KR101728738B1 - organic semiconductor compounds, its manufacturing method and organic semiconductor device using the same - Google Patents

Abstract

The present invention provides an organic semiconductor compound, a method for producing the same, and an organic semiconductor device containing the same.

Description

TECHNICAL FIELD The present invention relates to an organic semiconductor compound, a method for producing the same, and an organic semiconductor device employing the organic semiconductor compound.

The present invention relates to an organic semiconductor compound, a method for producing the same, and an organic semiconductor device employing the organic semiconductor compound, and more particularly, to an organic semiconductor compound including a benzodithiophene derivative having a silylethynyl group substituted with a substituent, To an organic semiconductor device.

A device using an organic semiconductor has a lower deposition cost than a conventional inorganic semiconductor device so that a semiconductor thin film can be formed on various substrates or a film can be formed at room temperature and thus a low cost or a thin film is formed on a polymer film, It is expected.

Organic semiconductor materials have been applied to a wide variety of devices or devices including, for example, organic field effect transistors (OFET), organic light emitting diodes (OLEDs), photodetectors, photovoltaic (PV), sensors, memory devices and logic circuits.

Organic semiconductor materials have been developed to produce more diverse and cheaper electronic devices. At present, polyacene compounds such as anthracene, tetracene and pentacene are widely studied as an organic semiconductor material together with polyphenylene vinylene, polypyrrole, polythiophene and oligothiophene. In these polyacene compounds, it is expected that as the length of the ring is extended, the pi system widens and a larger orbit overlap between adjacent molecules is formed, thereby improving charge mobility.

However, most polyacene compounds require a high crystallinity structure to provide molecular orientation that leads to good charge mobility and have been vapor-deposited with features that are somewhat insoluble in conventional solvents. Such vapor deposition requires the development of organic semiconductor materials suitable for a solution process based on costly and complicated equipment, which can reduce the amount of material used and energy consumed in production.

Therefore, studies on a compound suitable for the solution process based on the excellent electrochemical characteristics of the organic semiconductor compound itself have been continued. For example, Korean Patent Publication No. 2014-0025266 provides an organic semiconductor compound having a naphthalene dithiophene skeleton .

However, by improving the pi-pi stacking in the solid phase, it is possible to easily remove the impurities by a simple molecular structure while having a solid flat structure capable of minimizing the phase transition, There is a continuing demand for the development of an organic semiconductor compound having solubility.

Korean Laid-open Patent Publication No. 2014-0025266 (Publication date 2014. 03.04)

The present invention provides a novel organic semiconductor compound having high charge mobility and solubility and a method for producing the same.

The present invention also provides an organic semiconductor device containing a novel organic semiconductor compound.

The present invention provides a novel organic semiconductor compound, and the novel organic semiconductor compound of the present invention can be represented by the following formula (1).

[Chemical Formula 1]

[In the above formula (1)

Z is S or Se;

R ¹ To R ⁶ independently of each other (C1-C30) alkyl, (C1-C30) alkoxy, (C1-C30) alkylthio, (C6-C30) aralkyl (C1-C30) alkyl group;

A ¹ to A ³ and B ¹ to B ³ independently of one another are (C 6 -C 30) arylene or (C 3 -C 30) heteroarylene;

R ⁷ or R ⁸ independently from each other are hydrogen, (C 1 -C 30) alkyl, (C 2 -C 30) alkenyl, (C 3 -C 30) cycloalkyl, (C 6 -C 30) aryl, C6-C30) aryl (C1-C30) alkyl;

n or o is an integer from 1 to 3;

l, m, p and q are integers of 0 to 3;

The R ¹ To alkyl groups of R ^6, aralkyl, alkylthio or alkoxy group, A ¹ to A ^3, and B ¹ to arylene or heteroarylene, and R ^7, or alkyl, cycloalkyl, aryl, aralkyl and heteroaryl of R ⁸ in the B ³ is (C1-C30) alkyl, (C2-C30) alkenyl, (C2- C30) alkynyl, (C1-C30) alkoxy, an amino group, a hydroxyl group, a halogen group, a cyano group, a nitro group, a trifluoromethyl group and a Can be.]

The organic semiconductor compound of the present invention includes a benzodithiophene skeleton having a substituted silylethynyl group as a substituent, thereby improving pi-pi stacking on a solid phase to minimize phase transition The charge mobility is very high.

That is, the organic semiconductor compound of the present invention is a silyl substituted with a (C1-C30) alkyl group, a (C1-C30) alkoxy group, a (C1-C30) alkylthio group or a (C6- The benzodithiophene skeleton having a thienyl group as a substituent has a rigid planar structure to improve pi-pi stacking and thus has a very high charge mobility.

In addition, the organic semiconductor compound of the present invention can be easily applied to a solution process by increasing the solubility by introducing various functional groups on both sides of the benzodithiophene skeleton having a substituted silylethynyl group as a substituent.

In addition, the organic semiconductor compound of the present invention can obtain a compound having a higher purity than a polymer, and can improve the electrochemical characteristics of an organic semiconductor device employing a high purity organic semiconductor compound, .

The substituents comprising " alkyl ", " alkoxy " and other " alkyl " moieties described in this invention encompass both linear and branched forms. The term " aryl " in the present invention means an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen, and may be a single or fused ring containing 4 to 7, preferably 5 or 6 ring atoms, A ring system, and a form in which a plurality of aryls are connected by a single bond. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, and the like. "Heteroaryl" in the present invention includes 1 to 4 heteroatoms selected from B, N, O, S, P (= O), Si and P as aromatic ring skeletal atoms and the remaining aromatic ring skeletal atoms are carbon Means a 5 to 6 membered monocyclic heteroaryl and a polycyclic heteroaryl condensed with at least one benzene ring and may be partially saturated. The heteroaryl in the present invention also includes a form in which one or more heteroaryl is connected to a single bond.

&Quot; Alkenyl " as used in the present invention means a straight-chain, branched or cyclic hydrocarbon radical containing 2 to 30 carbon atoms and at least one carbon to carbon double bond, , Alkyl, and the like.

로 표시될 수 있으며, R과 R'가 연결되어 아릴 또는 헤테로아릴이 융합되거나 융합되지 않은 시클로알킬 또는 헤테로시클로알킬을 형성하는 구조 또한 본 발명에 기재된 알케닐에 해당되며, 일례로 본 발명에 기재된

와

도 본 발명의 알케닐에 포함된다. As a specific example,

And the structure in which R and R 'are linked to form a cycloalkyl or heterocycloalkyl fused or non-fused with aryl or heteroaryl corresponds also to the alkenyl described in the present invention. For example,

Wow

Are also included in the alkenyl of the present invention.

&Quot; Cycloalkyl ", alone or as part of another group described above, means a fully saturated and partially unsaturated hydrocarbon ring of 3 to 9 carbon atoms, including the case where aryl or heteroaryl is fused .

"Heterocycloalkyl" as described above means a fully saturated and partially unsaturated hydrocarbon ring containing oxygen, sulfur or nitrogen in the ring as a hetero atom, and the number of heteroatoms is 1-4, preferably 1- 2. Cycloalkyl in heterocycloalkyl is preferably monocycloalkyl or bicycloalkyl, including those in which an aromatic cyclic aryl or heteroaryl is fused and also includes a double bond or a triple bond.

In view of the solubility and electrical properties of the compound of formula (1) according to an embodiment of the present invention, Z is preferably S; R ¹ to R ⁶ may independently be a (C ¹ -C 30) alkyl group or a (C 1 -C 30) alkoxy group, preferably a (C 1 -C 30) alkyl group, more preferably a .

In the formula (1), A ¹ to A ³ and B ¹ to B ³ may be selected from the following structures, but are not limited thereto.

[In the above formula,

 Z is S or Se;

R ¹¹ to R ^20, R ²² to R ^29, R ³² to R ^38, R ⁴⁰ and R ⁴³ are independently hydrogen, halogen, hydroxy each other, cyano, (C1-C30) alkyl, (C1-C30) alkoxy (C6-C30) aryl (C1-C30) alkyl group;

R ²¹ , R ³⁰ to R ³¹ and R ³⁹ independently represent hydrogen or a (C 1 -C 30) alkyl group;

a is an integer of 1 to 4;

b, e and f are integers of 1 to 2;

c or d is an integer of 1 to 3.]

Preferably, in Formula 1 according to an embodiment of the present invention, Z is S;

R ¹ To R < ⁶ > independently from each other are a (C1-C30) alkyl group or a (C1-C30) alkoxy group;

A ¹ to A ³ and B ¹ to B ³ may be selected from the following structures.

[In the above formula,

R ¹¹ to R ^12, R ¹⁵ to R ^19, R ²¹ to R ^23, R ²⁵ to R ²⁶ and R ²⁹ are independently hydrogen, halogen, hydroxy, cyano, (C1-C30) alkyl, (C1- each other C30) alkoxy group or (C6-C30) aryl (C1-C30) alkyl group;

R ¹³ to R ¹⁴ , R ²⁰ , R ²⁴ , R ²⁷ to R ²⁸ independently from each other are hydrogen or a (C 1 -C 30) alkyl group;

b, e and f are integers of 1 to 2.]

More preferably, Formula 1 according to an embodiment of the present invention may be represented by Formula 2 or Formula 3 below.

(2)

(3)

[In the above formulas 2 to 3,

Z is S or Se;

Z ¹ to Z ⁴ are independently of each other S or Se;

R ¹ To R ⁶ independently of each other (C1-C30) alkyl, (C1-C30) alkoxy, (C1-C30) alkylthio, (C6-C30) aralkyl (C1-C30) alkyl group;

R ⁷ or R ⁸ independently from each other are hydrogen, (C 1 -C 30) alkyl, (C 2 -C 30) alkenyl, (C 3 -C 30) cycloalkyl, (C 6 -C 30) aryl, C6-C30) aryl (C1-C30) alkyl;

A ² , A ³ , B ² and B ³ are, independently of one another, (C6-C30) arylene or (C3-C30) heteroarylene;

R ⁵¹ to R ⁵⁴ independently represent hydrogen or a (C1-C30) alkyl group;

R ⁵⁵ to R ⁵⁶ independently represent a (C1-C30) alkyl group, a (C1-C30) alkoxy group, a (C1-C30) alkylthio group or a (C6-

l, m, p and q are integers of 0 to 3;

r and t are independently of each other an integer of 1 to 2;

The R ¹ To alkyl groups of R ^6, aralkyl, alkylthio or alkoxy, R ⁷ or the R ⁸ alkyl, alkenyl, cycloalkyl, aryl, aralkyl and heteroaryl, Alkyl of R ⁵¹ to R ⁵⁴ , alkyl, alkoxy, alkylthio group of R ⁵⁵ to R ⁵⁶ and aralkyl and A ² , A ³ , B arylene or heterocyclic of ² and B ³ arylene is (C1-C30) alkyl, (C2-C30) alkenyl, (C2-C30) alkynyl, (C1-C30) alkoxy, an amino group, a hydroxyl group, a halogen Which may be further substituted with one or more substituents selected from halogen, cyano, nitro, trifluoromethyl and (C1-C30) alkylsilyl groups.

Preferably, in the above formula 2 or 3 of the present invention, Z is S or Se;

Z ¹ to Z ⁴ are S;

R ¹ To R < ⁶ > independently from each other are a (C1-C30) alkyl group;

R ⁷ or R ⁸ independently from each other are hydrogen, (C 1 -C 30) alkyl or (C 2 -C 30) alkenyl;

A ² , A ³ , B ² and B ³ are (C3-C30) heteroarylene;

l, m, p and q are integers from 0 to 2;

The R ¹ To alkyl groups of R ^6, R ⁷ or R ⁸ alkenyl and alkyl al, Alkyl of R ⁵¹ to R ⁵⁴ , alkyl, alkoxy, alkylthio group of R ⁵⁵ to R ⁵⁶ and aralkyl and A ² , A ³ , The arylene or heteroarylene of B ² and B ³ is selected from a (C1-C30) alkyl, an amino group, a hydroxyl group, a halogen group, a cyano group, a nitro group, a trifluoromethyl group and a Lt; / RTI > may be further substituted with one or more substituents.

More preferably, R ⁷ or R ⁸ in the general formula (2) or (3) may be independently selected from hydrogen or the following structural formula.

[In the above formula,

R < ⁷¹ > is hydrogen or (C1-C30) alkyl;

R ⁷² or R ⁷³ independently of one another are an amino group, a hydroxyl group, a halogen group, a cyano group, a nitro group, a trifluoromethyl group (C 1 -C 30) alkyl or a (C 1 -C 30) silyl group;

u is an integer from 1 to 4;

and v is an integer of 1 to 9.]

Specifically, Formula 1 according to an embodiment of the present invention can be selected from the following compounds, but is not limited thereto.

The present invention also provides a method for preparing an organic semiconductor compound comprising reacting a compound represented by the following general formula (4) with a compound represented by the following general formula (5) and (6) to produce an organic semiconductor compound represented by the general formula (1).

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

[In the above formulas 4 to 6,

Z is S or Se;

R ¹ To R ⁶ independently of each other (C1-C30) alkyl, (C1-C30) alkoxy, (C1-C30) alkylthio, (C6-C30) aralkyl (C1-C30) alkyl group;

A ¹ to A ³ and B ¹ to B ³ independently of one another are (C 6 -C 30) arylene or (C 3 -C 30) heteroarylene;

R ⁷ or R ⁸ independently from each other are hydrogen, (C 1 -C 30) alkyl, (C 2 -C 30) alkenyl, (C 3 -C 30) cycloalkyl, (C 6 -C 30) aryl, C6-C30) aryl (C1-C30) alkyl;

n or o is an integer from 1 to 3;

l, m, p and q are integers of 0 to 3;

T is Sn (R ⁶¹ ) (R ⁶² ) (R ⁶³ ), R ⁶¹ to R ⁶³ is Independently of one another are (C1-C10) alkyl;

X ¹ and X ² are independently of each other halogen;

The R ¹ To alkyl groups of R ^6, aralkyl, alkylthio or alkoxy group, A ¹ to A ^3, and B ¹ to B ³ of the arylene or heteroaryl group of alkylene and R ⁷ or R ⁸ alkyl, alkenyl, cycloalkyl, aryl, aralkyl and heteroaryl (C1-C30) alkyl, (C2-C30) alkenyl, (C1-C30) alkoxy, an amino group, a hydroxyl group, a halogen group, a cyano group, a nitro group, a trifluoromethyl group and a (C1-C30) Can be further substituted.]

The present invention also relates to a process for preparing an organic semiconducting compound, which comprises reacting a compound represented by the following formula (4) with a compound represented by the following formula (7) to prepare an organic semiconductor compound represented by the following formula A method for producing the compound is provided.

 [Chemical Formula 4]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

R-H

[In the formulas (4) and (7) to (9)

Z is S or Se;

R ¹ To R ⁶ independently of each other (C1-C30) alkyl, (C1-C30) alkoxy, (C1-C30) alkylthio, (C6-C30) aralkyl (C1-C30) alkyl group;

A ¹ to A ³ and B ¹ to B ³ independently of one another are (C 6 -C 30) arylene or (C 3 -C 30) heteroarylene;

R ⁷ or R ⁸ independently from each other are hydrogen, (C 1 -C 30) alkyl, (C 2 -C 30) alkenyl, (C 3 -C 30) cycloalkyl, (C 6 -C 30) aryl, C6-C30) aryl (C1-C30) alkyl;

n or o is an integer from 1 to 3;

l, m, p and q are integers of 0 to 3;

T is Sn (R ⁶¹ ) (R ⁶² ) (R ⁶³ ), R ⁶¹ to R ⁶³ is Independently of one another are (C1-C10) alkyl;

X is halogen;

The R ¹ To alkyl groups of R ^6, aralkyl, alkylthio or alkoxy group, A ¹ to A ^3, and B ¹ to B ³ of the arylene or heteroaryl group of alkylene and R ⁷ or R ⁸ alkyl, alkenyl, cycloalkyl, aryl, aralkyl and heteroaryl (C1-C30) alkyl, (C2-C30) alkenyl, (C1-C30) alkoxy, an amino group, a hydroxyl group, a halogen group, a cyano group, a nitro group, a trifluoromethyl group and a (C1-C30) Can be further substituted.]

The compounds of the above formulas (4) and (5), which are used as starting materials in the process for preparing the compound represented by the above formula (1), can be prepared by a known organic synthesis method. Specifically, Taybet Bilkay et al. al., Organic Electronics, 2013 , 14, 344-353, TJ Marks et. al., J. Am. Chem. Soc. 2011 , 133, 8142-8145 and Yang Yang et. al., Macromolecules, 2009 , 42, 6564-6571.

The solvent used in the production method of the present invention can be any conventional organic solvent but may be any solvent such as dichloromethane, DCE, toluene, acetonitrile, ), Tetrahydrofuran (THF), N, N -dimethylformamide (DMF) and N, N -dimethylacetamide (DMA).

The reaction temperature can be used at the temperature used in conventional organic synthesis, but it can be varied depending on the amount of the reaction material and the starting material, and the reaction is completed after confirming that the starting material is completely consumed through TLC or the like. When the reaction is completed, the solvent may be distilled off under reduced pressure after the extraction process, and then the target product may be separated and purified through a conventional method such as column chromatography.

The present invention also provides an organic semiconductor device containing an organic semiconductor compound according to the present invention.

The organic semiconductor device according to the present invention has high efficiency by containing an organic semiconductor compound according to the present invention having excellent electrical characteristics, light stability and solubility.

The organic semiconducting compound according to the present invention has a high purity as a single molecule and has excellent electrical properties as well as high solubility, so that it can be applied to a solution process base, and a benzodithiophene skeleton having a substituted silylethynyl group Including charge transport and light stability.

Further, the process for producing an organic semiconductor compound according to the present invention can produce a novel organic semiconductor compound by a simple process, and an organic semiconductor device containing an organic semiconductor compound prepared according to the present invention has high solubility and is produced by a solution process It is economical and has high stability due to high light stability, high life and excellent electric characteristics.

The present invention can be more clearly understood by the following examples, and the following examples are merely illustrative purposes of the present invention and are not intended to limit the scope of the invention.

[Example 1] Preparation of Compound 3

Pd (PPh3) 4 (8 mol%) was refluxed at 120 ° C for 20 hours in a solution of compound 1 (0.16 mmol, 140 mg) and compound 2 (0.33 mmol, 200 mg) in anhydrous toluene solvent. After the reaction is completed, the reaction solution is extracted with water and dichloromethane, and then the organic layer is collected and dried with magnesium sulphate and concentrated. The desired compound was isolated using flash column chromatography (chloroform / hexane (7: 3)) to obtain 190 mg (yield 74%) of compound 3 as a dark blue solid.

^{1 H NMR (300 MHz, CDCl} 3, ppm): δ 9.045 (d, 2H, J = 4.17Hz), 8.955 (m, 2H), 7.752 (s, 2H), 7.646 (m, 2H), 7.501 (d , 2H, J = 4.14Hz), 7.283 (m, 2H), 4.058 (m, 8H), 1.946 (m, 4H), 1.59-1.10 (m, 74H), 1.000-0.803 (m, 24H)

 [Example 2] Preparation of Compound 7

Step 1. Preparation of compound 6

Compound 4 (2.85 mmol, 1.95 g) and compound 5 (2.04 mmol, 597 mg) for which the K ₂ CO ₃ solution in anhydrous toluene (8.16 mmol, 1.13 g) and aliquat336 (0.15 mmol%, trioctylmethylammonium chloride , Aldrich) Was added. To the reaction solution was added _{Pd (PPh 3) 4 (8} mol%) and refluxed for 15 hours at 120 ℃. After the reaction is completed, the reaction solution is extracted with water and dichloromethane, and then the organic layer is collected and dried with magnesium sulphate and concentrated. The desired compound was isolated using flash column chromatography (chloroform / hexane (2: 5)) to obtain 700 mg (45% yield) of Compound 6 as a purple solid.

^{1 H NMR (300 MHz, CDCl} 3, ppm): δ 8.065 (d, 1H, J = 4.20Hz), 8.636 (d, 1H, J = 4.23Hz), 7.272 (m, 3H), 7.205 (m, 3H ), 7.112 (d, IH, J = 3.84 Hz), 7.042 (m, IH), 4.093-3.876 (m, 4H), 1.983-1.765 (m, 2H), 1.440-1.204 0.825 (m, 12H).

EI-Mass: calculated mass for chemical formula: C38H43BrN2O2S4 is 767.92, obtained mass is 768.

Step 2. Preparation of compound 7

Compound 3 was prepared in the same manner as Compound 1 (0.20 mmol, 177 mg) and Compound 6 (0.41 mmol, 315 mg) to give 200 mg (yield 58%) of Compound 7 of Example 2.

^{1 H NMR (300 MHz, CDCl} 3, ppm): δ 9.106 (d, 2H, J = 4.14Hz), 9.024 (d, 2H, J = 4.16), 7.54 (s, 2H), 7.362 (d, 2H, J = 4.14), 7.195 (d , 4H, J = 4.44Hz), 7.130 (m, 4H), 7.014 (m, 4H), 4.015 (m, 8H,), 1.922 (m, 4H), 1.49-1.19 ( m, 74H), 1.020-0.783 (m, 24H).

[Example 3] Preparation of Compound 9

Compound 9 (yield: 71%) was obtained as a black solid in the same manner as Compound 3 (75 mg, 0.095 mmol) and Compound 8 (200 mg, 0.19 mmol)

^{1 H NMR (300 MHz, CDCl3} , δ): 9.10 (d, J = 4.17Hz, 2H), 8.98 (d, J = 3.64Hz, 2H), 7.72 (s, 1H), 7.60 (d, J = 4.88 , 2H), 7.47 (d, J = 4.0,2H), 7.28 (m, 2H), 4.07 (m, 8H), 1.71 , 24H).

[Example 4] Preparation of Compound 11

Compound 13 was obtained in the same manner as Compound 3 (70 mg, 0.079 mmol) and Compound 10 (210 mg, 0.17 mmol) according to the same procedure as in Example 1 to give 130 mg (yield 52%) of a black solid.

^{1 H NMR (300 MHz, CDCl3} , δ): 9.13 (d, J = 4.14,2H), 8.97 (d, 3.9 = Hz, 2H), 7.42 (s, 1H), 7.27 (m, 2H), 7.13 ( (m, 2H), 7.06 (m, 4H), 7.00 (m, 2H), 6.93 (m, 4H), 4.13-3.92 (m, 8H), 1.75-1.59 198H), 0.88-0.76 (m, 24H).

[Example 5] Preparation of Compound 13

Example 5 was prepared in the same manner as in the preparation of Compound 3 by using Compound 1 (100 mg, 0.13 mmol) and Compound 12 (220 mg, 2.7 mmol) to obtain 110 mg (yield 42% .

^{1 H NMR (300 MHz, CDCl3} , δ): 8.98 (d, J = 4.05Hz, 2H), 8.92 (d, 3.55Hz, 2H), 7.77 (s, 2H), 7.63 (d, 5Hz, 2H), 8H), 2.04-1.85 (m, 4H), 1.41-1.11 (m, 138H), 0.87-0.75 (m, 2H) 24H).

[Example 6] Preparation of Compound 16

Step 1. Preparation of compound 15

Compound 35 was obtained in the same manner as in the preparation of Compound 3 by using Compound 1 (300 mg, 0.34 mmol) and Compound 14 (414 mg, 0.719 mmol) (360 mg, yield 61%).

Step 2. Preparation of 16

3 to 4 drops of piperidine were added to a solution of Compound 15 (0.15 g, 0.097 mmol) in chloroform (25 ml), 3-hexylrhodanine (0.12 g, 0.58 mmol) was added and refluxed for 12 hours. After the reaction was completed, the reaction solution was extracted with water and dichloromethane, and then the organic layer was collected, dried with magnesium sulphate and concentrated. The desired compound was isolated using flash column chromatography (chloroform) to obtain 140 mg (yield 80%) of a black solid compound 16.

^{1 H NMR (300 MHz, CDCl3} , δ): 7.73 (s, 2H), 7.52 (s, 2H), 7.26-7.13 (m, 8H), 4.06 (m, 4H), 2.82 (m, 8H), 1.75 -1.62 (m, 12H), 1.47-0.88 (m, 94H), 0.88-0.86 (m, 8H).

[Example 7] Fabrication of an organic solar cell element containing a monomolecular organic semiconductor compound

A glass substrate coated with ITO (Indium Tin Oxide), which is a positive transparent electrode, was immersed in deionized water containing washing solution, washed in an ultrasonic washing machine for 15 minutes, again washed with deionized water, acetone and IPA And then dried in an oven at 130 ° C for 5 hours. The cleaned ITO glass substrate was subjected to ultraviolet / ozone treatment for 15 minutes, and then a PEDOT: PSS layer as a hole transport layer was coated on the ITO glass substrate to a thickness of 40 nm through a spin coating process. Then, a heat treatment process was performed at 140 ° C. for 10 minutes, and the device was transferred to a glove box filled with argon for applying the organic active layer. The organic active layer was prepared by dissolving the organic semiconductor compound prepared in the example of the present invention and PC ₇₁ BM in a solvent such as chloroform, diphenylether or chlorobenzene (CB) at a mixing ratio (weight ratio) PTFE) syringe filter was coated on the PEDOT: PSS layer with a thickness of 80 nm through a spin coating method (500 rpm). The device was then moved to a vacuum chamber for aluminum deposition of the cathode electrode. Aluminum was deposited to a thickness of 100 nm at a vacuum degree of 1 × 10 ^-6 torr.

Table 1 shows the composition ratios of the organic semiconductor solution including the organic semiconductor compound prepared in the example of the present invention and the electrical characteristics of the organic solar cell manufactured.

Example compound Mixed solution ratio (Example compound: PC ₇₁ BM) menstruum V _oc
(V) Jsc
(mA / cm ² ) FF
(%) PCE
(%) One 3 1.0: 1.6 CF 0.79 12.2 65 6.26 One 3 1.0: 1.6 CB + DPE (3 vol%) 0.77 11.2 62 5.34 2 7 1.0: 1.0 CF 0.75 10.9 66 5.39 3 9 1.0: 1.6 CF 0.70 8.0 65 3.64 4 11 1.0: 1.6 CF 0.69 9.9 62 4.23 5 13 1.0: 1.6 CF 0.71 9.8 60 4.17 6 16 1.0: 1.6 CF 0.72 10.1 60 4.36

CF; chloroform, DPE: diphenylether,

The organic semiconductor compound containing a benzodithiophene derivative having a silylethynyl group according to the present invention has a high solubility in a solvent and an excellent thermal stability as well as a high efficiency of an organic semiconductor device containing the same as shown in Table 1 Able to know.

Claims (11)

delete delete delete delete (2) or (3).
(2)

(3)

[In the above formulas 2 to 3,
Z is S or Se;
Z ¹ to Z ⁴ are independently of each other S or Se;
R ¹ To R ⁶ independently of each other (C1-C30) alkyl, (C1-C30) alkoxy, (C1-C30) alkylthio, (C6-C30) aralkyl (C1-C30) alkyl group;
R ⁷ or R ⁸ independently from each other are hydrogen, (C 2 -C 30) alkenyl, (C 1 -C 30) alkyl, (C 3 -C 30) cycloalkyl, (C 6 -C 30) aryl, C6-C30) aryl (C1-C30) alkyl;
A ² , A ³ , B ² and B ³ are, independently of one another, (C6-C30) arylene or (C3-C30) heteroarylene;
R ⁵¹ to R ⁵⁴ independently from each other are a (C1-C30) alkyl group;
R ⁵⁵ to R ⁵⁶ independently represent a (C1-C30) alkyl group, a (C1-C30) alkoxy group, a (C1-C30) alkylthio group or a (C6-
l, m, p and q are integers of 0 to 3;
r and t are independently of each other an integer of 1 to 2;
The R ¹ To alkyl groups of R ^6, aralkyl, alkylthio or alkoxy, R ⁷ or the R ⁸ alkyl, cycloalkyl, aryl, aralkyl and heteroaryl, Alkyl of R ⁵¹ to R ⁵⁴ , alkyl, alkoxy, alkylthio group of R ⁵⁵ to R ⁵⁶ and aralkyl and A ² , A ³ , B arylene or heterocyclic of ² and B ³ arylene is (C1-C30) alkyl, (C2-C30) alkenyl, (C2-C30) alkynyl, (C1-C30) alkoxy, an amino group, a hydroxyl group, a halogen Which may be further substituted with one or more substituents selected from halogen, cyano, nitro, trifluoromethyl and (C1-C30) alkylsilyl groups. 6. The method of claim 5,
Z is S or Se;
Z ¹ to Z ⁴ are S;
R ¹ To R < ⁶ > independently from each other are a (C1-C30) alkyl group;
R ⁷ or R ⁸ independently from each other are hydrogen, (C 1 -C 30) alkyl or (C 2 -C 30) alkenyl;
A ² , A ³ , B ² and B ³ are (C3-C30) heteroarylene;
l, m, p and q are integers from 0 to 2;
The R ¹ To alkyl groups of R ^6, R ⁷ or R ⁸ alkenyl and alkyl al, Alkyl of R ⁵¹ to R ⁵⁴ , alkyl, alkoxy, alkylthio group of R ⁵⁵ to R ⁵⁶ and aralkyl and A ² , A ³ , The arylene or heteroarylene of B ² and B ³ is selected from a (C1-C30) alkyl, an amino group, a hydroxyl group, a halogen group, a cyano group, a nitro group, a trifluoromethyl group and a ≪ / RTI > The method according to claim 6,
R < ⁷ > or R < ⁸ > independently from each other are hydrogen or an organic semiconductor compound represented by the following formula:

[In the above formula,
R < ⁷¹ > is hydrogen or (C1-C30) alkyl;
R ⁷² or R ⁷³ independently of one another are an amino group, a hydroxyl group, a halogen group, a cyano group, a nitro group, a trifluoromethyl group (C 1 -C 30) alkyl or a (C 1 -C 30) silyl group;
u is an integer from 1 to 4;
and v is an integer of 1 to 9.] ≪ / RTI > is selected from the following compounds.

delete Reacting a compound represented by the following formula (4) with a compound represented by the following formula (7) to prepare an organic semiconductor compound represented by the following formula (1) .
[Chemical Formula 1]

[Chemical Formula 4]

(7)

[Chemical Formula 8]

[Chemical Formula 9]
R ^7-1 -H
[In the formulas (1), (4) and (7) to (9)
Z is S or Se;
R ¹ To R ⁶ independently of each other (C1-C30) alkyl, (C1-C30) alkoxy, (C1-C30) alkylthio, (C6-C30) aralkyl (C1-C30) alkyl group;
A ¹ to A ³ and B ¹ to B ³ independently of one another are (C 6 -C 30) arylene or (C 3 -C 30) heteroarylene;
R ^7-1 is selected from (C 1 -C 30) alkyl, (C 2 -C 30) alkenyl, (C 3 -C 30) cycloalkyl, (C 6 -C 30) aryl, (C 3 -C 30) heteroaryl and C1-C30) alkyl;
R ⁷ or R ⁸ independently from each other are hydrogen, (C 1 -C 30) alkyl, (C 2 -C 30) alkenyl, (C 3 -C 30) cycloalkyl, (C 6 -C 30) aryl, C6-C30) aryl (C1-C30) alkyl;
n or o is an integer from 1 to 3;
l, m, p and q are integers of 0 to 3;
T is Sn (R ⁶¹ ) (R ⁶² ) (R ⁶³ ), R ⁶¹ to R ⁶³ is Independently of one another are (C1-C10) alkyl;
X is halogen;
The R ¹ To alkyl groups of R ^6, aralkyl, alkylthio or alkoxy group, A ¹ to A ^3, and B ¹ to B ³ of the arylene or heteroaryl group of alkylene and R ⁷ or R ⁸ alkyl, alkenyl, cycloalkyl, aryl, aralkyl and heteroaryl (C1-C30) alkyl, (C2-C30) alkenyl, (C1-C30) alkoxy, an amino group, a hydroxyl group, a halogen group, a cyano group, a nitro group, a trifluoromethyl group and a (C1-C30) Can be further substituted.] An organic semiconductor device comprising the organic semiconductor compound according to any one of claims 5 to 8.