1M THF solution) was added to intermediate M4 (4.6 g), and the mixture was refluxed and stirred for 3 hours. The reaction solution was cooled to room temperature, and extracted by adding ethyl acetate and 5% dilute hydrochloric acid. The organic layer was dried over anhydrous magnesium sulfate and filtered, and the organic layer was distilled off under reduced pressure. The residue was purified by preparative GPC (developing solvent THF) to obtain Compound 4 (0.83 g, yield 18%).
The obtained compound was identified by elemental analysis, NMR and MS spectrum.

  The compounds represented by the general formula (1) used in other examples were also synthesized in the same manner as the compound 4.

Comparative compound 1 used for the semiconductor active layer (organic semiconductor layer) of the comparative element was synthesized by methylating compound 4 using sodium hydride and methyl iodide. Comparative compounds 2 and 3 were synthesized according to the same method except that the materials used were changed.
The structures of Comparative Compounds 1 to 3 are shown below.

<Device fabrication and evaluation>
All materials used for device fabrication were subjected to sublimation purification, and it was confirmed by high performance liquid chromatography (Tosoh TSKgel ODS-100Z) that the purity (absorption intensity area ratio at 254 nm) was 99.5% or more.

<Forming a semiconductor active layer (organic semiconductor layer) with a compound alone>
Each of the compounds of the present invention or the comparative compound (each 1 mg) and toluene (1 mL) were mixed and heated to 100 ° C. to obtain a coating solution for a non-luminescent organic semiconductor device. This coating solution is cast on an FET characteristic measurement substrate heated to 90 ° C. in a nitrogen atmosphere to form an organic semiconductor thin film for a non-light-emitting organic semiconductor device, and the organic thin film transistor of Example 2 for FET characteristic measurement An element was obtained. As a substrate for FET characteristic measurement, a bottom provided with chromium / gold (gate width W = 100 mm, gate length L = 100 μm) disposed in a comb shape as source and drain electrodes, and SiO ₂ (film thickness 200 nm) as an insulating film. A silicon substrate having a gate / bottom contact structure (a schematic diagram of the structure is shown in FIG. 2) was used.

[Evaluation]
(A) Carrier mobility, (b) threshold voltage The FET characteristics of the organic thin film transistor elements of the examples and comparative examples are as follows. Semiconductor parameter analyzer (Agilent, 4156C) connected to a semi-auto prober (Vector Semicon, AX-2000) Was evaluated in terms of carrier mobility and threshold voltage under normal pressure and nitrogen atmosphere.
A voltage of −80 V was applied between the source electrode and the drain electrode of each organic thin film transistor element (FET element), the gate voltage was changed in the range of 20 V to −100 V, and the threshold voltage was obtained. Also, the expression I _d = (w / 2L) μC _i (V _g −V _th ) ² representing the drain current I _d (where L is the gate length, W is the gate width, and C _i is the unit area of the insulating layer) The carrier mobility μ was calculated using the capacitance of V, V _{g as} the gate voltage, and V _{th as} the threshold voltage.
The obtained results are shown in Table 1 below.
Note that the smaller the absolute value of the threshold voltage, the lower the drive voltage of the element, which is preferable.

(C) Solubility The compound of the present invention or the comparative compound (each 2% by mass, each 1% by mass or each 0.1% by mass) and toluene (1 mL) are mixed, heated to 100 ° C., and then at room temperature for 30 minutes. The concentration at which no precipitation was observed was determined, and the solubility in toluene was evaluated in the following four stages. Practically, AA, A or B evaluation is required, AA or A evaluation is preferable, and AA evaluation is more preferable.
AA: No precipitation at 2% by mass.
A: No precipitation at 1% by mass, and precipitation at 2% by mass.
B: No precipitation at 0.1% by mass, and precipitation at 1% by mass.
C: Precipitation occurs at 0.1% by mass.

(D) Film quality (domain size)
About the semiconductor active layer of the organic thin-film transistor element of Example 2, the domain size was measured in the range of 1 mm square using a polarizing microscope, and the average domain size was calculated. The obtained results were evaluated in the following three stages. In practice, there is no problem even with C evaluation, but A or B evaluation is preferable, and A evaluation is more preferable.
A: The average domain size exceeds 30 micrometers.
B: The average domain size exceeds 5 micrometers and is 30 micrometers or less.
C: The average domain size is 5 micrometers or less.

(E) Heat resistance When the organic thin-film transistor element of Example 2 was heated on the following conditions, it was examined whether mobility would fall. The obtained results were evaluated in the following three stages. In practice, there is no problem even with C evaluation, but A or B evaluation is preferable, and A evaluation is more preferable.
A: No change after heating at 150 ° C. for 10 minutes.
B: No change when heated at 100 ° C. for 10 minutes, but decreased at 150 ° C. for 10 minutes.
C: Decrease in heating at 100 ° C. for 10 minutes.

From Table 1 above, it was found that the compound of the present invention has good solubility in an organic solvent, and the organic thin film transistor element using the compound of the present invention has high carrier mobility and low driving voltage. Therefore, it turned out that the compound of this invention is preferably used as an organic-semiconductor material for nonluminous organic-semiconductor devices. In addition, the organic thin film transistor using the compound 14-2 in which the total number of carbon atoms of the substituents at the positions corresponding to R ²³ and R ²⁴ in the general formula (1) deviates from the upper limit value of the preferable range has a little carrier mobility. Although it was low and the driving voltage was a little high, there was no practical problem.
On the other hand, the organic thin film transistor element using Comparative Compounds 1 to 3 in which an alkyl group was introduced into the nitrogen atom of the general formula (1) had a low carrier mobility and a high driving voltage. Furthermore, the comparative compound 2 had low solubility in an organic solvent.
In addition, the organic thin-film transistor element using the compound of this invention had favorable film quality of the semiconductor active layer, and its element heat resistance was also favorable.

11 Substrate 12 Electrode 13 Insulator Layer 14 Semiconductor Active Layer (Organic Material Layer, Organic Semiconductor Layer)
15a, 15b Electrode 31 Substrate 32 Electrode 33 Insulator layer 34a, 34b Electrode 35 Semiconductor active layer (organic material layer, organic semiconductor layer)

Claims (25)

An organic thin film transistor comprising a compound represented by the following general formula (1) in a semiconductor active layer.
General formula (1)

(In General formula (1), R < ¹ > -R < ¹⁰ > represents a hydrogen atom or a halogen atom each independently.
R ²³ and R ²⁴ each independently represent a hydrogen atom or a substituent, and at least one of R ²³ and R ²⁴ is a substituent represented by the following general formula (W). )
-SLT General Formula (W)
(In the general formula (W), S represents — (CR ^S ₂ ) _n — (R ^S independently represents a hydrogen atom or a halogen atom, and n represents an integer of 0 to 17.) L represents the following general formula. A divalent linking group represented by any one of (L-1) to (L-15) or a divalent linking group represented by any one of the following general formulas (L-1) to (L-15) Represents a divalent linking group in which two or more are bonded, T is a substituted or unsubstituted alkyl group, an oligooxyethylene group having a repeating number v of oxyethylene units of 1 or more, and an oligosiloxane group having 1 or more silicon atoms Or a substituted or unsubstituted silyl group, wherein T represents a substituted or unsubstituted silyl group because L adjacent to T is represented by the following general formula (L-3) (Only when it is a linking group.)

(In the general formulas (L-1) to (L-15), the wavy line part represents the bonding position with S. In the general formula (L-10), m represents 4, and the general formulas (L-11) to (L-11) M in L-13) represents 2. R ′ in formulas (L-1), (L-2) and (L-10) to (L-14) each independently represents a hydrogen atom or a substituent. R ⁿ represents a hydrogen atom or a methyl group, and R ^si each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group.) The organic thin film transistor according to claim 1, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).
General formula (2)

(In General Formula (2), R ²³ and R ²⁴ each independently represent a hydrogen atom or a substituent, and at least one of R ²³ and R ²⁴ is a group represented by General Formula (W). )   3. The organic thin film transistor according to claim 1, wherein the total number of carbon atoms contained in S, L, and T is 5 to 18 in the general formula (1).   In the general formula (1), L is a divalent linking group represented by any one of the general formulas (L-1) to (L-6) and (L-10) to (L-15), or A divalent linking group in which two or more divalent linking groups represented by any one of the general formulas (L-1) to (L-6) and (L-10) to (L-15) are bonded. The organic thin film transistor according to any one of claims 1 to 3, wherein the organic thin film transistor is provided.   In the said General formula (1), L is a bivalent coupling group containing the bivalent coupling group represented by the said general formula (L-1), The any one of Claims 1-4 characterized by the above-mentioned. The organic thin film transistor according to item.   The general formula (1), wherein L is a divalent linking group represented by the general formula (L-1), and T is a substituted or unsubstituted alkyl group. The organic thin film transistor according to any one of 5.   In the said General formula (1), L is a bivalent coupling group containing the bivalent coupling group represented by the said general formula (L-6), It is any one of Claims 1-5 characterized by the above-mentioned. The organic thin film transistor according to item.   In the said General formula (1), T is a linear alkyl group, The organic thin-film transistor as described in any one of Claims 1-7 characterized by the above-mentioned.   In the said General formula (1), T is a branched alkyl group, The organic thin-film transistor as described in any one of Claims 1-7 characterized by the above-mentioned. A compound represented by the following general formula (1).
General formula (1)

(In General formula (1), R < ¹ > -R < ¹⁰ > represents a hydrogen atom or a halogen atom each independently.
R ²³ and R ²⁴ each independently represent a hydrogen atom or a substituent, and at least one of R ²³ and R ²⁴ is a substituent represented by the following general formula (W). )
-SLT General Formula (W)
(In the general formula (W), S represents — (CR ^S ₂ ) _n — (R ^S independently represents a hydrogen atom or a halogen atom, and n represents an integer of 0 to 17.) L represents the following general formula. A divalent linking group represented by any one of (L-1) to (L-15) or a divalent linking group represented by any one of the following general formulas (L-1) to (L-15) Represents a divalent linking group in which two or more are bonded, T is a substituted or unsubstituted alkyl group, an oligooxyethylene group having a repeating number v of oxyethylene units of 1 or more, and an oligosiloxane group having 1 or more silicon atoms Or a substituted or unsubstituted silyl group, wherein T represents a substituted or unsubstituted silyl group because L adjacent to T is represented by the following general formula (L-3) (Only when it is a linking group.)

(In the general formulas (L-1) to (L-15), the wavy line part represents the bonding position with S. In the general formula (L-10), m represents 4, and the general formulas (L-11) to (L-11) M in L-13) represents 2. R ′ in formulas (L-1), (L-2) and (L-10) to (L-14) each independently represents a hydrogen atom or a substituent. R ⁿ represents a hydrogen atom or a methyl group, and R ^si each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group.) The compound represented by the general formula (1) is a compound represented by the following general formula (2).
General formula (2)

(In General Formula (2), R ²³ and R ²⁴ each independently represent a hydrogen atom or a substituent, and at least one of R ²³ and R ²⁴ is a group represented by General Formula (W). )   In the said General formula (1), the sum total of the carbon number contained in S, L, and T is 5-18, The compound of Claim 10 or 11 characterized by the above-mentioned.   In the general formula (1), L is a divalent linking group represented by any one of the general formulas (L-1) to (L-6) and (L-10) to (L-15), or A divalent linking group in which two or more divalent linking groups represented by any one of the general formulas (L-1) to (L-6) and (L-10) to (L-15) are bonded. A compound according to any one of claims 10 to 12, characterized in that it is.   The general formula (1), wherein L is a divalent linking group including a divalent linking group represented by the general formula (L-1). The compound according to item.   The general formula (1), wherein L is a divalent linking group represented by the general formula (L-1), and T is a substituted or unsubstituted alkyl group. 15. The compound according to any one of 14.   In the general formula (1), L is a divalent linking group including a divalent linking group represented by the general formula (L-6). The compound according to item.   In the said General formula (1), T is a linear alkyl group, The compound as described in any one of Claims 10-16 characterized by the above-mentioned.   In the said General formula (1), T is a branched alkyl group, The compound as described in any one of Claims 10-16 characterized by the above-mentioned.   The organic-semiconductor material for nonluminous organic-semiconductor devices characterized by including the compound as described in any one of Claims 10-18.   An organic thin film transistor material comprising the compound according to any one of claims 10 to 18.   The coating solution for nonluminous organic-semiconductor devices characterized by including the compound as described in any one of Claims 10-18.   A coating solution for a non-luminescent organic semiconductor device, comprising the compound according to any one of claims 10 to 18 and a polymer binder.   The organic-semiconductor thin film for nonluminous organic-semiconductor devices characterized by including the compound as described in any one of Claims 10-18.   The organic-semiconductor thin film for nonluminous organic-semiconductor devices characterized by including the compound and polymer binder as described in any one of Claims 10-18.   The organic semiconductor thin film for a non-light-emitting organic semiconductor device according to claim 23 or 24, which is produced by a solution coating method.

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