JP6420143B2 - An organic semiconductor material characterized by a bent thienothiophene skeleton having a thiophene at the end. - Google Patents

Description

The present invention relates to a bent organic semiconductor material, and to an organic electronic device using the organic semiconductor material.

Organic semiconductors are expected to be applied to flexible displays such as organic EL and electronic paper, and it is expected that a large-area element can be produced at a lower cost than silicon semiconductors by application or printing, which are wet processes. In order to adapt to such a wet process, an organic semiconductor material having improved solubility in a solvent and having stability such as oxidation resistance is required.

Polyacene compounds such as pentacene and tetracene having high carrier mobility have long been known as organic semiconductor materials. However, this polyacene compound is unstable to light and oxidation, and further has low solubility in an organic solvent, so that it is difficult to use it in a wet process. Therefore, in order to improve chemical stability and solubility, benzothienobenzothiophene (hereinafter referred to as BTBT) or dinaphthothienothiophene (hereinafter referred to as DNTT) in which a chalcogen element such as sulfur or selenium is introduced into a part of the acene skeleton. Etc.) are being studied.

Among the DNTTs, dinaphtho [2,3-b: 2 ′, 3′-f] thieno [3,2-b] thienothiophene described in Non-Patent Document 1 and Patent Document 1 (hereinafter, proposal of Non-Patent Document 1) Have called this organic semiconductor DNTT, but here it is 2,3-DNTT.) Has been reported to show a high carrier mobility of 2.0 cm ² / Vs. However, 2,3-DNTT is stable in a solution state, but its solubility is 3.44 mg in 1 liter of dichloromethane at room temperature, and its solubility is low, making it difficult to use in a wet process. Therefore, the inventors of the present application are dinaphtho [2,1-b: 2 ′, 1′-f] thieno [3,2] which is stable in a solvent apart from 2,3-DNTT and has high solubility. -B] thiophene (hereinafter referred to as 2,1-DNTT) was developed and patented. (Patent Document 2, Patent Document 3)
In addition, dinaphtho [1,2-b: 1 ′, 2′-f] thieno [3,2-b] thiophene (hereinafter referred to as 1,2-DNTT) which has an isomer relationship with 2,1-DNTT is also used. Patented by the same applicant as Patent Documents 2 and 3 (Patent Document 4).

［化Ａ２］

［化Ａ３］

The general formulas of 2,3-DNTT, 2,1-DNTT, and 1,2-DNTT are shown in [Chemical A1], [Chemical A2], and [Chemical A3] below.
[Chemical A1]

[Chemical A2]

[Chemical A3]

On the other hand, in a condensed polycyclic aromatic compound having a structure similar to 2,3-DNTT, the solubility of the condensed polycyclic aromatic compound is improved by introducing a substituent into the aromatic ring adjacent to the central heterocyclic portion. There is also a patent application that has been found (Patent Document 5).

［化Ａ４］中、Ｘは、酸素、硫黄またはセレンである。 In addition, it has been clarified that in an organic semiconductor, when the molecular structure is linear, it tends to move as the temperature increases, thereby changing the molecular state and becoming unstable. Therefore, there is also a patent document in which a zigzag structure is required, dinaphthothiophene having a W-type structure which is chemically and physically stable and exhibits high carrier mobility, and a compound other than dinaphthothiophene as an organic semiconductor. (Patent Document 6). The chemical formula of the W-type structure of Patent Document 6 is shown in [Chemical Formula A4].
[Chemical A4]

In [Chemical A4], X is oxygen, sulfur or selenium.

［化Ａ５］中、Ａは、チオフェン、フラン、セレノフェン、ピロール環である。 As a result of examining an organic semiconductor material having a refractive thienothiophene skeleton in which the benzene ring at the end of 2,1-DNTT, which is an invention relating to the patent rights of the present inventors, is replaced with a thiophene ring, Patent Document 7 discloses di (benzo [b] thieno). [4,5-b: 4 ', 5'-f] thieno [3,2-b] thiophene (hereinafter, abbreviated 45DBT ³⁾ were found. The general formula of 45DBT ³ is shown in [Chemical A5].
45DBT ³ is an organic semiconductor material in which the benzene ring at the terminal of 1,2-DNTT is replaced with a thiophene ring.
[Chemical A5]

In [Chemical A5], A represents thiophene, furan, selenophene, or a pyrrole ring.

Up to now, there has been a problem that the transistor characteristics of 1,2-DNTT are less likely to appear than 2,1-DNTT. One of the reasons is that the HOMO level of 1,2-DNTT is −5.56 eV, which is deeper than the HOMO level of −5.40 eV of 2,1-DNTT, as shown in FIG. When the energy difference between the HOMO level of the electrode and the work function of the electrode is large, the hole injection barrier becomes large and carriers are difficult to flow, so that device characteristics such as carrier mobility are difficult to be obtained.

Therefore, 1, 2-DNTT and like relationships 2,1-DNTT, unlike 45DBT ^3, towards the isomer with more refracted molecular structure, is inferred HOMO level is shallow, also 2, By replacing the benzene ring at the terminal of 1-DNTT with a thiophene ring, it is assumed that the intermolecular interaction is stronger than 2,1-DNTT and heat resistance is improved by the terminal sulfur atom. Tried.
As a result, the inventors have invented an organic semiconductor characterized by a bent thienothiophene skeleton having excellent heat resistance and being easily soluble in an organic solvent and having a thiophene at the end.

WO2008 / 050726 JP 2009-302264 A JP 2010-161323 A JP 2010-258214 A JP 2013-197193 A JP2013-53140A WO2014 / 087300 A1

Tatsuya Yamamoto, Kazuo Takimiya "Journal of American Chemical Society" 2007, Vol. 129, 2224-2225

The problem to be solved is di (benzo [b] thieno) [4,5-b: 4 ′, 5′-f] thieno [3,2-b] thiophene, which is stable and has known solubility (45DBT ³ ) and higher than dinaphtho [2,3-b: 2 ′, 3′-f] thieno [3,2-b] thienothiophene (2,3-DNTT), bent with thiophene at the end It is an organic semiconductor material characterized by a type thienothiophene skeleton. The general formula is shown in [Chemical Formula 8].
[Chemical 8]

That is, the first invention is an organic semiconductor material characterized by a bent thienothiophene skeleton having a thiophene at the end represented by the chemical formula [Chemical Formula 1].
[Chemical 1]

Chemical [formula 1] R ⁸ substituted groups R1 in a hydrogen atom and a halogen atom, an aryl group having from 3 to 60 carbon atoms, heterocyclic group having a carbon number of 3 to 60, alkyl of from 1 to 30 carbon atoms Group, alkenyl group having 2 to 30 carbon atoms, alkynyl group having 2 to 30 carbon atoms, alkoxyl group having 1 to 30 carbon atoms, amino group having 1 to 60 carbon atoms, amide having 1 to 30 carbon atoms Group, imino group having 1 to 30 carbon atoms, carboxyl group having 1 to 30 carbon atoms, hydroxyl group, ester group having 1 to 30 carbon atoms, nitro group, nitrile group, sulfide group having 1 to 30 carbon atoms , A mercapto group, a sulfonyl group having 1 to 30 carbon atoms, and a silyl group having 1 to 60 carbon atoms, each of which may have a substituent. Preferred examples of the substituents R ¹ to R ⁸ are a hydrogen atom, a fluorine atom, an aryl group, a heterocyclic group, an alkyl group, an alkenyl group, an alkynyl group, and an amino group.

In the substituents R ¹ to R ⁸ , the halogen atom is fluorine, chlorine, bromine or iodine, and a preferred example is a fluorine atom.

In the substituents R ¹ to R ⁸ , the aryl group is an aromatic ring group having 3 to 60 carbon atoms, such as a phenyl group, 1-naphthyl group, 2-naphthyl group, biphenyl group, terphenyl group, anthryl group, phenanthryl. Group, chrysene and the like, and each of these groups may have a substituent.

The heterocyclic group in the substituents R ¹ to R ⁸ is a heterocyclic group having 3 to 60 carbon atoms, such as pyridine, pyrazine, triazine, pyrrole, quinoline, thiophene, benzothiophene, dibenzothiophene, thienothiophene, furan, benzofuran, Dibenzofuran, thiazole, benzothiazole and the like can be mentioned, and each of these groups may have a substituent.

In the substituents R ¹ to R ⁸ , the alkyl group is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, such as a methyl group, n-butyl group, n-pentyl group, n -Hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, isopropyl, t-butyl, cyclopropyl , A cyclohexyl group, an adamantyl group, an n-trifluoromethyl group, and the like, and each of these groups may have a substituent.

The alkenyl group in the substituents R ¹ to R ⁸ is an alkenyl group having 2 to 60 carbon atoms, and examples thereof include an ethenyl group, a methylethenyl group, an (n-octyl) ethenyl group, a phenylethenyl group, a naphthylethenyl group, and a biphenylethenyl group. , Terphenylethenyl group, perfluorophenylethenyl group and the like, and each of these groups may have a substituent.

The alkynyl group in the substituents R ¹ to R ⁸ is an alkynyl group having 2 to 60 carbon atoms, such as ethynyl group, methylethynyl group, (n-octyl) ethynyl group, phenylethynyl group, naphthylethynyl group, biphenylethynyl group. Group, terphenylethynyl group, perfluorophenylethynyl group and the like, and each of these groups may have a substituent.

In the substituents R ¹ to R ⁸ , the amino group is an amino group having 1 to 60 carbon atoms, and examples thereof include a diphenylamino group, a dinaphthylamino group, a dithienylamino group, and a dipyridylamino group. The group may have a substituent.

Examples of the substituent include a hydrogen atom and a halogen atom, an aryl group, a heterocyclic group, an alkyl group, a fluoroalkyl group, an alkenyl group, a fluoroalkenyl group, an alkynyl group, a fluoroalkynyl group, an alkoxyl group, a fluoroalkoxyl group, an amino group, Examples include amide group, imino group, carboxyl group, hydroxyl group, ester group, nitro group, nitrile group, sulfide group, mercapto group, sulfonyl group, and silyl group.

The formal name of [Chemical Formula 1] is di (benzo [b] thieno) [6,7-b: 6 ′, 7′-f] thieno [3,2-b] thiophene, hereinafter referred to as 67DBT ³ for short. To do.

The synthesis process of the 67DBT ³ organic semiconductor material represented by the chemical formula [Chemical Formula 1] described in the first invention is shown in Reaction Formula [Chemical Formula 4], but is not limited to the following synthesis method, and is a combination of known reactions. It is possible to synthesize.
[Chemical formula 4]

Compound A can be synthesized by reacting 2-bromothiophenol under basic conditions with 2-bromoacetaldehyde diethyl acetal and then with polyphosphoric acid.
As a method for synthesizing Compound A other than the above, a known method for synthesizing benzo [b] thiophene can be used. For example, an o-dihalobenzene such as o-dibromobenzene or 1-bromo-2-iodobenzene is converted into an organometallic compound using a known organolithium reagent such as n-BuLi or Mg, and sulfur is allowed to act on 2-bromoacetaldehyde. Compound A can be synthesized by using 2-halogenated acetaldehyde dialkyl acetal such as diethyl acetal and further using an acid catalyst such as polyphosphoric acid or diphosphoric acid.

Compound B can be synthesized by using a known organolithium reagent such as n-BuLi or Mg or the like as an organometallic compound and allowing a known formylating agent such as DMF or N-methylformanilide to act on compound A. it can.
67DBT ³ can be synthesized by allowing compound B to react with a halogen such as bromine or a known halogenating agent such as thionyl chloride and sulfur.

ただし、化学式［化２］中のＲ^１からＲ^８は、第１発明の［化１］のＲ^１からＲ^８と同じである。 Subsequently, the second invention is an organic semiconductor material characterized by a bent thienothiophene skeleton having a thiophene at the terminal represented by the chemical formula [Chemical Formula 2].
[Chemical 2]

However, ^{R 1 to R 8} of the formula [Formula 2] in is the same as ^{R 1 to R 8} in Formula 1] of the first invention.

Full name of the chemical formula [Formula 2] is di (benzo [b] thieno) [5,4-b: 5 ' , 4'-f] a thieno [3,2-b] thiophene, and 54DBT ^3.

Compound [Chemical Formula ^2] can synthesize 54DBT3 by reacting a known halogenating agent such as halogen such as bromine or thionyl chloride with sulfur in the same manner as Compound [Chemical Formula 1] of the first invention. . The reaction formula is shown in [Chemical Formula 5].
[Chemical formula 5]

ただし、化学式［化３］中のＲ^１からＲ^８は、第１発明の［化１］のＲ^１からＲ^８と同じである。 Subsequently, a third invention is an organic semiconductor material characterized by a bent thienothiophene skeleton having a thiophene at a terminal represented by the chemical formula [Chemical Formula 3].
[Chemical formula 3]

However, ^{R 1 to R 8} in the formula [Formula 3] is the same as ^{R 1 to R 8} in Formula 1] of the first invention.

The formal name of the chemical formula [Chemical Formula 3] is di (benzo [c] thieno) [5,4-b: 5 ′, 4′-f] thieno [3,2-b] thiophene, which is 54DBT ³ -C. .

Similarly to [Chemical Formula 1], Compound [Chemical Formula ^3] can synthesize 54DBT ³ -C by reacting aldehyde with a halogen such as bromine or a known halogenating agent such as thionyl chloride and sulfur. The reaction formula is shown in [Chemical Formula 6].
[Chemical 6]

Subsequently, a fourth invention is an organic electronic device made of an organic semiconductor material of any one of the chemical formulas [Chemical Formula 1], [Chemical Formula 2], and [Chemical Formula 3] described in the first invention to the third invention.

An organic electronic device as used herein refers to an electronic device that utilizes the electrical characteristics of the present compound. Specifically, an organic transistor, an organic light emitting diode, an organic diode, an organic laser, an organic thin film solar cell, an organic memory, etc. Is mentioned.

In order to use the compound of the present invention for these organic electronic devices, purification such as removal of impurities is required for high purity. Purification by gel method, gel permeation chromatography method, recrystallization method and the like.

Further, when the compound of the present invention is used for an organic electronic device, it is mainly used in the form of a thin film, and either a wet process or a dry process may be used as a method for forming the thin film. The compound of the present invention can be applied to a wet process having a large industrial merit by dissolving it in an organic solvent or the like.

Here, as the organic solvent, for example, known solvents such as dichloromethane, chloroform, chlorobenzene, cyclohexanol, toluene, xylene, nitrobenzene, methyl ethyl ketone, diglyme, and tetrahydrofuran can be used. In addition, when the compound of the present invention is dissolved in an organic solvent or the like, the temperature and pressure are not particularly limited, but the temperature for dissolution is preferably in the range of 0 to 200 ° C, more preferably in the range of 10 to 150 ° C. It is. Moreover, regarding the pressure to melt | dissolve, the range of 0.1-100 MPa is preferable, More preferably, it is the range of 0.1-10 MPa. Moreover, it is also possible to use something like supercritical carbon dioxide instead of the organic solvent.

The wet process here refers to a spin coating method, a dip coating method, a bar coating method, a spray coating method, an ink jet method, a screen printing method, a lithographic printing method, an intaglio printing method, a relief printing method, and the like. Can be used. In addition, the dry process mentioned here indicates a vacuum deposition method, a sputtering method, a CVD method, a laser deposition method, a molecular beam epitaxial growth method, a vapor phase transport growth method, and the like, and these known methods can be used.

Subsequently, the fifth invention is an organic electronic device comprising a combination of a plurality of organic semiconductor materials of any one of the chemical formulas [Chemical Formula 1], [Chemical Formula 2], and [Chemical Formula 3] described in the first to third inventions. It is.

Organic electronic device obtained by selecting and combining two types of organic semiconductor materials from any one of chemical formulas [Chemical Formula 1], [Chemical Formula 2], and [Chemical Formula 3], or selecting and combining all three types It is. The other matters are the same as in the fourth invention.

Examples of use of organic electronic devices using the organic semiconductor material of the present invention are shown in FIGS. 2 and 3 show examples of use in a field effect transistor (hereinafter referred to as FET). FETs are used as switching elements and amplifying elements because of their characteristics. In addition to a low gate current, the structure is planar, so that fabrication and integration by a wet process are easy and a large area can be achieved. Here, although the compound of the present invention is mainly used as a p-type semiconductor, it may function as an n-type semiconductor depending on a substituent or a solvent.

1st invention thru | or 3rd invention is dinaphtho [2,1-b: 2 ', 1'-f] thieno [3,2-b] thiophene (abbreviation 2, abbreviated as 2) which is an organic semiconductor material characterized by a thienothiophene skeleton. Di (benzo [b] thieno) [4,5-b, which is an isomer of the organic semiconductor according to the present application and has higher solubility in organic solvents and higher stability in solution than 1-DNT). : Compared with 4 ', 5'-f] thieno [3,2-b] thiophene (45DBT ³ ), it is estimated that it has higher solubility in organic solvents, and has a shallow HOMO level and can be driven at a low voltage. An organic semiconductor material is provided. The fourth and fifth inventions provide and protect organic electronic devices using these organic semiconductor materials.

FIG. 1 is a reference diagram of energy levels. FIG. 2 is a schematic view of a top contact FET. FIG. 3 is a schematic diagram of a bottom contact FET. Figure 4 is the ¹ H-NMR spectrum of 67DBT ^3. Figure 5 is a ¹ H-NMR spectrum of 8-67DBT ^3. Figure 6 is a ¹³ C-NMR spectrum of 8-67DBT ^3. Figure 7 is a ¹ H-NMR spectrum of 54DBT ^3. FIG. 8 shows the time course of the UV spectrum of pentacene. Figure 9 is a time course of UV spectra of 54DBT ^3. Figure 10 is a time course of UV spectra of 8-67DBT ^3. Figure 11 is a DSC chart of 54DBT ^3. FIG. 12 is a DSC chart of 2,1-DNTT.

Examples of the present invention are shown below.

The synthesis process of 67DBT ³ of the reaction formula [Chem. 4] will be described in detail, but the present invention is not limited only to these examples.
The target compound was determined by MS (mass spectrometry spectrum), ¹ H-NMR and ¹³ C-NMR as required. The equipment used is as follows.
MS: ABSCIEX Q-STAR
¹ H-NMR and ¹³ C-NMR: Agilent Technologies MercuryPlus

Operation 1
To 10 ml of a THF solution of 0.59 g (5.3 mmol) of sodium t-butoxide, 5 ml of a THF solution of 0.5 g (2.6 mmol) of 2-bromobenzenethiol was added dropwise. After stirring for 30 minutes, 0.62 g (3.2 mmol, 1.2 eq) of 2-bromoacetaldehyde diethyl acetal was added dropwise, and the mixture was stirred at room temperature for 1 hour. Water was added to the reaction mixture, and the mixture was extracted with toluene. The organic layer was concentrated under reduced pressure, 0.5 g of polyphosphoric acid was added, and the mixture was stirred overnight. Water was added to the reaction solution, extraction was performed with toluene, and the organic layer was concentrated under reduced pressure to obtain 0.3 g of Compound A in a yield of 54%.
The measurement results of 1H-NMR and 13C-NMR of Compound A are shown below.
1H-NMR (CDCl3, 400.4 MHz) δ = 7.23 (1H, t, J = 8.6 Hz), 7.41 (1H, d, J = 5.5 Hz), 7.47 (1H, d, J = 8.6 Hz), 7.47 (1H, d, J = 5.3 Hz), 7.74 (1H, dd, J = 0.8 Hz, 8.6 Hz).
13C-NMR (CDCl3, 100.7 MHz) [delta] = 116.1, 122.7, 124.9, 125.7, 127.3, 127.4, 140.7, 141.8.

Operation 2
In a nitrogen atmosphere, 2.8 ml (2.8 mmol, 2 eq) of iPrMgCl·LiCl (1M-THF solution) was added dropwise to 10 ml of a THF solution of 0.3 g (1.4 mmol) of Compound A, and the mixture was stirred at room temperature for 2 hours and then 0 ° C. Then, 0.29 ml (4.2 mmol, 3 eq) of N, N-dimethylformamide was added dropwise, and after the dropwise addition, the mixture was warmed to room temperature, treated with hydrochloric acid, extracted with toluene, and the organic layer was concentrated under reduced pressure. 15 g, 66% yield.
The measurement results of ¹ H-NMR and ¹³ C-NMR of Compound B are shown below.
¹ H-NMR (CDCl ₃ , 400.4 MHz) δ = 7.42 (1H, d, J = 5.5 Hz), 7.56 (1H, t, J = 7.2 Hz), 7.64 (1H, d, J = 5.6 Hz), 7.85 (1H, ddd, J = 0.4 Hz, 1.1 Hz, 7.2 Hz) 8.03 (1H, dd, J = 1.1 Hz, 7.8 Hz), 10.23 (1H, s).
¹³ C-NMR (CDCl ₃ , 100.7 MHz) δ = 122.9, 124.3, 129.8, 130.5, 130.9, 131.4, 137.1, 141.3, 191.3.

Operation 3
Under a nitrogen atmosphere, 0.1 ml of N, N-dimethylformamide was added to 5 ml of a toluene solution of 0.15 g (0.93 mmol) of Compound B. 0.9 g (7.4 mmol, 8 eq) thionyl chloride and 0.04 g (1.1 mmol, 1.2 eq) sulfur were added and heated to 220 ° C. and kept for 1 hour. After cooling, the reaction solution was filtered to obtain 67DBT in a yield of 11%.
The measurement results of MS and 1H-NMR of 67DBT ³ are shown below. Further, the 1H-NMR spectrum of 67DBT ³ is shown in FIG.
MS (APPI) m / z = 352
1H-NMR (CDCl3, 400.4 MHz) δ = 7.58 (2H, d, J = 5.28 Hz), 7.63 (2H, d, J = 5.28 Hz), 7.91 (2H, d, J = 8.6 Hz), 8.00 (2H, d, J = 8.6 Hz).

８−６７ＤＢＴ^３のＭＳ、^１Ｈ−ＮＭＲおよび^１３Ｃ−ＮＭＲの測定結果を以下に示す。また、８−６７ＤＢＴ^３の^１Ｈ−ＮＭＲスペクトルを図５に、^１３Ｃ−ＮＭＲスペクトルを図６に示す。
ＭＳ（ＡＰＰＩ） ｍ／ｚ＝５７６
^１Ｈ―ＮＭＲ（Ｃ_２Ｄ_２Ｃｌ_４， ４００．４ＭＨｚ）δ＝０．９１（６Ｈ，ｔ，Ｊ＝７．１Ｈｚ），１．３１（２０Ｈ，ｍ），１．８５（４Ｈ，ｍ），３．０４（４Ｈ，ｔ，Ｊ＝７．４Ｈｚ），７．２５（２Ｈ，ｓ），７．７６（２Ｈ，ｄ，Ｊ＝８．６Ｈｚ），７．９４（2Ｈ，ｄ，Ｊ＝８．６Ｈｚ）．
^１３Ｃ−ＮＭＲ（Ｃ_２Ｄ_２Ｃｌ_４， １００．７ＭＨｚ）δ＝１４．３，２２．７，２９．２，２９．３，２９．４，３０．９，３１．５，３１．９，１２０．１，１２０．２，１２１．２，１２７．０，１３１．８，１３２．１，１３７．７，１３９．０，１４６．７． 8-67DBT ³ was synthesized using the same synthesis method. The reason why 8-67DBT ³ is selected is that C ₈ H ₁₇ is added to the terminal thiophene ring. The reaction formula of 8-67DBT ³ is shown in [Chemical 7].
[Chemical 7]

The measurement results of MS, ¹ H-NMR and ¹³ C-NMR of 8-67DBT ³ are shown below. Further, the ¹ H-NMR spectrum of 8-67DBT ³ is shown in FIG. 5, and the ¹³ C-NMR spectrum is shown in FIG.
MS (APPI) m / z = 576
¹ H-NMR (C ₂ D ₂ Cl ₄ , 400.4 MHz) δ = 0.91 (6H, t, J = 7.1 Hz), 1.31 (20H, m), 1.85 (4H, m) 3.04 (4H, t, J = 7.4 Hz), 7.25 (2H, s), 7.76 (2H, d, J = 8.6 Hz), 7.94 (2H, d, J = 8.6 Hz).
¹³ C-NMR (C ₂ D ₂ Cl ₄ , 100.7 MHz) δ = 14.3, 22.7, 29.2, 29.3, 29.4, 30.9, 31.5, 31.9, 120.1, 120.2, 121.2, 127.0, 131.8, 132.1, 137.7, 139.0, 146.7.

54DBT ³ was synthesized using a similar synthesis method. The synthesis of 54DBT ³ is shown in the above reaction formula [Chem. 5].
The measurement results of MS and ¹ H-NMR of 54DBT ³ are shown below. The ¹ H-NMR spectrum of 54DBT ³ is shown in FIG.
MS (APPI) m / z = 352
¹ H-NMR (C ₂ D ₂ Cl ₄ , 400.4 MHz) δ = 7.76 (2H, d, J = 5.3 Hz), 7.96 (6H, m).

8, FIG. 9, FIG. 10, UV put pentacene dissolved in an organic solvent 1,1,2,2-Tetrachloroethane, 0 hours 54DBT ³ and 8-67DBT ^3, the time course of 24 hours and 48 hours The spectrum is shown. From these figures, it can be said that 54DBT ³ and 8-67DBT ³ are very stable with no change in spectrum even when left in a solution for 48 hours. On the other hand, it can be seen that the spectrum of pentacene changes greatly after 24 hours, is unstable in solution, and has decomposed.

Solubility was as follows: 2,3-DNTT was 3.4 mg / L in dichloromethane (literature value), 45DBT ³ was 45.5 mg / L, whereas 54DBT ³ was 166.7 mg / L. ³ is found to be more soluble than 45DBT ³ , 2,3-DNTT. The solubility of 8-67DBT ³ having an alkyl group is 1125 mg / L in dichloromethane, and the solubility is very high at 66 g / L in 80 ° C. toluene.

Moreover, as shown in [FIG. 11] and [FIG. 12], from the measurement result of DSC (differential scanning calorimeter), the melting point of 2,1-DNTT is 306.3-307.0 ° C., and the melting point of 54DBT ³ is Since 357.6-358.0 ° C., 54DBT ³ has a higher melting point than 2,1-DNTT and no phase transition point at low temperature, it can be said that it has excellent heat resistance.

1 Top contact FET
2 Bottom contact FET
3 Source
4 Drain 5 Organic semiconductor 6 Insulating film 7 Substrate (gate)

As described above, since it has high solubility in organic solvents and is stable, it is expected as an organic semiconductor material used in wet processes.

Claims (4)

An organic semiconductor material characterized by a bent thienothiophene skeleton having a thiophene at a terminal represented by the chemical formula [Chemical Formula 1]. [Chemical 1]

The substituents R ¹ to R ⁸ in the chemical formula [Chemical Formula 1] are a hydrogen atom and a halogen atom, an aryl group having 3 to 60 carbon atoms, a heterocyclic group having 3 to 60 carbon atoms, and 1 to 30 carbon atoms. Alkyl group, alkenyl group having 2 to 30 carbon atoms, alkynyl group having 2 to 30 carbon atoms, alkoxyl group having 1 to 30 carbon atoms, amino group having 1 to 60 carbon atoms, 1 to 30 carbon atoms Amido group, imino group having 1 to 30 carbon atoms, carboxyl group having 1 to 30 carbon atoms, hydroxyl group, ester group having 1 to 30 carbon atoms, nitro group, nitrile group, sulfide having 1 to 30 carbon atoms It includes at least one of a group, a mercapto group, a sulfonyl group having 1 to 30 carbon atoms, and a silyl group having 1 to 60 carbon atoms, and each of these groups may have a substituent. An organic semiconductor material characterized by a bent thienothiophene skeleton having a thiophene at a terminal represented by the chemical formula [Chemical Formula 2]. [Chemical 2]

However, ^{R 8} from ^{R 1} of the formula [Formula 2] in is the same as the ^{R 1} of Formula 1 of claim 1 and ^{R 8.} An organic electronic device comprising the organic semiconductor material represented by any one of the chemical formulas [Chemical Formula 1] and [Chemical Formula 2] according to claim 1. The organic electronic device formed by combining the organic-semiconductor material in any one of chemical formula [Chemical Formula 1] of [Chemical Formula 1], and [Chemical Formula 2].

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