JP2016050179A - Benzobis (thiadiazole) derivative and organic electronics device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a benzobis (thiadiazole) derivative that is easy and simple to synthesize and is excellent in electronic mobility (field-effect mobility).SOLUTION: The present invention provides a benzobis (thiadiazole) derivative represented by general formula (1) (where Rand Reach represent a predetermined group).SELECTED DRAWING: None

Description

  The present invention relates to a benzobis (thiadiazole) derivative and organic electronic devices such as an organic thin film transistor, an organic electroluminescence element, a display device, an organic thin film solar cell, an RFID tag, and a sensor using the same.

  Conventionally, benzobisthiazole compounds have attracted attention as compounds for organic thin film transistors (organic TFTs), organic electroluminescence elements (organic EL elements) or organic thin film solar cells, and research on various derivatives having benzobis (thiadiazole) as the main skeleton. Development is actively underway.

  In particular, in order to improve the mobility of holes and electrons, benzobis (thiadiazole) derivatives into which strong electron-withdrawing groups are introduced have been proposed. For example, Patent Document 1, Non-Patent Document 1, and Non-Patent Document 2 , A compound in which a trifluoromethylphenyl group or the like is bonded to benzobis (thiadiazole) via a thienylene group is disclosed. This compound has improved hole and electron mobility due to the introduction of a trifluoromethylphenyl group, which is a strong electron-withdrawing group.

  Also, Patent Document 2 discloses various benzobisthiadiazole compounds as materials for n-type organic semiconductors, but what was actually synthesized in the examples of the document is 4,8-bis [3, Only 5-bis (trifluoromethyl) phenyl] benzo [1,2-c; 4,5-c ′] bis [1,2,5] thiadiazole (see structural formula below).

  Also, it is generally known that benzobis (thiadiazole) is not the main skeleton, but introduction of a strong electron-withdrawing group into the thiophene ring can improve the electron stability and mobility of the compound. (For example, refer to Patent Document 3).

WO2013 / 141182 pamphlet JP 2013-124231 A JP 2009-280515 A

Chem. Commun. , 46, 3265 (2010) Applied Physics Lett. , 97, 133303 (2010)

  In Patent Document 2, various benzobisthiadiazole compounds are disclosed as n-type organic semiconductor materials. As described above, synthesized compounds are 4,8-bis [3,5-bis (trifluoromethyl). ) Phenyl] benzo [1,2-c; 4,5-c ′] bis [1,2,5] thiadiazole. Further, Patent Document 2 describes the results of cyclic voltammetry (CV) measurement of the above compound, but a device such as a thin film transistor (TFT) is produced using this compound, and the characteristics are not evaluated. For this reason, it cannot be said in Patent Document 2 that even the compounds actually synthesized in the above-described examples have been confirmed to have sufficient characteristics as organic semiconductor materials.

  Similarly, the general description of Patent Document 2 discloses a compound in which a benzobisthiadiazole compound is bonded with a thiophene that is a π-excess heteroaromatic ring. However, there are 2 electron-withdrawing substituents on the thiophene. It is preferred that they are connected. And the following example is shown as such a thiophene structure (the following (4-194) has three electron withdrawing groups couple | bonded).

  However, in these structures, out of 4 carbons to which a substituent on the thiophene ring can be bonded, 1 is a bond with benzobisthiadiazole, 2 (or 3) is an electron withdrawing group The synthesis of such compounds is expected to be extremely difficult because the electron density on the aromatic ring is significantly reduced. And including such compounds, the 4,8-bis [3,5-bis (trifluoromethyl) phenyl] benzo [1,2-c; 4,5-c ′] bis having the structural formula shown above. As described above, no compounds other than [1,2,5] thiadiazole have been synthesized in the Examples of Patent Document 2 in the first place.

  Under such circumstances of the prior art, an object of the present invention is to provide a benzobis (thiadiazole) derivative that is easy to synthesize and excellent in electron mobility (field effect mobility). Another object of the present invention is to provide organic electronic devices such as organic thin film transistors, organic electroluminescent elements, display devices, organic thin film solar cells, RFID tags, and sensors using the benzobis (thiadiazole) derivatives.

  The present invention relates to the following matters.

  1. A benzobis (thiadiazole) derivative represented by the following general formula (1):

(In the formula, two R ^{1 s} independently represent a hydrogen atom, a linear or branched alkyl group, or a group of the following formula (2), and the two R ^{2 s} independently represent a hydrogen atom, It represents either a linear or branched alkyl group or a group of the following formula (2), provided that ^one of two R ¹ and two R ² is one of the groups of the following formula (2) And the other is not any of the groups of the following formula (2).);

(In the formula, R represents a linear or branched alkyl group).

2. In the general formula (1), two R ¹ are independently any of the groups of the formula (2), and two R ² are independently a hydrogen atom or a linear or branched alkyl group. The benzobis (thiadiazole) derivative according to 1 above, wherein

3. The benzobis (thiadiazole) according to the above 1 or 2, wherein, in the general formula (1), two R ¹ are independently any of the groups of the formula (2), and two R ² are hydrogen atoms. ) Derivatives.

  4). The benzobis (thiadiazole) derivative according to any one of 1 to 3 above, wherein the group of the formula (2) is any of the groups of the following formula (3).

5). In the general formula (1), two R ¹ are independently any one of a trifluoromethyl group, a cyano group, and an acyl group (—C (═O) R), and the two R ² are hydrogen atoms. The benzobis (thiadiazole) derivative according to any one of 1 to 4 above.

  6). An organic electronic device provided with the organic layer containing the benzobis (thiadiazole) derivative in any one of said 1-5.

  7). The substrate has a gate electrode, a gate insulating layer, an organic semiconductor layer, a source electrode and a drain electrode, and the organic semiconductor layer comprises the benzobis (thiadiazole) derivative according to any one of 1 to 5 above. Including organic thin film transistor.

  8). 8. The organic thin film transistor according to 7 above, wherein the substrate is a flexible substrate.

  9. The substrate has an anode, a light emitting layer, a hole transport layer and / or an electron transport layer, and a cathode, and the hole transport layer and / or the electron transport layer is any one of 1 to 5 above. An organic electroluminescence device comprising the benzobis (thiadiazole) derivative described in 1.

  10. A display device that drives and lights an organic electroluminescence element using an organic thin film transistor, wherein the organic thin film transistor is the organic thin film transistor according to 7 or 8 above.

  11. 9. An active matrix type display device in which pixel elements each including the organic thin film transistor according to 7 or 8 and an organic electroluminescence element are arranged in a matrix.

  12 12. The display device according to 10 or 11 above, wherein the organic electroluminescence element is the organic electroluminescence element according to 9 above.

  13. 10. A display device that drives and lights an organic electroluminescence element using an organic thin film transistor, wherein the organic electroluminescence element is the organic electroluminescence element described in 9 above.

  14 The substrate has an anode, a charge separation layer containing a hole transport material and an electron transport material, and a cathode, and the charge separation layer comprises the benzobis (thiadiazole) derivative according to any one of 1 to 5 above. Including organic thin-film solar cells.

  15. The substrate has an anode, a charge separation layer including a hole transport material and an electron transport material, a hole transport layer and / or an electron transport layer, and a cathode, and the hole transport layer and / or the electron The organic thin-film solar cell in which a transport layer contains the benzobis (thiadiazole) derivative in any one of said 1-5.

  16. 16. The organic thin-film solar cell as described in 14 or 15 above, wherein the substrate is a flexible substrate.

  17. 9. An RFID tag that operates using an organic thin film transistor, wherein the organic thin film transistor is the organic thin film transistor according to 7 or 8 above.

  18. 9. A sensor that operates using an organic thin film transistor, wherein the organic thin film transistor is the organic thin film transistor according to 7 or 8 above.

  According to the present invention, a benzobis (thiadiazole) derivative that is excellent in electron mobility (field effect mobility) and can be easily synthesized can be provided. Since the benzobis (thiadiazole) derivative of the present invention is excellent in electron mobility (field effect mobility), for example, organic thin film transistors, organic electroluminescence elements, display devices, organic thin film solar cells, RFID tags, sensors, and other organic materials. It can be suitably used for an electronic device. Moreover, it can be used suitably for many other devices.

It is sectional drawing which shows the layer structure of an example of the organic thin-film transistor (organic TFT) of this invention. It is sectional drawing which shows the layer structure of an example of the organic electroluminescent element (organic EL element) of this invention. It is sectional drawing which shows the layer structure of an example of the display device of this invention. It is sectional drawing which shows the layer structure of an example of the organic thin film solar cell of this invention. It is a figure which shows the transfer characteristic of the organic TFT of Example E-1c. It is a figure which shows the transfer characteristic of the organic TFT of Example E-4a. It is a figure which shows the transfer characteristic of the organic TFT of the comparative example E-6a.

  Hereinafter, the benzobis (thiadiazole) derivative and the organic electronics device of the present invention will be described in detail.

<Benzobis (thiadiazole) derivative>
The benzobis (thiadiazole) derivative of the present invention is represented by the following general formula (1). Hereinafter, the groups R ¹ and R ² in the following general formula (1) will be described.

In the general formula (1), the two R ¹ independently represents a hydrogen atom, a linear or branched alkyl group, or any group of the following formula (2). Moreover, two R < ² > shows either a hydrogen atom, a linear or branched alkyl group, or the group of following formula (2) independently.

The linear or branched alkyl group in the groups R ¹ and R ² has 1 to 30 carbon atoms from the viewpoint of improving the solubility and field effect mobility of the benzobis (thiadiazole) derivative of the present invention. Is preferable, the number of carbon atoms is more preferably 3 to 25, and the number of carbon atoms is particularly preferably 5 to 20. Moreover, about a branched alkyl group, the branched chain and the principal chain part may couple | bond together and it may form the cyclic structure. That is, the branched alkyl group includes a cycloalkyl group.

  Specific examples of the linear alkyl group include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group. , Tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, and the like, and the following structures are also included (in addition, there are also those that overlap with those exemplified above) ).

  In the structure shown above, the asterisk is a bond. The same applies to the following.

  Next, specific examples of the branched alkyl group include, for example, isopropyl group, 1-methylpropyl group, 1-methylbutyl group, t-butyl group, 2-methylhexyl group, 2-ethylhexyl group, and 3-methylhexyl group. , 3-ethylhexyl group, 2-methyloctyl group, 2-ethyloctyl group, 3-methyloctyl group, 3-ethyloctyl group, etc. Some may overlap with those illustrated).

^{One of} the groups R ¹ and R ² described above is any of the groups of the above formula (2), and the other is not any of the groups of the above formula (2) (that is, a hydrogen atom or direct A chain or branched alkyl group). Thus, in the benzobis (thiadiazole) derivative of the present invention, one electron-withdrawing group (group of the above formula (2)) is bonded to each thiophene ring bonded to the central benzobis (thiadiazole) nucleus. It has excellent field effect mobility and is easy to synthesize.

As described above, ^{one of the} groups R ¹ and R ² is any of the groups of the above formula (2). In the group of the formula (2), R represents a linear or branched alkyl group.

  R is preferably a linear or branched alkyl group having 1 to 30 carbon atoms from the viewpoint of improving the solubility and field effect mobility of the benzobis (thiadiazole) derivative of the present invention, and a linear chain having 1 to 20 carbon atoms. A linear or branched alkyl group is more preferable, and a linear or branched alkyl group having 1 to 15 carbon atoms is particularly preferable.

Specific examples of such R include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, Undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, etc.
Examples of the branched alkyl group include isopropyl group, 1-methylpropyl group, t-butyl group, 1-methylbutyl group, 2-methylhexyl group, 2-ethylhexyl group, 3-methylhexyl group, 3-ethylhexyl group, Examples include 2-methyloctyl group, 2-ethyloctyl group, 3-methyloctyl group, and 3-ethyloctyl group.

  Among the groups of the formula (2) described above, any of the groups of the following formula (3) is preferable from the viewpoint that the benzobis (thiadiazole) derivative of the present invention exhibits n-type transistor characteristics.

In the formula, R is as defined above. Among these, a trifluoromethyl group, a cyano group, and an acyl group (—C (═O) R) are more preferable from the same viewpoint.

(Preferred combinations of R ¹ and R ² according to embodiments of the present invention)
In the general formula (1) described above, in one embodiment of the present invention, two R ¹ are independently any of the groups of the formula (2), and two R ² are independently hydrogen atoms. Or a linear or branched alkyl group. On the other hand, the two R ^{1 s} are independently a hydrogen atom or a linear or branched alkyl group, and the two R ^{2 s} are independently any one of the groups of the formula (2). preferable.

Moreover, in another embodiment of this invention, it is preferable that two R < ¹ > is independently either of the groups of said Formula (2), and R < ² > is a hydrogen atom. On the other hand, it is also preferable that R ¹ is a hydrogen atom and two R ² are independently any one of the groups of the formula (2).

In still another embodiment of the present invention, it is preferable that two R ^{1 s} are independently any one of a trifluoromethyl group, a cyano group, and an acyl group, and R ² is a hydrogen atom. On the other hand, it is also preferable that R ¹ is a hydrogen atom and two R ² are independently any one of a trifluoromethyl group, a cyano group, and an acyl group.

Two or more of R ^{1 described,} the two R ^2, are both respectively, may be the same or different, but usually the like Benzobisu (thiadiazole) for ease of synthesis of the derivatives of the present invention, It is preferable that they are the same.

(Benzobis (thiadiazole) derivatives)
Examples of the benzobis (thiadiazole) derivative of the present invention described above include compounds represented by the following formulas (11) to (84). However, in the formula, R is as defined in the above formula (2).

(Method for synthesizing benzobis (thiadiazole) derivatives)
The benzobis (thiadiazole) derivative of the present invention can be synthesized from known starting materials by combining known reactions, and the synthesis method is not particularly limited. For example, the following reaction scheme (tination) It can be synthesized according to step A or B and the coupling step).

(Tinning step A or B)

(Coupling process)

In the above reaction scheme, R, R ¹ and R ² are as defined above, Bu represents a butyl group, and X ¹ and X ² independently represent a halogen atom (must be a bromine atom or an iodine atom). Is preferred).

(Tinning process A)
The tinning step A is performed when the benzobis (thiadiazole) derivative of the present invention in which R ¹ or R ² which is the group of the formula (2) is other than an acyl group (—C (═O) R) is synthesized. In the tinning step A, a carbon atom adjacent to the S atom of thiophene and a carbon atom adjacent to the carbon atom, each having R ¹ and R ² bonded thereto, are prepared. The compound is commercially available or can be synthesized from thiophene.

On the other hand, by reacting a predetermined organostannation reagent in the presence of a base, the position of the carbon atom adjacent to the S atom in which R ¹ is not bonded to thiophene is organotinylated. As the base, n-BuLi (Bu represents a butyl group) and LDA (lithium diisopropylamide) are preferable. The same applies to the following tin forming step B.

(Tinning process B)
The tinning step B is carried out when synthesizing the benzobis (thiadiazole) derivative of the present invention in which R ¹ or R ² which is the group of the formula (2) is an acyl group (—C (═O) R). In the tinning step B, a compound in which the carbon atom adjacent to the S atom of thiophene is halogenated is prepared. The compound is commercially available and can be easily synthesized from thiophene.

On the other hand, Friedel-Crafts alkanoylation is performed to introduce a —C (═O) R group into the thiophene ring, followed by reaction with a predetermined organotin reagent in the presence of a base and a palladium catalyst (Pd cat). Thus, the carbon atom at the position where the halogen (X ¹ ) was bonded is converted into an organotin.

Examples of the palladium catalyst used here include tetrakis (triphenylphosphine) palladium (Pd (PPh ₃ ) ₄ ), dichlorobis (triphenylphosphine) palladium (PdCl ₂ (PPh ₃ ) ₂ ), and bis (tri-tert-butyl). One or more palladium complexes such as phosphine) palladium (Pd (PtBu ₃ ) ₂ ), palladium acetate (Pd (OAc) ₂ ), palladium chloride (PdCl ₂ ) are preferable, and PdCl ₂ (PPh ₃ ) ₂ and Pd (PPh ₃ ) ₄ is more preferable.

(Coupling process)
In the coupling step, first, benzobis (thiadiazole) (formula (94)) in which a bromine atom is introduced at the benzene ring position is prepared. The said compound is marketed and can also be synthesize | combined by a well-known raw material and reaction.

  The benzobis (thiadiazole) of the present invention is reacted with the compound obtained in the stannation step A or B in the presence of a palladium catalyst according to the target benzobis (thiadiazole) derivative of the present invention. ) Derivatives can be synthesized. In the above scheme, the case where the compound obtained in the tinning step A is reacted is shown. The amount of the palladium catalyst used here is preferably 0.01 to 0.5 mol with respect to 1 mol of benzobis (thiadiazole) in which a bromine atom is introduced at the benzene ring position. More preferably, 0.1 to 0.5 mol is used.

  The method for synthesizing the benzobis (thiadiazole) derivative of the present invention described above is a simple synthesis method that includes two steps of the stannation step and the coupling step and can synthesize the target compound in only two steps. Other steps may be included as necessary.

  After completion of the reaction of the reaction scheme described above, the benzobis (thiadiazole) of the present invention is subjected to general operations such as filtration, concentration, extraction, distillation, sublimation, recrystallization, column chromatography and the like from the obtained reaction solution. Derivatives can be isolated and purified. In order to remove impurities with different solubilities and improve compound purity, it is convenient and preferable to incorporate Soxhlet extraction with an organic solvent into the purification step.

(Solubility of benzobis (thiadiazole) derivatives)
The benzobis (thiadiazole) derivative of the present invention is usually water or various organic solvents such as methanol, ethanol, propanol, ethylene glycol, isobutanol, 2-butanol, 2-ethyl-1-butanol, n-octanol, Alcohols such as benzyl alcohol and terpineol;
Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, acetophenone, and isophorone:
Esters such as methyl acetate, ethyl acetate, butyl acetate, methyl benzoate, butyl benzoate, methyl salicylate, ethyl malonate, 2-ethoxyethane acetate, and 2-methoxy-1-methylethyl acetate;
Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N-methylpyrrolidone, N-ethylpyrrolidone, and hexamethylphosphoric triamide;
Ureas such as 1,3-dimethyl-2-imidazolidinone and 1,3-dimethylimidazolidine-2,4-dione;
Sulfoxides such as dimethyl sulfoxide and diethyl sulfoxide;
Sulfones such as sulfolane;
Nitriles such as acetonitrile, propionitrile, butyronitrile, and benzonitrile;
Lactones such as γ-butyrolactone;
Diethyl ether, diisopropyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, tert-butyl methyl ether, anisole, phenetole, 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, 1,4-dimethoxybenzene, 1,2- Ethers such as methylanisole, 1,3-methylanisole, 1,4-methylanisole, 1,2-methylenedioxybenzene, 2,3-dihydrobenzofuran, phthalane, octyloxybenzene, diphenyl ether, and ethyl cellosolve;
Carbonates such as dimethyl carbonate and 1,2-butylene glycol carbonate;
Thioethers such as thioanisole and ethyl phenyl sulfide;
Benzene, toluene, xylene, mesitylene, pseudocumene, hemimelliten, durene, isodurene, prienten, ethylbenzene, cumene, tert-butylbenzene, cyclohexylbenzene, triisopropylbenzene, phenylacetylene, indane, methylindane, indene, tetralin, naphthalene, 1- Aromatic hydrocarbons such as methylnaphthalene, 2-methylnaphthalene, phenyloctane, and diphenylmethane;
Phenols such as phenol, 1,2-cresol, 1,3-cresol, 1,4-cresol, 1,2-methoxyphenol, 1,3-methoxyphenol, and 1,4-methoxyphenol;
Chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,2,4-trichlorobenzene, bromobenzene, 1,2-dibromobenzene, 1,3-dibromobenzene, 1,4-dichlorotoluene, 1 -Chloronaphthalene, 2,4-dichlorotoluene, 2-chloro-1,3-dimethylbenzene, 2-chlorotoluene, 2-chloro-1,4-dimethylbenzene, 4-chloro-1,2-dimethylbenzene, 2 Halogenated aromatic hydrocarbons such as 1,5-dichlorotoluene, m-chlorotoluene, 1-chloro-2,3-dimethylbenzene, 4- (trifluoromethoxy) anisole, and trifluoromethoxybenzene;
Aliphatic hydrocarbons such as hexane, heptane, octane, cyclohexane, and limonene;
Halogenated aliphatic hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,3-dichloropropane, and 1,2-dibromoethane;
It is soluble in pyridines such as 2,6-dimethylpyridine and 2,6-ditert-butylpyridine.

  “Soluble in water or organic solvent” means that it is preferably 0.03 wt% with respect to water or organic solvent at normal pressure and below boiling point, preferably 80 ° C. or less, more preferably 15 ° C. to 30 ° C. or less. As described above, it means that it has a solubility of 0.1 wt% or more. The benzobis (thiadiazole) derivative of the present invention is not required to be soluble in water and all organic solvents, but is soluble in water or at least one of the organic solvents listed above. The organic solvent includes a mixed solvent of a plurality of organic solvents, and the benzobis (thiadiazole) derivative of the present invention is not soluble in any of the organic solvents alone, but is soluble in the mixed solvent. There is also a possibility.

  Examples of the organic solvent include halogenated aromatic hydrocarbons, aromatic hydrocarbons, and the like from the viewpoint of the film forming property of the organic semiconductor thin film of the organic semiconductor ink of the present invention described below and the semiconductor characteristics thereof. , And halogenated aliphatic hydrocarbons can be preferably used.

  Suitable halogenated aromatic hydrocarbons include chlorobenzene and 1,2-dichlorobenzene.

  Suitable aromatic hydrocarbons include toluene, xylene, mesitylene, tetralin, cyclohexylbenzene, and 1-methylnaphthalene.

  Suitable halogenated aliphatic hydrocarbons include chloroform and 1,2-dichloroethane.

  Furthermore, other organic solvents suitable from the same viewpoint as above include methyl benzoate, methyl salicylate, anisole, 4-methylanisole, and metacresol.

(Semiconductor properties of benzobis (thiadiazole) derivatives)
The benzobis (thiadiazole) derivative of the present invention described above is centered on the benzobis (thiadiazole) ring represented by the above general formula (1), and an aromatic thiophene ring is bonded to this, and each thiophene ring has an electron. Since any of the groups represented by the attractive formula (2) is bonded, the electron mobility is excellent, and it can be used as an excellent n-type organic semiconductor material.

  Moreover, the benzobis (thiadiazole) derivative exhibits n-type semiconductor characteristics over the p-type semiconductor characteristics, and thus is extremely useful as an organic semiconductor material in transistor elements and the like.

In this specification, “showing n-type semiconductor characteristics predominately over p-type semiconductor characteristics” is when the following conditions are satisfied.
The n-type field effect mobility is 10 ⁴ times or more that of the p-type field effect mobility.

<Organic semiconductor ink>
As described above, the benzobis (thiadiazole) derivative of the present invention exhibits n-type semiconductor characteristics and is usually soluble in water and organic solvents, so the benzobis (thiadiazole) derivative of the present invention is dissolved in water and organic solvents. The obtained solution can be used as an organic semiconductor ink. In addition, these water and organic solvent may be used independently, and 2 or more types may be mixed and used for them.

  If an organic semiconductor ink can be used, it is easy to handle and can be stored. Furthermore, as a method for forming the organic semiconductor layer, vapor deposition and coating are generally used. However, a special apparatus and environment are necessary for the vapor deposition, and the cost is very high as compared with the coating. That is, if the organic semiconductor ink of the present invention is used, the formation cost of the organic semiconductor layer can be greatly reduced.

  The organic semiconductor ink of the present invention contains one or more benzobis (thiadiazole) derivatives of the present invention, and can also contain one or more other organic semiconductors. Further, the organic semiconductor ink of the present invention includes an additive for adjusting the viscosity of the ink, an additive for controlling the hydrophilicity or water repellency of the ink, an antioxidant, a light stabilizer, a surface conditioner (leveling agent). ), A surfactant, a storage stabilizer, a lubricant, a wettability improver, and a coupling agent, and the like can be added.

  Examples of the additive for adjusting the viscosity of the ink include an insulating polymer compound. Insulating polymer compounds are synthetic resins, plastics, synthetic rubbers, etc., specifically polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyester, phenol resin, acrylic resin, amide resin, nylon, vinylon, Examples include polyisoprene, polybutadiene, acrylic rubber, acrylonitrile rubber, and urethane rubber. Addition of these makes it possible to optimize the viscosity of the organic semiconductor ink and improve the film forming property.

  The content of the benzobis (thiadiazole) derivative of the present invention in the organic semiconductor ink is not particularly limited and can be appropriately selected. For example, the content can be about 0.001 wt% to 10 wt%, and further 0.01 wt% to About 1 wt% is preferable from the viewpoint of film forming properties. Moreover, when the said ink contains another organic semiconductor, content of these and the said benzobis (thiadiazole) derivative can be 0.001-10 wt%, for example. Moreover, the addition amount of said various additives can be suitably selected from a conventionally well-known range.

  Examples of the other organic semiconductors include polymer semiconductor compounds. Here, the polymer semiconductor compound is a polymer compound characterized by exhibiting semiconductor characteristics, and specifically includes a polyacetylene polymer, a polydiacetylene polymer, a polyparaphenylene polymer, and a polyaniline polymer. Polymer, polytriphenylamine polymer, polythiophene polymer, polypyrrole polymer, polyparaphenylene vinylene polymer, polyethylenedioxythiophene polymer, copolymer polymer with naphthalenediimide as one component, perylene Examples thereof include a copolymer polymer containing diimide as one component and a copolymer polymer containing diketopyrrolopyrrole as one component.

  Among these polymer semiconductor compounds, polyaniline polymer, polythiophene polymer, polypyrrole polymer, polyparaphenylene vinylene polymer, copolymer polymer containing naphthalenediimide as one component, and perylene diimide as one component And a copolymer polymer containing diketopyrrolopyrrole as one component are suitable.

  Still other organic semiconductors include, for example, low molecular semiconductor compounds other than the benzobis (thiadiazole) derivative of the present invention. The low molecular weight semiconductor compound herein is a low molecular weight compound characterized by exhibiting semiconductor characteristics, and specifically includes acene, phenylene vinylene, triphenylamine, fluorene, azaacene, thienoacene, thiophene, benzothiophene, Examples include thienothiophene, thiazole, thiazolothiazole, tetrathiafulvalene, phthalocyanine, porphyrin, naphthalene diimide, perylene diimide, benzothiadiazole, naphthobithiadiazole, diketopyrrolopyrrole, fullerene, and derivatives thereof.

  Among these low-molecular semiconductor compounds, acene, thienoacene, thiophene, thienothiophene, tetrathiafulvalene, naphthalene diimide, perylene diimide, diketopyrrolopyrrole, fullerene, and derivatives thereof are preferable.

  As other organic semiconductors, for example, Chem. Rev. 2012, Vol. 112, pp. The organic semiconductor described in 2208-2267 can also be mentioned.

  Furthermore, the organic semiconductor ink of the present invention can contain a conductive polymer compound as an additional component, if necessary. Here, the conductive polymer compound is a polymer compound characterized by exhibiting electrical conductivity, specifically, a polyacetylene polymer, a polydiacetylene polymer, a polyparaphenylene polymer, Polyaniline polymer, polytriphenylamine polymer, polythiophene polymer, polypyrrole polymer, polyparaphenylene vinylene polymer, polyethylenedioxythiophene polymer, and a mixture of polyethylenedioxythiophene and polystyrenesulfonic acid (Generic name, PEDOT-PSS).

  Among these conductive polymer compounds, polyacetylene polymers, polyparaphenylene polymers, polyaniline polymers, polytriphenylamine polymers, polythiophene polymers, polypyrrole polymers, and polyparaphenylene vinylenes. Polymers and the like are preferred. As an effect of these additions, in addition to the optimization of the viscosity of the ink and the improvement of the film forming property, the improvement of the electron mobility can be mentioned.

In addition, the organic semiconductor ink of the present invention can contain the following low-molecular compound as an additive for controlling the physical properties of the ink, if necessary. Specifically, aliphatic hydrocarbons such as decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, and icosane,
Aliphatic alcohols such as hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, and eicosanol;
Hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, eicosylamine, etc. Aliphatic amines,
Hexanethiol, heptanethiol, octanethiol, nonanethiol, decanethiol, undecanethiol, dodecanethiol, tridecanethiol, tetradecanthiol, pentadecanethiol, hexadecanethiol, heptadecanethiol, octadecanethiol, nonadecanethiol, eicosanethiol, phenyl Methanethiol, (2-methylphenyl) methanethiol, (3-methylphenyl) methanethiol, (4-methylphenyl) methanethiol, (2-fluorophenyl) methanethiol, (3-fluorophenyl) methanethiol, (4 -Fluorophenyl) aliphatic thiols such as methanethiol and 2-phenylethanethiol, and
Benzenethiol, 2-methylbenzenethiol, 3-methylbenzenethiol, 4-methylbenzenethiol, 2-ethylbenzenethiol, 3-ethylbenzenethiol, 4-ethylbenzenethiol, 2-aminobenzenethiol, 3-aminobenzenethiol, 4- Aminobenzenethiol, 2-isopropylbenzenethiol, 3-isopropylbenzenethiol, 4-isopropylbenzenethiol, 2- (dimethylamino) benzenethiol, 3- (dimethylamino) benzenethiol, 4- (dimethylamino) benzenethiol, etc. An aromatic thiol of

  As an effect of these additions, in addition to optimizing the viscosity of the organic semiconductor ink and improving the film forming property, there is an improvement in charge mobility. Among these low molecular weight compounds, aliphatic thiols and aromatic thiols are suitable for the purpose of improving mobility by improving the wettability of the ink.

  By applying the organic semiconductor ink of the present invention described above, a layer or thin film of the benzobis (thiadiazole) derivative of the present invention can be formed. The organic semiconductor ink of the present invention can be applied by a known method such as a spin coat method, a drop cast method, a cast method, and a Langmuir-Blodgett method. In addition, as a coating method, a known method generally known as a printing technique can be used. For example, printing can be performed by an inkjet method, a screen method, an offset method, a gravure method, a flexo method, a microcontact method, or the like. it can.

  When the solvent component is removed after the organic semiconductor ink of the present invention is applied on a substrate, a layer containing the benzobis (thiadiazole) derivative of the present invention or a thin film containing the organic benzobis (thiadiazole) derivative (hereinafter also referred to as an organic semiconductor layer). Although formed, the solvent component removal conditions can be appropriately selected.

  For example, the solvent component is preferably air-dried or air-dried at room temperature, but when the boiling point of the solvent is high and difficult to remove, the solvent is removed under reduced pressure near room temperature or heated to about 50 ° C. to 200 ° C. It can be removed or both can be used together and heat-treated under reduced pressure.

  Furthermore, the layer or thin film can be heat-treated for the purpose of improving the semiconductor properties of the layer containing the benzobis (thiadiazole) derivative of the present invention or the thin film containing it. The heat treatment conditions in this case can be appropriately selected, and examples include a method of heat treatment at about 50 ° C. to 250 ° C. for 0.1 hour to 24 hours. This step may also serve as a solvent removal step.

  In addition, for the purpose of improving the semiconductor properties of the layer or thin film, a treatment for exposing the layer or thin film to solvent vapor may be performed.

Examples of the solvent used in this step include water and various organic solvents such as methanol, ethanol, propanol, ethylene glycol, isobutanol, 2-butanol, 2-ethyl-1-butanol, n-octanol, benzyl alcohol, and Alcohols such as terpineol;
Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, acetophenone, and isophorone:
Esters such as methyl acetate, ethyl acetate, butyl acetate, methyl benzoate, butyl benzoate, methyl salicylate, ethyl malonate, 2-ethoxyethane acetate, and 2-methoxy-1-methylethyl acetate;
Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N-methylpyrrolidone, N-ethylpyrrolidone, and hexamethylphosphoric triamide;
Ureas such as 1,3-dimethyl-2-imidazolidinone and 1,3-dimethylimidazolidine-2,4-dione;
Sulfoxides such as dimethyl sulfoxide and diethyl sulfoxide;
Sulfones such as sulfolane;
Nitriles such as acetonitrile, propionitrile, butyronitrile, and benzonitrile;
Lactones such as γ-butyrolactone;
Diethyl ether, diisopropyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, tert-butyl methyl ether, anisole, phenetole, 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, 1,4-dimethoxybenzene, 1,2- Ethers such as methylanisole, 1,3-methylanisole, 1,4-methylanisole, 1,2-methylenedioxybenzene, 2,3-dihydrobenzofuran, phthalane, octyloxybenzene, diphenyl ether, and ethyl cellosolve;
Carbonates such as dimethyl carbonate and 1,2-butylene glycol carbonate;
Thioethers such as thioanisole and ethyl phenyl sulfide;
Benzene, toluene, xylene, mesitylene, pseudocumene, hemimelliten, durene, isodurene, prienten, ethylbenzene, cumene, tert-butylbenzene, cyclohexylbenzene, triisopropylbenzene, phenylacetylene, indane, methylindane, indene, tetralin, naphthalene, 1- Aromatic hydrocarbons such as methylnaphthalene, 2-methylnaphthalene, phenyloctane, and diphenylmethane;
Phenols such as phenol, 1,2-cresol, 1,3-cresol, 1,4-cresol, 1,2-methoxyphenol, 1,3-methoxyphenol, and 1,4-methoxyphenol;
Chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,2,4-trichlorobenzene, bromobenzene, 1,2-dibromobenzene, 1,3-dibromobenzene, 1,4-dichlorotoluene, 1 -Chloronaphthalene, 2,4-dichlorotoluene, 2-chloro-1,3-dimethylbenzene, 2-chlorotoluene, 2-chloro-1,4-dimethylbenzene, 4-chloro-1,2-dimethylbenzene, 2 Halogenated aromatic hydrocarbons such as 1,5-dichlorotoluene, m-chlorotoluene, 1-chloro-2,3-dimethylbenzene, 4- (trifluoromethoxy) anisole, and trifluoromethoxybenzene;
Aliphatic hydrocarbons such as hexane, heptane, octane, cyclohexane, and limonene;
Halogenated aliphatic hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,3-dichloropropane, and 1,2-dibromoethane;
Examples thereof include pyridines such as 2,6-dimethylpyridine and 2,6-ditert-butylpyridine.

  Among these, halogenated aromatic hydrocarbons, aromatic hydrocarbons, and halogenated aliphatic hydrocarbons can be suitably used.

  Suitable halogenated aromatic hydrocarbons include chlorobenzene and 1,2-dichlorobenzene.

  Suitable aromatic hydrocarbons include toluene, xylene, mesitylene, tetralin, cyclohexylbenzene, and 1-methylnaphthalene.

  Suitable halogenated aliphatic hydrocarbons include chloroform and 1,2-dichloroethane.

Other suitable solvents include methyl benzoate, methyl salicylate, anisole, 4-methylanisole, and metacresol.
In addition, these solvents may be used independently and may mix and use 2 or more types.

In the solvent vapor exposure treatment step, for example, a layer containing a benzobis (thiadiazole) derivative or a thin film containing the solvent and the solvent are not directly in contact with the layer or thin film and the solvent (in a liquid state). This is achieved by leaving it in a certain space. In order to increase the amount of solvent vapor, the solvent may be heated to about 40 ° C to 150 ° C. After this solvent vapor exposure process,
In order to remove the solvent adhering to the layer or thin film in the step, drying and heat treatment similar to the above can be appropriately selected and carried out.

<Organic electronics devices>
The benzobis (thiadiazole) derivative of the present invention is excellent in electron mobility (field effect mobility). For example, organic electronic devices such as organic thin film transistors, organic electroluminescent elements, display devices, organic thin film solar cells, RFID tags, and sensors. Can be suitably used. Each of these various devices includes an organic layer containing an organic semiconductor as a constituent member, and this organic layer contains the benzobis (thiadiazole) derivative of the present invention.

  The benzobis (thiadiazole) derivative of the present invention includes backlight, optical communication, electrophotography, illumination light source, recording light source, exposure light source, reading light source, sign, signboard, interior, logistics management, inventory management, product management, It can be used for a wide range of applications such as individual identification, temperature measurement, pressure measurement, load measurement, light / dark measurement, and biological information measurement. Below, the said organic electronics device is demonstrated separately.

(Organic thin film transistor)
First, the organic thin film transistor (hereinafter also referred to as organic TFT) of the present invention will be described. In the organic thin film transistor of the present invention, the organic semiconductor layer which is a constituent member thereof contains the benzobis (thiadiazole) derivative of the present invention. This derivative is effective when used in an organic semiconductor layer of an organic TFT because it can easily align the molecular orientation and achieve high field-effect mobility.

  The organic thin film transistor of the present invention can employ known structures and materials except that the organic semiconductor layer contains the benzobis (thiadiazole) derivative of the present invention.

  The thickness of the organic semiconductor layer is preferably thin as long as necessary functions are not lost. The film thickness of the organic semiconductor layer for exhibiting a necessary function is usually 1 nm to 10 μm, preferably 5 nm to 5 μm, more preferably 10 nm to 1 μm.

  FIG. 1 shows a layer structure of an example of the organic TFT of the present invention. The organic TFT shown in FIG. 1 has a bottom gate-top contact structure, and a gate electrode 12, a gate insulating layer 13, an organic semiconductor layer 16, a drain electrode 14 and a source electrode 15 are provided on a substrate 11. They are laminated in this order.

  As the substrate 11, for example, a material such as glass, quartz, silicon, or ceramic, or a plastic material can be used. As described above, the benzobis (thiadiazole) derivative of the present invention is usually soluble in water or an organic solvent, and an organic semiconductor layer can be formed by applying it as an organic semiconductor ink after being dissolved therein. In the application, unlike the vapor deposition, the substrate 11 is not placed in a high temperature environment. Accordingly, if the other electrodes are formed in an environment that is not at a high temperature, a material having low heat resistance can be used as the substrate 11.

  For this reason, various plastic materials including those having low heat resistance can be used as the substrate 11. However, a flexible material can be used as the plastic material. A flexible substrate can be obtained. As a result, the organic TFT can be arranged not only on a flat surface but also on a curved surface or the like, and the degree of design freedom of the entire organic electronic device including the organic TFT is increased.

  Next, as the gate electrode 12, for example, metals such as gold, platinum, chromium, tungsten, tantalum, nickel, copper, aluminum, silver, magnesium, and calcium, or alloys thereof, polysilicon, amorphous silicon, graphite Materials such as tin-doped indium oxide (ITO), zinc oxide, and conductive polymers can be used. Using these materials, the gate electrode 12 can be formed by a known film production method such as a vacuum deposition method, an electron beam deposition method, an RF sputtering method, or a printing method.

Examples of the gate insulating layer 13 include SiO ₂ , Si ₃ N ₄ , SiON, Al ₂ O ₃ , Ta ₂ O ₅ , amorphous silicon, polyimide resin, polyvinyl phenol resin, polyparaxylylene resin, polystyrene resin, poly Materials such as methyl methacrylate resin, polyfluorocarbon resin, and divinyltetramethylsiloxane benzocyclobutene resin can be used. Using these materials, the gate insulating layer 13 can be formed on the gate electrode 12 (so as to cover the gate electrode 12) by a known film manufacturing method similar to that for the gate electrode 12.

  In the organic thin film transistor of the present invention, the organic semiconductor layer 16 includes one or more benzobis (thiadiazole) derivatives of the present invention, and can be formed by a known film manufacturing method such as vacuum deposition or spin coating. Preferably, the organic semiconductor layer 16 is formed on the gate insulating layer 13 by a coating (printing) method using the organic semiconductor ink of the present invention.

  The drain electrode 14 and the source electrode 15 are made of, for example, metals such as gold, platinum, chromium, tungsten, tantalum, nickel, copper, aluminum, silver, magnesium, and calcium, or alloys thereof, polysilicon, amorphous silicon, and graphite. , Tin-doped indium oxide (ITO), zinc oxide, and a conductive polymer can be used to form the film by a known film manufacturing method similar to that for the gate electrode 12.

(Organic electroluminescence device)
Next, the organic electroluminescence element (hereinafter referred to as organic EL element) of the present invention will be described. In the organic EL device of the present invention, the hole transport layer and / or the electron transport layer which are constituent members thereof contain the benzobis (thiadiazole) derivative of the present invention. Since the benzobis (thiadiazole) derivative of the present invention is excellent in electron transport properties, it is effective when used in an organic EL device, particularly in an electron transport layer.

  The organic EL device of the present invention can employ known structures and materials except that the hole transport layer and / or the electron transport layer contain the benzobis (thiadiazole) derivative of the present invention.

  An organic EL element is an element in which an organic compound layer including a light emitting layer and a hole transport layer and / or an electron transport layer is formed between an anode and a cathode on a substrate. Typically, (substrate / anode / hole transport layer / light emitting layer / cathode), (substrate / anode / light emitting layer / electron transport layer / cathode), (substrate / anode / hole transport layer / light emitting layer / electron) It is composed of an element structure such as a transport layer / cathode.

  In FIG. 2, the layer structure of an example of the organic EL element of this invention is shown. The organic EL element shown in FIG. 2 is formed by laminating an anode 22, a hole transport layer 23, a light emitting layer 24, an electron transport layer 25 and a cathode 26 in this order on a substrate 21.

  When a predetermined DC voltage is applied between the anode 22 and the cathode 26 to the organic EL element configured as described above, light emission with high luminance can be obtained from the light emitting layer 24. The mechanism of this light emission is considered as follows.

  That is, when a predetermined DC voltage is applied between the two layers, holes flowing from the anode 22 into the hole transport layer 23 are transported to the light emitting layer 24. On the other hand, electrons injected from the cathode 26 into the electron transport layer 25 are transported to the light emitting layer 24, diffused and moved in the light emitting layer 24, recombined with holes, and become electrically neutralized. When this recombination is performed, predetermined energy is released, and the organic light emitting material in the light emitting layer 24 is excited to an excited state by the energy. Light is emitted when the state returns to the ground state.

  In particular, by using the benzobis (thiadiazole) derivative of the present invention having a high field effect mobility for the electron transport layer 25 of the organic EL element, electrons can be efficiently injected into the light emitting layer, and the light emission efficiency can be increased. .

  As the substrate 21, for example, a transparent material such as glass and plastic can be used. Here, the hole transport layer 23 and the electron transport layer 25 can be formed by a coating method using the organic semiconductor ink of the present invention, and a flexible substrate can be used as the substrate 21 as described above. This is the same as the case of the organic TFT.

  The anode 22 is usually made of a material that transmits light. Specifically, it is preferable to use tin-doped indium oxide (ITO), indium oxide, tin oxide, indium oxide, and a zinc oxide alloy. Further, a thin film of metal such as gold, platinum, silver, and magnesium alloy can be used. Furthermore, organic materials such as polyaniline, polythiophene, polypyrrole, and derivatives thereof can also be used. The anode 22 can be formed by a well-known film forming method such as a vacuum evaporation method, an electron beam evaporation method, an RF sputtering method, or a coating (printing) method.

  As the cathode 26, it is preferable to use an alkaline metal such as Li, K, and Na, or an alkaline earth metal such as Mg and Ca, which has a low work function, from the viewpoint of electron injection. It is also preferable to use stable Al or the like. In order to achieve both stability and electron injection properties, a layer containing two or more kinds of materials may be used. These materials are described in detail, for example, in JP-A-2-15595 and JP-A-5-121172. Have been described. The cathode 26 can be formed by a well-known film forming method such as a vacuum evaporation method, an electron beam evaporation method, or an RF sputtering method.

  As the light emitting layer 24, it is preferable to use a host material such as a quinolinol complex or an aromatic amine to which a coloring material such as a coumarin derivative, DCM, quinacridone, or rubrene is added (doping). The light emitting layer 24 can also be formed. Moreover, an efficient organic EL element can be produced by forming the light emitting layer 24 by doping an iridium metal complex. The light emitting layer 24 can be formed by a known film forming method such as a vacuum deposition method, a sputtering method, or a coating (printing) method.

  The hole transport layer 23 and / or the electron transport layer 25 includes the benzobis (thiadiazole) derivative of the present invention. When the derivative includes the derivative, the hole transport layer 23 and the electron transport layer 25 correspond to the present invention. The organic semiconductor ink can be suitably formed by a coating method.

  When the benzobis (thiadiazole) derivative of the present invention is not used for the hole transport layer 23, examples of the hole transport layer 23 include N, N′-bis (3-methylphenyl) -N, N′-bis (phenyl). ) -Benzidine (TPD), N, N′-bis (naphthalen-1-yl) -N, N′-bis (phenyl) -2,2′-dimethylbenzidine (α-NPD), and 2,2-bis A material such as (3- (N, N-di-p-tolylamino) phenyl) biphenyl (3DTAPBP) can be used.

  When the benzobis (thiadiazole) derivative of the present invention is not used for the electron transport layer 25, the electron transport layer 25 is, for example, 2- (4-biphenyl) -5- (4-tert-butylphenyl) -1,3, 4-oxazole (PBD), 1,3-bis [2- (4-tert-butylphenyl) -1,3,4-oxadiazo-5-yl] benzene (OXD-7), and 2,2 ′, 2 Materials such as ''-(1,3,5-benzentriyl) -tris (1-phenyl-1-H-benzimidazole (TPBi)) can be used.

  As a film forming method of the hole transport layer 23 and the electron transport layer 25, the same method as the film forming method of the light emitting layer 24 is used. Moreover, although these thickness is suitably selected from a conventionally well-known range, it is 1 nm-1 micrometer normally, Preferably it is 1 nm-100 nm.

  In addition, the organic EL element of the present invention can be configured to provide an electron injection layer, a hole injection layer, an electron block layer, a hole block layer, a protective layer, or the like in addition to the above layers. These layers can also be formed by the same method as the film forming method of the light emitting layer 24.

<Display device>
Next, the display device of the present invention will be described. The display device of the present invention includes an organic EL element and an organic TFT electrically connected thereto, and controls driving (switching transistor) and lighting (driving transistor) of the organic EL element by the organic TFT. The display device is the organic TFT of the present invention as described above, or the organic EL element is the organic EL element of the present invention as described above. In the display device of the present invention, from the viewpoint of high field effect mobility, the organic TFT is preferably the organic TFT of the present invention, and the organic EL element is preferably the organic EL element of the present invention.

  FIG. 3 shows an example of the configuration of the display device of the present invention. The display device shown in FIG. 3 includes an organic EL element 120 including a cathode 101, an electron transport layer 102, a light emitting layer 103, a hole transport layer 104, and an anode 105 on a substrate 111 with a barrier layer 112 interposed therebetween. The organic TFT 121 includes a gate electrode 106, a gate insulating layer 107, an organic semiconductor layer 108, a source electrode 109, and a drain electrode 110. The upper part of these layer structures is covered with a protective film 113.

  This display device has a structure in which the cathode 101 (electrode on the side close to the substrate 111) of the organic EL element 120 and the drain electrode 110 of the organic TFT 121 are electrically connected. By applying a voltage to the gate electrode 106, a current flows between the source and drain electrodes, and the organic EL element 120 emits light. Moreover, it can also be set as the structure where the anode and the drain electrode of organic TFT were electrically connected.

  In the present invention, as described above, the organic TFT of the present invention using the benzobis (thiadiazole) derivative of the present invention and the organic EL of the present invention are used for both the organic TFT and the organic EL element driven / lighted by the organic TFT. Although it is preferably an element, any one of them may be of a known material and configuration that does not contain the benzobis (thiadiazole) derivative of the present invention.

  Further, as shown in FIG. 3, an active matrix display device can be manufactured by arranging pixel elements in which organic TFTs for driving / lighting control and organic EL elements are combined in a matrix. Active matrix display devices are less susceptible to unnecessary voltage being applied to non-selected points even when the number of pixels is large, and are less likely to cause field efficiency degradation or degradation even at high duty. It has the advantage of being excellent in performance.

  The display device (display) of the present invention can employ known structures and materials except that the organic TFT of the present invention and / or the organic EL element of the present invention are used, and can be obtained by a known method. Can be manufactured.

<Organic thin film solar cell>
Next, the organic thin film solar cell of the present invention (hereinafter referred to as an organic PV element) will be described. The organic PV device of the present invention has an anode, a charge separation layer containing a hole transport material and an electron transport material, and a cathode on a substrate, and the charge separation layer is a benzobis (thiadiazole) derivative of the present invention. Is included.

  Furthermore, the organic PV element of the present invention has an anode, the charge separation layer, a hole transport layer and / or an electron transport layer, and an anode on a substrate, and the hole transport layer and / or electron transport. The thing of the structure in which a layer contains the benzobis (thiadiazole) derivative of this invention is also mentioned.

  Since the benzobis (thiadiazole) derivative of the present invention is excellent in electron transport property, it is effective when used in an organic PV element, particularly in a charge separation layer or an electron transport layer.

  The organic PV element of the present invention can employ known structures and materials other than the above configuration.

  An organic PV element is an element in which at least one organic compound layer including a charge separation layer is formed between an anode and a cathode on a substrate. Typically, (substrate / anode / charge separation layer / cathode), (substrate / anode / charge separation layer / electron transport layer / cathode), (substrate / anode / hole transport layer / charge separation layer / electron transport layer) / Cathode).

  In FIG. 4, the layer structure of an example of the organic PV element of this invention is shown. The organic PV element shown in FIG. 4 is formed by laminating an anode 32, a charge separation layer 33, and a cathode 34 in this order on a substrate 31.

  When the organic PV element configured as described above is irradiated with light, holes and electrons are generated in the charge separation layer 33, and a current can be taken out when the anode 32 and the cathode 34 are connected. The mechanism of this power generation is considered as follows.

  That is, when the charge separation layer 33 is irradiated with light, the light is absorbed and the energy excites organic molecules to generate charge separation, generating holes and electrons. The holes are transported to the anode 32 by the hole transport material in the charge separation layer 33, and the electrons are transported to the cathode 34 by the electron transport material in the charge separation layer 33 and taken out to an external circuit.

  By using the benzobis (thiadiazole) derivative of the present invention having a high field effect mobility for the charge separation layer 33 of the organic PV element, holes and electrons can be efficiently extracted from the charge separation layer 33, and the power generation efficiency can be improved. Can be increased. Further, by using the benzobis (thiadiazole) derivative of the present invention for the electron transport layer, electrons can be efficiently transported to the cathode, and power generation efficiency can be increased.

  As the substrate 31, for example, a transparent material such as glass or plastic can be used. Here, the charge separation layer 33, the hole transport layer, and the electron transport layer can be formed by a coating method using the organic semiconductor ink of the present invention, and a flexible substrate can be used as the substrate 31. Is the same as in the case of the organic TFT described above.

  As the anode 32, a light transmitting material is usually used. Specifically, tin-doped indium oxide (ITO), indium oxide, tin oxide, indium oxide, or a zinc oxide alloy is preferable. Metal thin films such as gold, platinum, silver, and magnesium alloys can also be used. Furthermore, organic materials such as polyaniline, polythiophene, polypyrrole, and derivatives thereof can also be used. The anode 32 can be formed by a known film forming method such as a vacuum evaporation method, an electron beam evaporation method, an RF sputtering method, or a coating (printing) method.

  As the cathode 34, it is preferable to use an alkali metal such as Li, K, and Na, or an alkaline earth metal such as Mg and Ca, which has a small work function, from the viewpoint of electron extraction. It is also preferable to use stable Al or the like. In order to achieve both stability and electron extraction, a layer containing two or more materials may be used. The cathode 34 can be formed by a well-known film forming method such as a vacuum evaporation method, an electron beam evaporation method, or an RF sputtering method.

  For the charge separation layer 33, the benzobis (thiadiazole) derivative of the present invention is used as an organic semiconductor material. The benzobis (thiadiazole) derivative to be used may be one kind or plural kinds. Furthermore, the charge separation layer 33 can also contain one or more other organic semiconductor compounds.

As a material constituting the charge separation layer together with the benzobis (thiadiazole) derivative, for example, poly (3-hexylthiophene-2,5-diyl) (P3HT) and poly [2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylene vinylene] (MEH-PPV) and the like.
As an electron transport material, fullerene C60, (6,6) -phenyl-C61 butyric acid methyl ester (C61-PCBM), fullerene C70, (6,6) -phenyl-C71 butyric acid methyl ester (C71-PCBM), etc. Is mentioned.

  The charge separation layer 33 can be formed by a known film forming method such as a vacuum deposition method, a sputtering method, or a coating (printing) method. The charge separation layer 33 is formed by a coating (printing) method using the organic semiconductor ink of the present invention. Preferably 33 is formed. The thickness of the charge separation layer 33 is appropriately selected from a conventionally known range, but is usually 5 nm to 1 μm, preferably 10 nm to 500 nm.

  The organic PV device of the present invention can further be provided with a hole transport layer and / or an electron transport layer. The benzobis (thiadiazole) derivative of the present invention can also be suitably used for these layers. The benzobis (thiadiazole) derivative to be used may be one kind or plural kinds. Furthermore, the hole transport layer and the electron transport layer can also contain one or more other compounds.

  When the benzobis (thiadiazole) derivative of the present invention is not used for the hole transport layer or the electron transport layer, examples of the hole transport layer include poly (3,4-ethylenedioxythiophene) poly (styrenesulfonate) (PEDOT- A material such as PSS) can be used, and as the electron transport layer, for example, a material such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) can be used.

  As the film forming method of the hole transport layer and the electron transport layer, the same method as the film forming method of the charge separation layer 33 is used. Moreover, although these thickness is suitably selected from a conventionally well-known range, it is 1 nm-1 micrometer normally, Preferably it is 1 nm-100 nm.

<RFID tag>
Next, the RFID tag (Radio Frequency IDentification tag) of the present invention will be described. The RFID tag of the present invention operates using an organic TFT, and the organic TFT is the organic TFT of the present invention as described above.

  The RFID tag includes an integrated circuit unit (hereinafter referred to as an IC unit) and an antenna unit, and an ID stored in the IC unit, that is, individual identification information and the like is wirelessly connected to the reader / writer device via the antenna unit. This is an electronic device that can communicate and can read information stored in the IC unit by a reader / writer device in a non-contact manner, or can write in the IC unit.

  By attaching an RFID tag to an article or printing on an article, information management, distribution management, solid authentication, and the like of the article can be performed and applied to various fields. Since the benzobis (thiadiazole) derivative of the present invention can achieve high field effect mobility, when used in the organic semiconductor layer of the organic TFT constituting the IC portion of the RFID tag, the responsiveness of the RFID tag can be improved.

  The RFID tag of the present invention can be created by combining known circuits described in, for example, Solid-State Electronics 84 (2013) 167-178.

  The RFID tag of the present invention can adopt a known structure and material except that the organic TFT of the present invention is used, and can be manufactured by a known method.

  The IC part of the RFID tag may include a plurality of organic TFTs. In that case, among the plurality of organic TFTs, all the organic TFTs may be the organic TFT of the present invention, and some of the organic TFTs may be the organic TFT of the present invention.

(sensor)
Next, the sensor of the present invention will be described. The sensor of the present invention operates using an organic TFT, and the organic TFT is the organic TFT of the present invention as described above.

  The sensor can be applied to a system in which the physical state of the organic semiconductor constituting the organic TFT changes due to an external stimulus applied to the organic TFT, and as a result, the current and / or voltage obtained from the organic TFT changes. .

  Examples of the sensor of the present invention include a temperature sensor and an optical sensor that detect temperature and light when the organic semiconductor constituting the organic TFT receives heat and light and the physical state of the organic semiconductor changes.

  In addition, there are a bending stress sensor and a pressure sensor that detect stress and pressure when the organic semiconductor constituting the organic TFT receives stress and the physical state of the organic semiconductor changes.

  In addition, there is a chemical sensor that detects the chemical substance by changing the physical state of the organic semiconductor due to the influence of a specific chemical substance such as water molecule or oxygen molecule on the organic semiconductor constituting the organic TFT. It is done.

  Furthermore, there is a chemical sensor that detects the chemical substance when the metal electrode constituting the organic TFT is affected by a specific chemical substance and a change occurs in the current and / or voltage obtained from the organic TFT.

  Since the benzobis (thiadiazole) derivative of the present invention can achieve high field effect mobility, when used in the organic semiconductor layer of the organic TFT constituting the sensor, the responsiveness and dynamic range of the sensor can be enhanced.

  In addition, the sensor of this invention can employ | adopt a well-known structure and material except using the organic TFT of this invention, and can be manufactured by a well-known method.

  The sensor may include a single organic TFT or a plurality of organic TFTs depending on the application. When a plurality of organic TFTs are provided, all of the organic TFTs may be the organic TFT of the present invention, and some of the organic TFTs may be the organic TFT of the present invention.

  In the various organic electronic devices of the present invention described above, a plastic substrate can be used as the substrate. The plastic used as the substrate is preferably excellent in heat resistance, dimensional stability, solvent resistance, electrical insulation, workability, low air permeability and low moisture absorption. Examples of such plastics include polyethylene terephthalate, polyethylene naphthalate, polystyrene, polycarbonate, polyacrylate, and polyimide.

  In the case of a plastic substrate, it is preferable to provide a moisture permeation preventive layer (gas barrier layer) on the electrode side surface of the substrate, the surface opposite to the electrode, or both. As a material constituting the moisture permeation preventing layer, inorganic materials such as silicon nitride and silicon oxide are preferably mentioned. The moisture permeation preventing layer can be formed by a known film manufacturing method such as RF sputtering. Moreover, you may provide a hard-coat layer and an undercoat layer as needed.

  Furthermore, for the substrate in the organic electronic device of the present invention, for the purpose of adjusting the surface energy of the substrate surface and controlling the affinity with the material laminated on the substrate, it is treated with hexamethyldisilazane, polystyrene, etc. It is possible to perform a surface modification treatment of the substrate, such as coating with a resin or UV ozone treatment.

  EXAMPLES Next, although an Example is given and this invention is demonstrated concretely, this invention is not restrict | limited to these Examples.

[Production and evaluation of organic TFT]
In the following examples, unless otherwise specified, bottom gate-top contact elements were produced on a silicon substrate and evaluated according to the following organic TFT production procedures.

<Producing procedure of organic TFT>
When going through the production of an organic semiconductor layer by spin coating,
(Production of TFT substrate)-(Production of organic semiconductor layer by spin coating method)-(Production of source electrode and drain electrode)
Or
(Production of TFT substrate)-(Surface modification of TFT substrate)-(Production of organic semiconductor layer by spin coating method)-(Production of source electrode and drain electrode)
An organic TFT was fabricated by the procedure described above.

When going through the production of an organic semiconductor layer by vacuum deposition,
(Fabrication of TFT substrate)-(Fabrication of organic semiconductor layer by vacuum deposition method)-(Fabrication of source electrode and drain electrode)
Or
(Production of TFT substrate)-(Surface modification of TFT substrate)-(Production of organic semiconductor layer by vacuum deposition method)-(Production of source electrode and drain electrode)
An organic TFT was fabricated by the procedure described above.

(Production of TFT substrate)
As a substrate of the organic TFT, a commercially available silicon wafer having a surface formed with 200 nm thick thermal silicon oxide was used. The silicon wafer had a low resistance and functioned as the gate electrode of the organic TFT. A silicon oxide film was used as the gate insulating film. This silicon wafer was washed with a mixed solution of hydrogen peroxide and sulfuric acid, and the surface was cleaned by UV ozone treatment immediately before use in the next step. The substrate thus processed is hereinafter referred to as “bare substrate”.

(TFT substrate surface modification)
The “bare substrate” was immersed in commercially available hexamethyldisilazane and allowed to stand for 12 hours or more to modify the substrate surface. The substrate thus treated is hereinafter referred to as “HMDS modified substrate”.

  A “bare substrate” was spin-coated with a commercially available solution of polystyrene in xylene at 0.5 wt%, and then heated at 150 ° C. for 1 hour to produce a polystyrene thin film of approximately 20 nm on the substrate surface. The substrate thus treated is hereinafter referred to as “PS substrate”.

  A “bare substrate” was spin-coated with a mixed solution of polyvinylphenol and melamine using propylene glycol monomethyl ether acetate prepared from commercially available polyvinylphenol and melamine as these solvents, and then heated at 180 ° C. for 1 hour to form a substrate. A polyvinylphenol-melamine thin film having a thickness of about 20 nm was formed on the surface. The substrate thus treated is hereinafter referred to as “PVP substrate”.

(Preparation of organic semiconductor layer by spin coating)
Using the synthesized compound (organic semiconductor compound), the solvent and solute concentration solution (organic semiconductor ink) described in each item are prepared, and the organic semiconductor ink is used to spin the substrate on each item by spin coating. In addition, an organic semiconductor layer having a thickness of about 20 to 50 nm was formed. Thereafter, thermal annealing was performed under the conditions described in each section as necessary. Spin coating and thermal annealing were performed in a nitrogen atmosphere unless otherwise specified.

(Preparation of organic semiconductor layer by vacuum evaporation)
Using the synthesized compound (organic semiconductor compound), an organic semiconductor layer having a thickness of about 50 nm was formed on the substrate described in each item by a vacuum deposition method. The inside of the vapor deposition apparatus chamber during the formation of the organic semiconductor layer was set to a pressure of 2 × 10 ^{−5 to} 6 × 10 ⁻⁴ Pa, the organic semiconductor compound was put in a crucible, and heated by a filament wound around the crucible to perform vapor deposition. The deposition rate was 0.2 ± 0.1 liter per second.

(Production of source and drain electrodes)
A source electrode and a drain electrode were formed on the organic semiconductor layer by depositing gold by a vacuum deposition method using a metal mask. The channel width and channel length of the organic TFT were 1000 μm and 70 μm, respectively. The film thickness of the source and drain electrodes was about 50 nm.

(Evaluation of field effect mobility)
The field effect mobility (μ) was obtained from the result of measuring the transfer characteristics of the produced organic TFT using a semiconductor characteristic evaluation system 4200-SCS type manufactured by KEITHLEY.

The field effect mobility (μ) can be calculated using the following formula (formula A) representing the drain current I _d .
I _d = (W / 2L) μC _i (V _g −V _t ) ² (Formula A)

Here, L and W are a channel length and a channel width. C _i is a capacitance per unit area of the gate insulating film. V _g is a gate voltage, and V _t is a threshold voltage. The transfer characteristic measurement shows the threshold voltage and the drain current at a certain gate voltage, so that the field effect mobility can be obtained.

[Example S-1]
<Synthesis of Compound (15)>
According to the following synthesis scheme, compound (15), which is a benzobis (thiadiazole) derivative of the present invention, was synthesized. Hereinafter, each step will be described.

(Synthesis of Compound (15b))
A solution obtained by adding 2 g (13.2 mmol) of compound (15a) and 40 ml of anhydrous tetrahydrofuran to a 100 ml four-necked flask equipped with a stirrer and a thermometer under an argon atmosphere is cooled to −55 ° C. or lower, and − While maintaining the temperature at 55 ° C. or lower, 9.0 ml of 1.6 N normal butyl lithium hexane solution was slowly added dropwise thereto.

  After stirring for 1 hour, 4.28 ml (15.8 mmol) of tributyltin chloride was added dropwise to the reaction solution, and the mixture was warmed to room temperature and stirred for 1 hour. The reaction was stopped with methanol and purified with a reverse phase silica gel column to obtain 4.9 g of compound (15b) as a yellow liquid.

The physical property values of the compound (15b) were as follows. Hereinafter, the measurement was performed at room temperature (25 ° C.) unless otherwise specified.
¹ H-NMR (400 MHz; CDCl ₃ ; δ (ppm)); 0.88-0.92 (m, 9H), 1.05-1.26 (m, 6H), 1.31-1.39 ( m, 6H), 1.45-1.67 (m, 6H), 7.06-7.12 (m, 1H), 7.52-7.53 (m, 1H)
CI-MS; 443 (M + 1)

(Synthesis of Compound (15))
In a 100 ml eggplant-shaped flask equipped with a reflux tube, 0.98 g (2.79 mmol) of the compound (94), 30 ml of toluene, 4.9 g (11.2 mmol) of the compound (15b), and 0.2% of bistriphenylphosphine palladium dichloride. 59 g (0.84 mmol) was added and allowed to react with stirring at 100 ° C. for 4 hours. The reaction solution was cooled, filtered, and washed with toluene to purify, and 0.19 g of Compound (15) was obtained as a red-purple solid.

The physical property values of the compound (15) were as follows.
¹ H-NMR (400 MHz; 1,2-dichlorobenzene-d ₄ : 140 ° C .; δ (ppm)); 7.62-7.63 (m, 2H), 8.98-8.99 (m, 2H )
EI-MS; 494 (M + 1)

[Example S-2]
<Synthesis of Compound (22)>

(Synthesis of Compound (22b))
A solution obtained by adding 5 g (45.8 mmol) of compound (22a) and 400 ml of anhydrous tetrahydrofuran to a 500 ml four-necked flask equipped with a stirrer and a thermometer in an argon atmosphere was cooled to −70 ° C. or lower, and −70 ° C. 31.0 ml (50.4 mmol) of 2.0 N lithium diisopropylamine solution was added dropwise thereto while maintaining the temperature at or below.

  After stirring for 15 minutes, 17.1 g (50.4 mmol) of tributyltin chloride was added dropwise, and the temperature was raised to room temperature. Purification with a normal phase silica gel column gave 4.99 g of compound (22b) as a yellow liquid.

The physical property values of the compound (22b) were as follows.
¹ H-NMR (400 MHz; CDCl ₃ ; δ (ppm)); 0.80-1.00 (m, 9H), 1.04-1.26 (m, 6H), 1.26-1.42 ( m, 6H), 1.42-1.70 (m, 6H), 7.08-7.20 (m, 1H), 7.66-7.76 (m, 1H)
EI-MS; 399 (M)

(Synthesis of Compound (22))
Compound (22) was obtained in the same manner as in [Example S-1] <Synthesis of compound (15)> except that compound (22b) was used instead of compound (15b).

The physical property values of the compound (22) were as follows.
¹ H-NMR (400 MHz; deuterated dichlorobenzene; 140 ° C.); 7.50-7.60 (m, 2H), 8.84-8.96 (m, 2H)
TOF-MS (ASAP +); 408.9594 (M + 1); Calc. 408.959

[Example S-3]
<Synthesis of Compound (23-1)>

(Synthesis of Compound (23-1b))
To a 1000 ml four-necked flask equipped with a stirrer and a thermometer, 25.8 g (158.4 mmol) of compound (23-1a), 500 ml of anhydrous methylene chloride, and 11 ml of acetyl chloride were added under an argon atmosphere. Cooled in the bath.

  While maintaining the temperature in the reaction system, 42.2 g of aluminum chloride was slowly added and stirred overnight at room temperature. The reaction solution was added to a 6N aqueous hydrochloric acid solution, followed by liquid separation, washing and concentration to obtain 31 g of a crude product. Methanol was added to the crude product and filtered, and the obtained filtrate was concentrated to dryness to obtain 15 g of compound (23-1b) as white crystals.

The physical property values of the compound (23-1b) were as follows.
¹ H-NMR (400 MHz; CDCl ₃ ; δ (ppm)); 2.51 (s, 3H), 7.11-7.43 (m, 2H)
CI-MS; 204 (M + 1)

(Synthesis of Compound (23-1c))
In a 1000 ml four-necked flask equipped with a stirrer and a thermometer, 15 g (75.2 mmol) of the compound (23-1b), 500 ml of toluene, 162 g (279.3 mmol) of bistributyltin, 15.2 g of triethylamine (under argon atmosphere) 150.2 mmol) and 13.35 g (11.6 mmol) of palladium tetrakistriphenylphosphine were added and reacted at 110 ° C. with heating and stirring.

  After completion of the reaction, toluene was concentrated under reduced pressure, hexane was added and the mixture was purified with Wakogel (registered trademark) 50NH2, to obtain 4.56 g of compound (23-1c) as a pale yellow oil.

The physical property values of the compound (23-1c) were as follows.
¹ H-NMR (400 MHz; CDCl ₃ ; δ (ppm)); 1.67-0.88 (m, 27H), 2.57 (s, 3H), 7.18-7.78 (m, 2H)
CI-MS; 415 (M)

(Synthesis of Compound (23-1))
Compound (23-1) was obtained in the same manner as in [Example S-1] <Synthesis of compound (15)> except that compound (23-1c) was used instead of compound (15b).

The physical property values of the compound (23-1) were as follows.
¹ H-NMR (400 MHz; 1,2-dichlorobenzene-d ₄ ; 140 ° C .; δ (ppm)); 2.51 (s, 6H), 7.70-7.71 (m, 2H), 8. 94-8.96 (m, 2H)
EI-MS; 442 (M)

[Example S-4]
<Synthesis of Compound (23-2)>

(Synthesis of Compound (23-2b))
Compound (23-2b) was obtained in the same manner as in [Example S-3] <Synthesis of compound (23-1b)> except that octanoyl chloride was used instead of acetyl chloride.

The physical property values of the compound (23-2b) were as follows.
¹ H-NMR (400 MHz; CDCl ₃ ; δ (ppm)); 0.86-0.90 (m, 3H), 1.22-1.44 (m, 8H), 1.68-1.75 ( m, 2H), 2.79-2.83 (m, 2H), 7.08-7.09 (m, 1H), 7.43-7.44 (m, 1H)
EI-MS; 290 (M + 2), 288 (M)

(Synthesis of Compound (23-2c))
Compound (23-2c) was obtained in the same manner as in the above (Synthesis of compound (23-1c)) except that compound (23-2b) was used instead of compound (23-1b).

The physical property values of the compound (23-2c) were as follows.
¹ H-NMR (400 MHz; CDCl ₃ ; δ (ppm)); 0.86-0.93 (m, 12H), 1.05-1.25 (m, 6H), 1.27-1.39 ( m, 14H), 1.48-1.78 (m, 8H), 2.86-2.90 (m, 2H) 7.14-7.20 (m, 1H), 7.76-7.78. (M, 1H)
EI-MS; 443 (M-56)

(Synthesis of Compound (23-2))
[Example S-1] Compound (23-2) was obtained in the same manner as in <Synthesis of compound (15)> except that compound (23-2c) was used instead of compound (15b).

The physical property values of the compound (23-2) were as follows.
¹ H-NMR (400 MHz; 1,2-dichlorobenzene-d ₄ ; 140 ° C .; δ (ppm)); 0.84-0.87 (m, 6H), 1.28-1.46 (m, 16H) ) 1.79-1.86 (m, 4H), 2.92-2.96 (m, 4H), 7.77-7.78 (m, 2H), 8.96-8.97 (m) 2H)
TOF-HRMS (ASAP +); 611.1638 (M + 1); Calcd. 611.1643

[Comparative Example S-5]
<Synthesis of Compound (91)>

(Synthesis of Compound (91))
[Example S-1] Compound (91) was obtained in the same manner as in <Synthesis of Compound (15)> except that Compound (91a) was used instead of Compound (15b).

The physical property values of the compound (91) were as follows.
¹ H-NMR (400 MHz, CDCl ₃ ; δ (ppm)); 7.34-7.36 (m, 2H), 7.71-7.72 (m, 2H), 9.03-9.04 ( m, 2H)
EI-MS; 358 (M)

[Comparative Example S-6]
<Synthesis of Compound (92)>

(Synthesis of Compound (92b))
Compound (92b) was obtained in the same manner as in [Example S-1] (synthesis of compound (15b)) except that compound (92a) was used instead of compound (15a).

The physical property values of the compound (92b) were as follows.
¹ H-NMR (400 MHz, CDCl ₃ ; δ (ppm)); 0.86-0.91 (m, 12H), 1.05-1.09 (m, 6H), 1.27-1.72 ( m, 24H), 2.83-2.87 (m, 2H), 6.89-6.90 (m, 1H), 6.97-6.98 (m, 1H)
CI-MS; 486 (M-1)

(Synthesis of Compound (92))
Compound (92) was obtained in the same manner as in [Example S-1] <Synthesis of compound (15)> except that compound (92b) was used instead of compound (15b).

The physical property values of the compound (92) were as follows.
¹ H-NMR (400 MHz, CDCl ₃ ; δ (ppm)); 0.87-0.90 (m, 6H), 1.25-1.47 (m, 20H), 1.77-1.84 ( m, 4H), 2.92-2.96 (m, 4H), 6.94-6.96 (m, 2H), 8.69-8.71 (m, 2H)
EI-MS; 582 (M ^<+> )

[Comparative Example S-7]
<Synthesis of Compound (93)>

(Synthesis of Compound (93b))
Compound (93b) was obtained in the same manner as in [Example S-3] (synthesis of compound (23-1c)) except that compound (93a) was used instead of compound (23-1b).

The physical property values of the compound (93b) were as follows.
¹ H-NMR (400 MHz; CDCl ₃ ; δ (ppm)); 0.82 to 0.98 (m, 9H), 0.98 to 1.22 (m, 6H), 1.24 to 1.40 ( m, 6H), 1.40-1.66 (m, 6H), 7.48-7.57 (m, 1H), 7.60-7.67 (m, 1H)
CI-MS; 400 (M + 1)

(Synthesis of Compound (93))
Compound (93) was obtained in the same manner as in [Example S-1] <Synthesis of compound (15)> except that compound (93b) was used instead of compound (15b).

The physical property values of the compound (93) were as follows.
¹ H-NMR (400 MHz; 1,2-dichlorobenzene-d ₄ ; 140 ° C .; δ (ppm)); 9.08-9.14 (m, 1H), 9.14-9.20 (m, 1H )
TOF-MS (ASAP +); 408.9453 (M + 1); Calc. 408.959

<Example E-1a>
Using the compound (15) obtained in Example S-1, an organic semiconductor layer was formed on a “bare substrate” by vacuum deposition, and a source electrode and a drain electrode were further formed thereon by the above-described method. An organic TFT was prepared and evaluated.

(Evaluation of organic TFT)
When the transfer characteristics of the produced organic TFT were measured under the condition that the drain voltage was 100 V, the organic TFT showed n-type semiconductor characteristics.

As a result of calculating the field effect mobility (μ) using the above (formula A), in the organic TFT of the compound (15) on the “bare substrate”, the field effect mobility of 8.7 × 10 ⁻³ cm ² / Vs. It was found that the degree was obtained.

<Example E-1b>
Using the compound (15) obtained in Example S-1, an organic semiconductor layer was formed on a “HMDS substrate” by vacuum deposition, and a source electrode and a drain electrode were further formed thereon by the method described above. An organic TFT was prepared and evaluated.

(Evaluation of organic TFT)
When the transfer characteristics of the produced organic TFT were measured under the condition that the drain voltage was 100 V, the organic TFT showed n-type semiconductor characteristics.

As a result of calculating the field effect mobility (μ) using the above (formula A), in the organic TFT of the compound (15) on the “HMDS substrate”, a field effect transfer of 5.1 × 10 ⁻² cm ² / Vs. It was found that the degree was obtained.

<Example E-1c>
Using the compound (15) obtained in Example S-1, an organic semiconductor layer was formed on a “PS substrate” by vacuum deposition, and a source electrode and a drain electrode were further formed thereon by the method described above. An organic TFT was prepared and evaluated.

(Evaluation of organic TFT)
When the transfer characteristics of the produced organic TFT were measured under the condition that the drain voltage was 100 V, the organic TFT showed n-type semiconductor characteristics. The obtained transfer characteristics are shown in FIG. The horizontal axis in FIG. 5 is the gate voltage (V), and the vertical axis is the drain current (A). A curve with black circles is fore, and a curve with white circles is back.

As a result of calculating the field effect mobility (μ) using the above (Formula A), the organic TFT of the compound (15) on the “PS substrate” has a field effect mobility of 9.2 × 10 ⁻² cm ² / Vs. It was found that the degree was obtained.

<Example E-2a>
Using the compound (22) obtained in Example S-2, an organic semiconductor layer was formed on the “HMDS substrate” by vacuum deposition, and a source electrode and a drain electrode were further formed thereon by the method described above. An organic TFT was prepared and evaluated.

(Evaluation of organic TFT)
When the transfer characteristics of the produced organic TFT were measured under the condition that the drain voltage was 100 V, the organic TFT showed n-type semiconductor characteristics.

As a result of calculating the field effect mobility (μ) using the above (formula A), in the organic TFT of the compound (22) on the “HMDS substrate”, a field effect transfer of 6.0 × 10 ⁻³ cm ² / Vs is obtained. It was found that the degree was obtained.

<Example E-2b>
Using the compound (22) obtained in Example S-1, an organic semiconductor layer was formed on a “PS substrate” by vacuum deposition, and a source electrode and a drain electrode were further formed thereon by the method described above. An organic TFT was prepared and evaluated.

(Evaluation of organic TFT)
When the transfer characteristics of the produced organic TFT were measured under the condition that the drain voltage was 100 V, the organic TFT showed n-type semiconductor characteristics.

As a result of calculating the field effect mobility (μ) using the above (formula A), in the organic TFT of the compound 22) on the “PS substrate”, the field effect mobility of 3.1 × 10 ⁻³ cm ² / Vs is obtained. Was found to be obtained.

<Example E-3a>
Using the compound (23-1) obtained in Example S-3, an organic semiconductor layer was formed on a “bare substrate” by a vacuum deposition method, and a source electrode and a drain electrode were further formed thereon by the above-described method. Then, an organic TFT element was produced and evaluated.

(Evaluation of organic TFT)
When the transfer characteristics of the produced organic TFT were measured under the condition that the drain voltage was 100 V, the organic TFT showed n-type semiconductor characteristics.

As a result of calculating the field effect mobility (μ) using the above (formula A), in the organic TFT of the compound (23-1) on the “bare substrate”, the field effect mobility of 6 × 10 ⁻⁴ cm ² / Vs. It was found that the degree was obtained.

<Example E-3b>
Using the compound (23-1) obtained in Example S-3, an organic semiconductor layer was formed on the “HMDS substrate” by vacuum vapor deposition, and the source electrode and drain electrode were further formed thereon by the above-described method. The organic TFT was formed and evaluated.

(Evaluation of organic TFT)
When the transfer characteristics of the produced organic TFT were measured under the condition that the drain voltage was 100 V, the organic TFT showed n-type semiconductor characteristics.

As a result of calculating the field effect mobility (μ) using the above (formula A), the field effect mobility of 8 × 10 ⁻⁴ cm ² / Vs is obtained in the organic TFT of the compound (23-1) on the “HMDS substrate”. It was found that the degree was obtained.

<Example E-3c>
Using the compound (23-1) obtained in Example S-3, an organic semiconductor layer was formed on a “PS substrate” by a vacuum deposition method, and a source electrode and a drain electrode were further formed thereon by the above-described method. Then, an organic TFT element was produced and evaluated.

(Evaluation of organic TFT)
When the transfer characteristics of the produced organic TFT were measured under the condition that the drain voltage was 100 V, the organic TFT showed n-type semiconductor characteristics.

As a result of calculating the field effect mobility (μ) using the above (formula A), in the organic TFT of the compound (23-1) on the “PS substrate”, an electric field of 1.0 × 10 ⁻³ cm ² / Vs. It was found that effective mobility can be obtained.

<Example E-4a>
Using the compound (23-2) obtained in Example S-4, the organic semiconductor layer is formed on the “bare substrate” by spin coating to form the source electrode and the drain electrode as described above. An organic TFT was prepared and evaluated. The conditions for producing the organic semiconductor layer are as follows.

(Preparation conditions for organic semiconductor layer)
Compound (23-2) was added to chloroform so as to have a concentration of 0.1 wt%, and 0.18 mL of the solution (organic semiconductor ink) prepared by heating at 80 ° C. was dropped on the “bare substrate”, and 30 rpm at 1000 rpm. Spin coating was performed for 2 seconds to form an organic semiconductor layer having a thickness of about 20 nm. Thereafter, the “bare substrate” on which the organic semiconductor layer was formed was heated at 240 ° C. for 35 minutes.

(Evaluation of organic TFT)
When the transfer characteristics of the produced organic TFT were measured under the condition that the drain voltage was 100 V, the organic TFT showed n-type semiconductor characteristics. The obtained transfer characteristics are shown in FIG. The horizontal axis in FIG. 6 is the gate voltage (V), and the vertical axis is the drain current (A). A curve with black circles is fore, and a curve with white circles is back.

As a result of calculating the field effect mobility (μ) using the above (Formula A), the organic TFT of the compound (23-2) on the “bare substrate” has an electric field of 5.0 × 10 ⁻³ cm ² / Vs. It was found that effective mobility can be obtained.

<Example E-4b>
Using the compound (23-2) obtained in Example S-4, the organic semiconductor layer is formed on the “PVP substrate” by spin coating, and the source and drain electrodes are formed as described above. Then, an organic TFT element was produced and evaluated. The conditions for producing the organic semiconductor layer are as follows.

(Preparation conditions for organic semiconductor layer)
Compound (23-2) was added to chloroform so as to have a concentration of 0.1 wt%, and 0.18 mL of the solution (organic semiconductor ink) prepared by heating at 80 ° C. was dropped on the “PVP substrate” and 30 rpm at 1000 rpm. Spin coating was performed for 2 seconds to form an organic semiconductor layer having a thickness of about 20 nm. Thereafter, the “PVP substrate” on which the organic semiconductor layer was formed was heated at 120 ° C. for 35 minutes.

(Evaluation of organic TFT)
When the transfer characteristics of the produced organic TFT were measured under the condition that the drain voltage was 100 V, the organic TFT showed n-type semiconductor characteristics.

As a result of calculating the field effect mobility (μ) using the above (formula A), in the organic TFT of the compound (23-2) on the “PVP substrate”, an electric field of 1.4 × 10 ⁻² cm ² / Vs. It was found that effective mobility can be obtained.

<Comparative Example E-5a>
Using the compound (91) obtained in Comparative Example S-5, an organic semiconductor layer was formed on a “bare substrate” by vacuum deposition, and a source electrode and a drain electrode were further formed thereon by the above-described method. An organic TFT was prepared and evaluated.

(Evaluation of organic TFT)
When the transfer characteristics of the manufactured organic TFT were measured under the condition that the drain voltage was 100 V, the organic TFT did not show the transfer characteristics of the transistor.

<Comparative Example E-5b>
Using the compound (91) obtained in Comparative Example S-5, an organic semiconductor layer was formed on the “HMDS substrate” by vacuum deposition, and a source electrode and a drain electrode were further formed thereon by the method described above. An organic TFT was prepared and evaluated.

(Evaluation of organic TFT)
When the transfer characteristics of the manufactured organic TFT were measured under the condition that the drain voltage was 100 V, the organic TFT did not show the transfer characteristics of the transistor.

<Comparative Example E-5c>
Using the compound (91) obtained in Comparative Example S-5, an organic semiconductor layer was formed on the “PS substrate” by vacuum deposition, and a source electrode and a drain electrode were further formed thereon by the method described above. An organic TFT was prepared and evaluated.

(Evaluation of organic TFT)
When the transfer characteristics of the manufactured organic TFT were measured under the condition that the drain voltage was 100 V, the organic TFT did not show the transfer characteristics of the transistor.

<Comparative Example E-6a>
Using the compound (92) obtained in Comparative Example S-6, an organic semiconductor layer is formed on the “bare substrate” by spin coating, and the source and drain electrodes are formed as described above. An organic TFT was fabricated and evaluated. The conditions for producing the organic semiconductor layer are as follows.

(Preparation conditions for organic semiconductor layer)
Compound (92) is added to toluene to a concentration of 0.3 wt%, 0.18 mL of the solution (organic semiconductor ink) prepared at room temperature is dropped on the “bare substrate”, and spin coating is performed at 1000 rpm for 30 seconds. An organic semiconductor layer having a thickness of about 20 nm was formed.

(Evaluation of organic TFT)
When the transfer characteristics of the produced organic TFT were measured under the condition that the drain voltage was 100 V, the organic TFT showed p-type and n-type semiconductor characteristics (bipolar semiconductor characteristics). The obtained transfer characteristics are shown in FIG. In FIG. 7, the horizontal axis represents the gate voltage (V), and the vertical axis represents the drain current (A). A curve with black circles is fore, and a curve with white circles is back.

As a result of calculating the field effect mobility (μ) using the above (formula A), the organic TFT of the compound (92) on the “bare substrate” has an n-type semiconductor characteristic of 2.4 × 10 ⁻¹ cm. field-effect mobility of ² / Vs is, as the semiconductor characteristics of the p-type, field effect mobility of 2.4 × ¹⁰ -2 ^cm 2 / Vs was found to be obtained, respectively.

<Comparative Example E-7a>
Using the compound (93) obtained in Comparative Example S-7, an organic semiconductor layer was formed on a “bare substrate” by vacuum deposition, and a source electrode and a drain electrode were further formed thereon by the method described above. An organic TFT was prepared and evaluated.

(Evaluation of organic TFT)
When the transfer characteristics of the manufactured organic TFT were measured under the condition that the drain voltage was 100 V, the organic TFT did not show the transfer characteristics of the transistor.

<Comparative Example E-7b>
Using the compound (93) obtained in Comparative Example S-7, an organic semiconductor layer was formed on the “HMDS substrate” by vacuum deposition, and further a source electrode and a drain electrode were formed thereon by the above-described method. An organic TFT was prepared and evaluated.

(Evaluation of organic TFT)
When the transfer characteristics of the manufactured organic TFT were measured under the condition that the drain voltage was 100 V, the organic TFT did not show the transfer characteristics of the transistor.

<Comparative Example E-7c>
Using the compound (93) obtained in Comparative Example S-7, an organic semiconductor layer was formed on a “PS substrate” by vacuum deposition, and a source electrode and a drain electrode were further formed thereon by the method described above. An organic TFT was prepared and evaluated.

(Evaluation of organic TFT)
When the transfer characteristics of the manufactured organic TFT were measured under the condition that the drain voltage was 100 V, the organic TFT did not show the transfer characteristics of the transistor.

  From the above results, it was found that the benzobis (thiadiazole) derivative of the present invention exhibits high field effect mobility.

  According to the present invention, it is possible to provide a benzobis (thiadiazole) derivative that is easy to synthesize, has excellent electron mobility (field effect mobility), and can form a thin film by coating.

  Further, since the benzobis (thiadiazole) derivative of the present invention has a high field effect mobility, a high field effect mobility characteristic can be realized by using this compound for a semiconductor layer of an organic TFT. Moreover, high luminous efficiency is realizable by using this compound for an organic electroluminescent element, especially an electron carrying layer. Furthermore, high photoelectric conversion efficiency is realizable by using this compound for the charge-separation layer and electron carrying layer of an organic thin-film solar cell.

  In addition, a display device in which the organic TFT of the present invention and a pixel element formed by combining the organic EL element of the present invention or another organic EL element are arranged has an advantage of excellent luminous efficiency and responsiveness. doing. The organic TFT of the present invention can be suitably used as an organic TFT for operating an RFID tag or a sensor.

11, 21, 31, 111 Substrate 12, 106 Gate electrode 13, 107 Gate insulating layer 14, 110 Drain electrode 15, 109 Source electrode 16, 108 Organic semiconductor layer 22, 105 Anode 23, 104 Hole transport layer 24, 103 Light emission Layers 25 and 102 Electron transport layer 26 and 101 Cathode 112 Barrier layer 113 Protective layer 120 Organic EL element 121 Organic TFT
32 Anode 33 Charge separation layer 34 Cathode

Claims (18)

A benzobis (thiadiazole) derivative represented by the following general formula (1):

(In the formula, two R ^{1 s} independently represent either a hydrogen atom, a linear or branched alkyl group, or a group of the following formula (2);
Two R ² independently represent any one of a hydrogen atom, a linear or branched alkyl group, or a group of the following formula (2),
However, one of the two R ¹ and the two R ² is any of the groups of the following formula (2), and the other is not any of the groups of the following formula (2). );

(In the formula, R represents a linear or branched alkyl group). In the general formula (1), two R ¹ are independently any of the groups of the formula (2),
The benzobis (thiadiazole) derivative according to claim 1, wherein two R ² are independently a hydrogen atom or a linear or branched alkyl group. In the general formula (1), two R ¹ are independently any of the groups of the formula (2),
The benzobis (thiadiazole) derivative according to claim 1 or 2, wherein two R ² are hydrogen atoms. The benzobis (thiadiazole) derivative according to any one of claims 1 to 3, wherein the group of the formula (2) is any of the groups of the following formula (3).
In the general formula (1), two R ¹ are independently any one of a trifluoromethyl group, a cyano group, and an acyl group (—C (═O) R),
The benzobis (thiadiazole) derivative according to claim 1, wherein two R ² are hydrogen atoms.   An organic electronic device provided with the organic layer containing the benzobis (thiadiazole) derivative of any one of Claims 1-5. On the substrate, it has a gate electrode, a gate insulating layer, an organic semiconductor layer, a source electrode and a drain electrode,
The organic thin-film transistor in which the said organic-semiconductor layer contains the benzobis (thiadiazole) derivative of any one of Claims 1-5.   The organic thin film transistor according to claim 7, wherein the substrate is a flexible substrate. On the substrate, it has an anode, a light emitting layer, a hole transport layer and / or an electron transport layer, and a cathode.
The organic electroluminescent element in which the said hole transport layer and / or the said electron transport layer contain the benzobis (thiadiazole) derivative of any one of Claims 1-5. A display device that drives and lights an organic electroluminescence element using an organic thin film transistor,
A display device, wherein the organic thin film transistor is the organic thin film transistor according to claim 7 or 8.   An active matrix display device in which pixel elements each including the organic thin film transistor according to claim 7 or 8 and an organic electroluminescence element are arranged in a matrix.   The display device according to claim 10 or 11, wherein the organic electroluminescence element is the organic electroluminescence element according to claim 9. A display device that drives and lights an organic electroluminescence element using an organic thin film transistor,
A display device, wherein the organic electroluminescence element is the organic electroluminescence element according to claim 9. On a substrate, it has an anode, a charge separation layer containing a hole transport material and an electron transport material, and a cathode.
The organic thin-film solar cell in which the said charge separation layer contains the benzobis (thiadiazole) derivative of any one of Claims 1-5. On a substrate, it has an anode, a charge separation layer containing a hole transport material and an electron transport material, a hole transport layer and / or an electron transport layer, and a cathode.
The organic thin-film solar cell in which the said positive hole transport layer and / or the said electron carrying layer contain the benzobis (thiadiazole) derivative of any one of Claims 1-5.   The organic thin-film solar cell according to claim 14 or 15, wherein the substrate is a flexible substrate. An RFID tag that operates using an organic thin film transistor,
An RFID tag, wherein the organic thin film transistor is the organic thin film transistor according to claim 7 or 8. A sensor that operates using an organic thin film transistor,
A sensor, wherein the organic thin film transistor is the organic thin film transistor according to claim 7 or 8.