KR101694961B1 - small molecule asymmetric organic semiconductor compounds, its manufacturing method and organic semiconductor device using the same - Google Patents

Abstract

The present invention provides a monomolecular organic semiconductor compound and an organic semiconductor device employing the monomolecular organic semiconductor compound. The monomolecular organic semiconductor compound of the present invention has a substituent having a different structure in its central skeleton to increase electrical characteristics and solubility, Have excellent efficiency.

Description

TECHNICAL FIELD [0001] The present invention relates to a single-molecule asymmetric organic semiconductor compound, a method of manufacturing the same, and an organic semiconductor device employing the organic semiconductor compound,

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

A device using an organic semiconductor compound is not as complicated in film forming conditions as compared with a conventional inorganic semiconductor device and can form a semiconductor thin film on various substrates or can be formed at room temperature and thus can be manufactured at a low cost or by forming a thin film on a polymer film, Anger is expected.

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

In particular, in an organic solar cell, a donor material and an acceptor material are used together as a photoactive layer. In order to exhibit a photoelectric conversion performance with high efficiency, a domain size of a donor material and an acceptor material is extremely important. Currently, a compound having a symmetrical benzene-dithiophene structure has been used as a donor semiconductor material showing high efficiency of photoelectric conversion performance. However, symmetric structures have limitations in the control of morphology.

WO 2010-058692

The present invention provides novel monomolecular asymmetric organic semiconductor compounds.

The present invention also provides a novel monomolecular asymmetric organic semiconductor compound.

The present invention also provides an organic semiconductor device employing the monomolecular asymmetric organic semiconductor compound of the present invention.

The present invention provides a novel monomolecular asymmetric organic semiconductor compound which is excellent in electrical characteristics and high in solubility and applicable to a solution process base.

The monomolecular asymmetric organic semiconductor compound of the present invention is represented by the following formula (1).

[Chemical Formula 1]

[In the above formula (1)

Z is O, S or Se;

R ¹ is (C ¹ -C 20) alkyl, (C 3 -C 20) cycloalkyl, (C 3 -C 20) heterocycloalkyl, (C 6 -C 20) aryl or (C 3 -C 20) heteroaryl;

R ² is (C1-C20) alkyl, (C3-C20) _{^{cycloalkyl, - (i -O (R 1-1}} )) j -R 1-2 or - (R ^1-3) _k -NR ^1-4 and R ^1-5,

Wherein R ^1-1 or R ^1-3 is independently (C1-C10) alkylene,

R ^1-2 and R ^1-4 to R ^1-5 are independently of each other hydrogen, (C 1 -C 10) alkyl or (C 1 -C 10) alkoxy; i, j and k are integers from 1 to 5;

A ¹ to A ³ and B ¹ to B ³ independently of one another are (C 6 -C 20) arylene or (C 3 -C 20) heteroarylene;

에서 선택되며;R ⁷ or R ⁸ are each independently hydrogen, (C1-C20) alkyl, (C3-C20) cycloalkyl, (C6-C20) aryl, (C3-C20) heteroaryl, (C6-C20) aralkyl (C1- C10) alkyl or

Lt; / RTI >

n or o is an integer from 1 to 3;

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

R 'is hydrogen or (C1-C20) alkyl;

Alkyl group of the R ^1, cycloalkyl, heterocycloalkyl, aryl or heteroaryl, alkyl or to the R ^2, A ¹ to A ^3, and B ¹ to B ³ of the arylene or heteroarylene, and R ⁷ and R ⁸ alkyl, cycloalkyl, aryl, aralkyl and heteroaryl (C1-C20) alkyl, (C2-C20) alkenyl, (C2 -C20) alkynyl, (C1-C20) alkoxy, amino group, hydroxyl group, halogen group, cyano group, nitro group, trifluoromethyl group and silyl group.

The monomolecular asymmetric organic semiconductor compound of the present invention has a structure in which a benzene ring is fused with a difuran, dithiophene or dicerenophen, that is, a benzodifuran, benzodithiophene or benzodiselenophene fused ring, High charge mobility.

The monomolecular asymmetric organic semiconductor compound of the present invention also has an asymmetric substituent in the benzene present in the center of the benzodifuran, benzodithiophene or benzodiselenophene fused ring to have a high open-circuit voltage and to control morphology And the organic semiconductor device employing the organic semiconductor device has high efficiency.

In order to increase the efficiency of the organic semiconductor device including the monomolecular asymmetric organic semiconductor compound according to an embodiment of the present invention, Z is S in the formula (1), R ¹ is (C ¹ -C 20) alkyl or (C3-C20) heteroaryl, and R < ² > may be (C1-C20) alkyl.

In the formula (1), A ¹ to A ³ and B ¹ to B ³ may be selected from the following structures.

       [In the above formula,

 Z is O, S or Se;

R ¹¹ to R ⁴³ independently represent hydrogen, halogen, hydroxy, cyano, (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy or (C 6 -C 20) aryl (C 1 -C 10) alkyl;

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.]

The monomolecular asymmetric organic semiconductor compound according to an embodiment of the present invention is represented by Formula 1 wherein Z is S, R ¹ is (C ¹ -C 20) alkyl or (C 3 -C 20) heteroaryl, R ² is (C ¹ -C 20) C20) alkyl, A &^lt; ¹ > to A &^lt; ³ & B ¹ to B ³ may be selected from the following structures.

[In the above formula,

R ¹¹ to R ²⁹ independently represent hydrogen, halogen, hydroxy, cyano, (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy or (C 6 -C 20) aryl (C 1 -C 10) alkyl;

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

The formula (1) according to an embodiment of the present invention may more preferably be represented by the following formula (2) or (3).

(2)

(3)

[In the above formulas (2) and (3)

Z is O, S or Se;

R ¹ is (C ¹ -C 20) alkyl or (C 3 -C 20) heteroaryl;

R ² is (C 1 -C 20) alkyl;

R ³ to R ⁶ and R ¹¹ are independently of each other hydrogen, (C 1 -C 20) alkyl group, (C 6 -C 20) aryl (C 1 -C 10) alkyl;

A ² , A ³ , B ² and B ³ are, independently of one another, (C6-C20) arylene or (C3-C20) heteroarylene;

에서 선택되며;R ⁷ and R ⁸ are independently of each other hydrogen, (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl, (C 6 -C 20) aryl, (C 3 -C 20) heteroaryl, C10) alkyl or

Lt; / RTI >

n or o is an integer from 1 to 3;

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

R 'is hydrogen or (C1-C20) alkyl;

Alkyl group of the R ^1, cycloalkyl, heterocycloalkyl, aryl or heteroaryl, alkyl or to the R ^2, A ¹ to A ^3, and B ¹ to B ³ of the arylene or heteroarylene, and R ⁷ and R ⁸ alkyl, cycloalkyl, aryl, aralkyl and heteroaryl (C1-C20) alkyl, (C2-C20) alkenyl, (C2 -C20) alkynyl, (C1-C20) alkoxy, amino group, hydroxyl group, halogen group, cyano group, nitro group, trifluoromethyl group and silyl group.

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 and includes, for example, thienothienophen, N-alkylthienopyrro-dione . The heteroaryl in the present invention also includes a form in which one or more heteroaryl is connected to a single bond.

The present invention also provides a process for preparing a novel monomolecular asymmetric organic semiconductor compound represented by Formula 1, wherein the compound represented by Formula 1 is reacted with a compound represented by Formula 5, : ≪ / RTI >

[Chemical Formula 4]

[Chemical Formula 5]

[In the above formulas (4) and (5)

Z is O, S or Se;

R ¹ is (C ¹ -C 20) alkyl, (C 3 -C 20) cycloalkyl, (C 3 -C 20) heterocycloalkyl, (C 6 -C 20) aryl or (C 3 -C 20) heteroaryl;

R ² is (C1-C20) alkyl, (C3-C20) _{^{cycloalkyl, - (i -O (R 1-1}} )) j -R 1-2 or - (R ^1-3) _k -NR ^1-4 and R ^1-5,

Wherein R ^1-1 or R ^1-3 is independently (C1-C10) alkylene,

R ^1-2 and R ^1-4 to R ^1-5 are independently of each other hydrogen, (C 1 -C 10) alkyl or (C 1 -C 10) alkoxy, i, j and k are integers from 1 to 5;

에서 선택되며;R ⁷ or R ⁸ are each independently hydrogen, (C1-C20) alkyl, (C3-C20) cycloalkyl, (C6-C20) aryl, (C3-C20) heteroaryl, (C6-C20) aralkyl (C1- C10) alkyl or

Lt; / RTI >

R 'is hydrogen or (C1-C20) alkyl;

A ¹ to A ³ independently of one another are (C 6 -C 20) arylene or (C 3 -C 20) heteroarylene,

n is an integer from 1 to 3;

l or m is an integer of 0 to 3;

T is Sn (R ⁵¹ ) (R ⁵² ) (R ⁵³ ), R ⁵¹ to R ⁵³ are (C1-C10) alkyl;

X is halogen;

Alkyl group of the R ^1, cycloalkyl, heterocycloalkyl, aryl or heteroaryl, alkyl or to the R ^2, A ¹ to A ³ of the arylene or heteroarylene, and R ^7, cycloalkyl, aryl (C2-C20) alkynyl, (C1-C20) alkoxy, an amino group, a hydroxyl group, a halogen group, a cyano group, A nitro group, a trifluoromethyl group, and a silyl group.

는

와 동일하거나 상이한 치환기일 수 있다. In the process for preparing the compound of formula 1 according to an embodiment of the present invention, the compound of formula 4 is reacted with the compound of formula 5,

The

May be the same or different.

The present invention also relates to a process for preparing a compound represented by the following formula (5-2) by reacting a compound represented by the following formula (4) with a compound represented by the following formula (5-1) And then reacting the organic semiconductor compound to produce an organic semiconductor compound.

[Chemical Formula 4]

[Formula 5-1]

[Formula 5-2]

[Formula 5-3]

R ^7-1 -H

[In the formulas (1), (4) and (5-1) to (5-3)

Z is O, S or Se;

R ¹ is (C ¹ -C 20) alkyl, (C 3 -C 20) cycloalkyl, (C 3 -C 20) heterocycloalkyl, (C 6 -C 20) aryl or (C 3 -C 20) heteroaryl;

R ² is (C1-C20) alkyl, (C3-C20) _{^{cycloalkyl, - (i -O (R 1-1}} )) j -R 1-2 or - (R ^1-3) _k -NR ^1-4 and R ^1-5,

Wherein R ^1-1 or R ^1-3 is independently (C1-C10) alkylene,

R ^1-2 and R ^1-4 to R ^1-5 are independently of each other hydrogen, (C 1 -C 10) alkyl or (C 1 -C 10) alkoxy, i, j and k are integers from 1 to 5;

에서 선택되며;R ⁷ or R ⁸ are each independently hydrogen, (C1-C20) alkyl, (C3-C20) cycloalkyl, (C6-C20) aryl, (C3-C20) heteroaryl, (C6-C20) aralkyl (C1- C10) alkyl or

Lt; / RTI >

R 'is hydrogen or (C1-C20) alkyl;

이며;R ^7-1 is selected from (C 1 -C 20) alkyl, (C 2 -C 20) alkenyl, (C 3 -C 20) heterocycloalkyl, (C 6 -C 20) aryl, (C 3 -C 20) heteroaryl, (C1-C20) alkyl or

;

A ¹ to A ³ and B ¹ to B ³ independently of one another are (C6-C20) arylene or (C3-C20) heteroarylene,

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 ⁵¹ ) (R ⁵² ) (R ⁵³ ), R ⁵¹ to R ⁵³ are (C1-C10) alkyl;

X is halogen;

Alkyl group of the R ^1, cycloalkyl, heterocycloalkyl, aryl or heteroaryl, alkyl or to the R ^2, A ¹ to A ^3, and B ¹ to B ³ of the arylene or heteroarylene, R ⁷ and R ⁸ alkyl, alkenyl, cycloalkyl, aryl, aralkyl and heteroaryl alkyl, and R ^7-1, alkenyl, heterocycloalkyl, aryl (C1-C20) alkyl, (C2-C20) alkenyl, (C2-C20) alkynyl, C20) cycloalkyl, an amino group, a hydroxyl group, a halogen group, a cyano group, a nitro group, a trifluoromethyl group and a silyl group.

In the process for preparing an organic semiconductor compound of Formula 1 according to an embodiment of the present invention, the compound of Formula 4 may be prepared by reacting a compound of Formula 6 with a compound of Formula 7 or Formula 8.

[Chemical Formula 6]

(7)

(X ¹ ) Sn (R ⁵¹ ) (R ⁵² ) (R ⁵³ )

[Chemical Formula 8]

( ^R57 ) ( ^R56 ) ( ^R56 ) Sn-Sn ( ^R51 ) ( ^R52 ) ( ^R53 )

[In the above Chemical Formulas 6 to 8,

Z is O, S or Se;

R ¹ is (C ¹ -C 20) alkyl, (C 3 -C 20) cycloalkyl, (C 3 -C 20) heterocycloalkyl, (C 6 -C 20) aryl or (C 3 -C 20) heteroaryl;

R ² is (C1-C20) alkyl, (C3-C20) _{^{cycloalkyl, - (i -O (R 1-1}} )) j -R 1-2 or - (R ^1-3) _k -NR ^1-4 and R ^1-5,

Wherein R ^1-1 or R ^1-3 is (C 1 -C 10) alkylene,

R ^1-2 and R ^1-4 to R ^1-5 are independently of each other hydrogen, (C 1 -C 10) alkyl or (C 1 -C 10) alkoxy, i, j and k are integers from 1 to 5;

X ¹ is halogen;

R ⁵¹ - R ⁵⁶ is Independently of one another are (C1-C10) alkyl;

Alkyl group of the R ^1, cycloalkyl, heterocycloalkyl, aryl or heteroaryl, alkyl or to the R ^2, R ⁵¹ to The alkyl of R ⁵⁶ is selected from the group consisting of (C 1 -C 20) alkyl, (C 2 -C 20) alkenyl, (C 2 -C 20) alkynyl, A trifluoromethyl group, and a silyl group.]

(6) may be prepared by reacting a compound represented by the following formula (9) with the following formula (10) to prepare a compound of formula (11); And

And reacting the compound of formula (11) with a compound of formula (12) to prepare the compound of formula (6).

[Chemical Formula 9]

[Chemical formula 10]

R ¹ MX ²

(11)

[Chemical Formula 12]

R ² X ³

[In the above formulas (9) to (12)

Z is O, S or Se;

R ¹ is (C ¹ -C 20) alkyl, (C 3 -C 20) cycloalkyl, (C 3 -C 20) heterocycloalkyl, (C 6 -C 20) aryl or (C 3 -C 20) heteroaryl;

R ² is (C1-C20) alkyl, (C3-C20) _{^{cycloalkyl, - (i -O (R 1-1}} )) j -R 1-2 or - (R ^1-3) _k -NR ^1-4 and R ^1-5,

Wherein R ^1-1 or R ^1-3 is independently (C1-C10) alkylene,

R ^1-2 and R ^1-4 to R ^1-5 are independently of each other hydrogen, (C 1 -C 10) alkyl or (C 1 -C 10) alkoxy; i, j and k are integers from 1 to 5;

M is an alkali metal or an alkaline earth metal;

X ² or X ³ independently of one another are halogen;

Said alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl, and alkyl, or between kilo alkyl of R ² in R ¹ is halogen, (C1-C10) alkyl, (C1-C10) alkoxy, amino, hydroxy or nitro ≪ / RTI >

The reaction temperature and the reaction time are not limited in the method of preparing the monomolecular asymmetric organic semiconductor compound represented by Formula 1 according to an embodiment of the present invention, The step of reacting the compound represented by the formula (9) with the compound of the formula (10) to produce the compound of the formula (11) can be carried out at room temperature and 15 to 35 ° C for 5 hours to 30 hours, respectively. The step of preparing the compound of Formula 6 may be carried out at 80 to 110 ° C for 2 to 12 hours.

In formula (10) according to an embodiment of the present invention, M may be an alkali metal or an alkaline earth metal, preferably an alkaline earth metal, for example Mg.

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 a monomolecular asymmetric organic semiconductor compound of the present invention.

The monomolecular asymmetric organic semiconducting compound of the present invention is an organic semiconducting compound having a high purity as a single molecule and having excellent electrical characteristics as well as having a substituent which is asymmetric with respect to the central skeleton of the monomolecular asymmetric organic semiconductor compound, And has high charge mobility.

In addition, since the monomolecular asymmetric organic semiconductor compound of the present invention has high solubility, it can be applied to a solution process base, thereby making it economically large-scale.

In addition, the method for producing a monomolecular asymmetric organic semiconductor compound of the present invention can produce a monomolecular asymmetric organic semiconductor compound by a simple process.

Further, the organic semiconductor device employing the monomolecular asymmetric organic semiconductor compound of the present invention has a high open-circuit voltage and a high charge mobility, so that the efficiency is excellent.

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

Example 1 Synthesis of 8-Hydroxy-8-methylbenzo [1,2- b : 4,5- b ' ] dithiophen-4-one

Benzo [1,2- b : 4,5- b '] dithiophene-4,8-dione 4.4 g (20 mmol) was added to a 1000 ml flask containing 700 ml of anhydrous toluene and stirred at room temperature for 1 hour The temperature was then lowered to 0 ^° C. 7 ml (21 mmol) of 3M methyl magnesium bromide was added dropwise over 30 minutes. The reaction mixture was stirred at room temperature overnight and then quenched with 10 ml of 1N HCl. After three times extraction with diethyl ether, water was removed with MgSO ₄ and the solvent was removed. The residue was dissolved in 50 ml of a mixed solvent of ethyl acetate: diethyl ether (1: 1) and filtered. The solvent was removed from the filtrate and vacuum dried to obtain 4.13 g of the title compound (yield 87.5%) as a brown solid. The synthesized solid was used in the next step without further purification.

Example 2 Synthesis of 4- (2-ethylhexyloxy) -8-methylbenzo [1,2- b : 4,5- b ' ] dithiophene

Containing 3.67 g (15.5 mmol) of 8-Hydroxy-8-methylbenzo [1,2- b : 4,5- b ' ] dithiophen-4-one synthesized in Example 1 and 2.0 g (31.1 mmol) of zinc dust 80 ml of a 2M NaOH solution was added to a 250 ml flask, and the mixture was refluxed for 1 hour. After 2-ethylhexyl bromide 6 g (31.1 mmol) and into the tetrabutylammonium bromide (0.5 g, 1.6 mmol ) a catalytic amount of swelling, and the reaction mixture was refluxed for 6 hours in the cold NH ₄ Cl solution of 150 ml, CH ₂ Cl ₂ And extracted three times with 100 ml. The organic extracts were washed with Na ₂ SO ₄ , then the solvent was removed using a rotary evaporator and the residue was purified by silica gel column chromatography using a CH ₂ Cl ₂ : hexane (1: 8) solvent as mobile phase to give 3.05 g %) Of 4- (2-ethylhexyloxy) -8-methylbenzo [1,2- b : 4,5- b ' ] dithiophene as a pale yellow oil.

^{1 H NMR (300 MHz, CDCl} 3): δ (ppm) 7.51 (1H, d, J = 5.5); 7.42 (2 H, s); 7.37 (1H, d, J = 5.6); 4.19 (2H, d, J = 5.5); 2.75 (3 H, s); 1.79 (1 H, m); 1.59 (4 H, m); 1.39 (4 H, m); 1.01 (6 H, m).

¹³ C NMR (125 MHz, CDCl ₃ ):? (Ppm) 147.10; 139.13; 138.22; 129.65; 128.57; 126.54; 125.48; 121.78; 121.00; 120.50; 76.09; 40.74; 30.51; 29.26; 23.90; 23.16; 17.72; 14.19; 11.35.

MS (EI): Calcd, 332.1; found (M + l) ⁺ 333.

Example 3 Synthesis of 8-Hydroxy-8-octylbenzo [1,2- b : 4,5- b ' ] dithiophen-4-one

Benzo [1,2- b : 4,5- b '] dithiophene-4,8-dione 4.4 g (20 mmol) was added to a 1000 ml flask containing 700 ml of anhydrous toluene and stirred at room temperature for 1 hour The temperature was then lowered to 0 ^° C. 21 ml (21 mmol) of 1M n-octyl magnesium bromide was added dropwise over 30 minutes. The reaction mixture was stirred at room temperature overnight and then quenched with 10 ml of 1N HCl. After three times extraction with diethyl ether, water was removed with MgSO ₄ and the solvent was removed. The residue was dissolved in 50 ml of a mixed solvent of ethyl acetate: diethyl ether (1: 1), filtered, and filtered to remove solvent. Vacuum drying was conducted to obtain 6.60 g of the title compound (yield 98.7%) as a brown solid. The synthesized solid was used in the next step without further purification.

Example 4 Synthesis of 4-Heptyloxy-8-octylbenzo [1,2- b : 4,5- b ' ] dithiophene

Containing 3.20 g (9.57 mmol) of 8-hydroxy-8-octylbenzo [1,2- b : 4,5- b ' ] dithiophen-4-one synthesized in Example 3 and 1.24 g (19.1 mmol) of zinc dust 50 ml of 2M NaOH solution was added to a 250 ml flask, and the mixture was refluxed for 1 hour. Since n-heptyl bromide 3.4 g (19.1 mmol) and into the tetrabutylammonium bromide (0.3 g, 0.96 mmol ) a catalytic amount of swelling, and the reaction mixture was refluxed for 6 hours in the cold NH ₄ Cl solution of 150 ml, CH ₂ Cl ₂ And extracted three times with 70 ml. The organic extracts were washed with Na ₂ SO ₄ , then the solvent was removed using a rotary evaporator and the residue was purified by silica gel column chromatography using CH ₂ Cl ₂ : hexane (1: 8) as a mobile phase to give 3.24 g (Yield 81 %) Of 4-heptyloxy-8-octylbenzo [1,2- b : 4,5- b ' ] dithiophene as a pale yellow oil.

¹ H NMR (500 MHz, CDCl ₃ ):? (Ppm) 7.51 (1H, doublet, J = 5.8); 7.43 (2 H, s); 7.38 (1H, d, J = 5.6); 4.30 (2H, t, J = 6.5); 3.14 (2H, t, J = 7.8); 1.88 (2 H, m); 1.79 (2 H, m); 1.59 (2 H, m); 1.33 (16 H, m); 0.89 (6 H, m).

¹³ C NMR (125 MHz, CDCl ₃ ):? (Ppm) 146.88; 138.67; 137.75; 130.06; 129.02; 126.61; 126.48; 125.37; 121.78; 120.41; 73.94; 33.19; 31.92; 31.87; 30.61; 29.96; 29.67; 29.50; 29.27; 29.17; 26.07; 22.69; 22.66; 14.14.

MS (EI): Calcd, 416.2; found (M + 1) < ⁺ >

Example 5 Synthesis of 4-Octyl-8-octyloxybenzo [1,2- b : 4,5- b ' ] dithiophene

Containing 7.21 g (21.55 mmol) of 8-hydroxy-8-octylbenzo [1,2- b : 4,5- b ' ] dithiophen-4-one synthesized in Example 3 and 2.80 g (43.1 mmol) of zinc dust 120 ml of 2M NaOH solution was added to a 250 ml flask, and the mixture was refluxed for 1 hour. Since n-octyl bromide 8.32 g (43.1 mmol) and into the tetrabutylammonium bromide (0.7 g, 2.16 mmol ) a catalytic amount of swelling, and the reaction mixture was refluxed for 6 hours in the cold NH ₄ Cl solution of 150 ml, CH ₂ Cl ₂ And extracted three times with 100 ml. The organic extract was washed with Na ₂ SO ₄ , then the solvent was removed using a rotary evaporator, and 6.70 g (yield 72%) was obtained through silica gel column chromatography using a CH ₂ Cl ₂ : hexane (1: 8) %) Of 4-octyl-8-octyloxybenzo [1,2- b : 4,5- b ' ] dithiophene as a pale yellow oil.

¹ H NMR (300 MHz, CDCl ₃ ):? (Ppm) 7.50 (1H, doublet, J = 5.6); 7.43 (2 H, s); 7.37 (1H, d, J = 5.6); 4.30 (2H, t, J = 6.8); 3.14 (2H, t, J = 7.6); 1.88 (2 H, m); 1.79 (2 H, m); 1.56 (2 H, m); 1.30 (18H, m); 0.88 (6 H, m).

_{^{13 C NMR (125MHz, CDCl 3}} ): δ (ppm) 146.89; 138.67; 137.76; 130.06; 129.01; 126.60; 126.47; 125.35; 121.77; 120.41; 73.93; 33.19; 31.92; 31.86; 30.61; 29.96; 29.67; 29.50; 29.45; 29.31; 29.27; 26.11; 22.69; 14.13.

MS (EI): Calcd, 430.2; found (M + 1) < ⁺ & gt ^; 431.3.

Example 6 Synthesis of 4- (2-ethylhexyl) -8-octyloxybenzo [1,2- b : 4,5- b ' ] dithiophene

Containing 3.2 g (9.57 mmol) of 8-hydroxy-8-octylbenzo [1,2- b : 4,5- b ' ] dithiophen-4-one synthesized in Example 3 and 1.24 g (19.13 mmol) of zinc dust 60 ml of a 2M NaOH solution was added to a 250 ml flask, and the mixture was refluxed for 1 hour. Then 3.7 g (19.13 mmol) of 2-ethylhexylbromide and a catalytic amount of tetrabutylammonium bromide (0.31 g, 0.96 mmol) were added and the mixture was refluxed for 6 hours. The reaction mixture was poured into 100 ml of cold NH ₄ Cl solution and 50 ml of CH ₂ Cl ₂ . The organic extract was washed with Na ₂ SO ₄ , then the solvent was removed using a rotary evaporator, and the residue was purified by silica gel column chromatography using a CH ₂ Cl ₂ : hexane (1: 8) solvent as a mobile phase to obtain 3.4 g %) Of 4- (2-ethylhexyl) -8-octyloxybenzo [1,2- b : 4,5- b ' ] dithiophene as a pale yellow oil.

^{1 H NMR (500 MHz, CDCl} 3): δ (ppm) 7.52 (1H, d, J = 5.6); ^{7.44 (2H, dd, J 1} = 1.8, J 2 = 5.6); 7.37 (1H, d, J = 5.6); 4.20 (2 H, m); 3.15 (2H, t, J = 7.7); 1.85 (3H, m); 1.70 (4H, m); 1.62-1.30 (14 H, m); 1.03 (3H, t, J = 7.4); 0.95 (3H, t, J = 7.2); 0.89 (3H, t, J = 7.2).

¹³ C NMR (125 MHz, CDCl ₃ ):? (Ppm) 147.11; 138.72; 137.81; 129.88; 128.75; 126.47; 125.30; 121.77; 120.38; 76.01; 40.73; 33.19; 31.94; 30.49; 29.96; 29.75; 29.69; 29.52; 29.30; 29.24; 23.89; 23.16; 22.71; 14.89; 14.15; 11.34.

MS (EI): Calcd, 430.2; found (M + 1) < ⁺ & gt ^; 431.

Example 7 Synthesis of 8-Decyl-8-hydroxybenzo [1,2-: 4,5 - '] dithiophen-4-one

Benzo [1,2- b : 4,5- b '] dithiophene-4,8-dione (3.3 g, 20 mmol) was added to a 500 ml flask containing 700 ml of anhydrous toluene and stirred at room temperature for 1 hour The temperature was then lowered to 0 ^° C. 16.5 ml (16.5 mmol) of 1M n-decyl magnesium bromide is added dropwise over 30 minutes. The reaction mixture was stirred at room temperature overnight and then quenched with 10 ml of 1N HCl. After three times extraction with diethyl ether, water was removed with MgSO ₄ and the solvent was removed. The residue was dissolved in 50 ml of diethyl ether solvent and filtered. The solvent was removed from the filtrate and vacuum dried to obtain 5.1 g of a brown oil (yield: 93.6%). The synthesized compound was used in the next step without further purification.

Example 8 Synthesis of 4-Decyl-8-decyloxybenzo [1,2-: 4,5 - '] dithiophene

250 ml containing 5.59 g (15.4 mmol) of 8-decyl-8-hydroxybenzo [1,2-: 4,5- '] dithiophen-4-one synthesized in Example 7 and 2.0 g (30.8 mmol) 90 ml of 2M NaOH solution was added to the flask, and the mixture was refluxed for 1 hour. Since n-octyl bromide 6.82 g (30.8 mmol) and a catalytic amount of tetrabutylammonium bromide (0.5 g, 1.5 mmol ) into the swelling, and the reaction mixture was refluxed for 6 hours in the cold NH ₄ Cl solution of 150 ml, CH ₂ Cl ₂ And extracted three times with 100 ml. The organic extract was washed with Na ₂ SO ₄ , then the solvent was removed using a rotary evaporator, and the residue was purified by silica gel column chromatography using a CH ₂ Cl ₂ : hexane (1: 8) solvent as mobile phase to obtain 4.6 g %) Of 4-Decyl-8-decyloxybenzo [1,2-: 4,5 - '] dithiophene as a pale yellow oil.

^{1 H NMR (300 MHz, CDCl} 3): δ (ppm) 7.50 (1H, d, J = 5.2); 7.43 (2 H, s); 7.36 (1H, d, J = 5.5); 4.29 (2H, t, J = 6.6); 3.14 (2H, t, J = 7.7); 1.87 (2 H, m); 1.78 (2 H, m); 1.54 (2 H, m); 1.26 (26H, broad); 0.88 (6 H, m).

MS (EI): Calcd, 486.3; found (M + 1) < ⁺ >

Example 9 Synthesis of 2,6-Bis (trimethyltin) -4-decyl-8-decyloxybenzo [1,2- b : 4,5- b ' ] dithiophene

Embodiment a 4-Decyl-8-decyloxybenzo synthesized in Example 8: After the [1,2- 4,5 '] dithiophene 4.6 g (9.45 mmol) dissolved in anhydrous THF in a 200 ml argon atmosphere, to -78 ^o C After cooling, 13.0 ml (20.8 mmol) of 1.6 M n-BuLi was added dropwise over 30 minutes. After stirring at the same temperature for 30 minutes, the temperature was gradually raised to room temperature for 30 minutes. After cooling to -78 ^° C again, 20.8 mmol of 1 M trimentyltin chloride dissolved in THF was added. The reaction solution was slowly warmed to room temperature and stirred overnight. The reaction was terminated by the addition of 30 ml of cold water and extracted three times with diethyl ether. The organic extracts were washed twice with water, the water was removed with Na ₂ SO ₄ , the solvent was removed in vacuo and recrystallized from ethanol to obtain 4.1 g (53%) of colorless needle-like crystals.

^{1 H NMR (300 MHz, CDCl} 3): δ (ppm) 7.55 (1H, t, J = 14.3); 7.45 (1H, t, J = 14.5); 4.31 (2H, t, J = 6.7): 3.17 (2H, t, J = 7.7); 1.84 (4 H, m); 1.58 (2 H, m); 1.27 (26 H, broad); 0.88 (6 H, m); 0.44 (18H, m).

^{13 C NMR (125 MHz, CDCl} 3): δ (ppm) 145.50; 143.04; 140.75; 139.82; 138.99; 132.78; 131.14; 129.55; 128.23; 125.14; 73.59; 33.25; 31.95; 30.61; 29.94; 29.73; 29.68; 29.64; 29.53; 29.51; 29.39; 26.15; 22.71; 14.14; -8.29; -8.32.

Example 10 Synthesis of 4,8-dihydrobenzo [1,2-b: 4,5-b '] dithiophene-4-hydroxy-4- [2- (2-ethylhexyl) thiophen] -8-one

1.170 g (48.0 mmol) of magnesium metal and 30 ml of anhydrous THF were added to the flask and stirred at room temperature. 6.61 g (24.0 mmol) of 2-bromo-5- (2-ethylhexyl) thiophene was added dropwise and the mixture was refluxed for 5 hours. In another flask, benzo [1,2- b: 4,5- b ' ] dithiophene-4,8-dione 4.41 g (20.0 mmol) and then stirred for one hour the flask containing dry toluene at room temperature 650 ml of 0 ^o C to lower the temperature. The reaction mixture was stirred at room temperature overnight, and then a solution of 5% (2-ethylhexyl) thiophene-2-yl magnesium bromide was slowly added dropwise to 2-bromo-5- (2-ethylhexyl) thiophene toluene. The reaction was terminated with 15 ml of HCl. After three times extraction with diethyl ether, water was removed with MgSO ₄ and the solvent was removed. The residue was dissolved in a diethyl ether solvent and filtered. The solvent was removed from the filtered portion and vacuum dried to obtain 8.13 g of a brown solid (yield: 97.6%). The synthesized compound was used in the next step without further purification.

_{^{1 H NMR (CDCl 3, 300MHz}} , δppm): 7.50 (d, 1H), 7.36 (d, 1H), 7.34 (d, 1H), 7.32 (d, 1H), 6.52 (m, 2H), 3.17 (s , 2.66 (d, 2H), 1.30-1.25 (m, 9H), 0.88-0.83 (m, 6H).

Example 11 Synthesis of 2,6- 4- [2- (2-ethylhexyl) thiophen-5-yl] -8-octyloxy benzo [1,2- b; 3,4-b] dithiophene

Dihydrobenzo [1,2-b: 4,5-b '] dithiophene-4-hydroxy-4- 2- (2-ethylhexyl) thiophen-8-one synthesized in Example 10 19.5 mmol) and 2.54 g (39 mmol) of zinc dust were placed in a 250 ml flask, and the mixture was refluxed for 2 hours. Then 7.54 g (39 mmol) of n-octyl bromide and a catalytic amount of tetrabutylammonium bromide (0.7 g, 2.16 mmol) were added and refluxed for 6 hours. Then, 50 ml of NH ₄ Cl solution was added to the reaction mixture, ether. The organic extracts were washed with anhydrous MgSO ₄ and the solvent was removed using a rotary evaporator. The residue was subjected to silica gel column chromatography using CH ₂ Cl ₂ : hexane (1: 9) as a mobile phase to give 7.07 g (Yield: 70.6% ) Of 2,6- 4- [2- (2-ethylhexyl) thiophen-5-yl] -8-octyloxy benzo [1,2- b; 3,4-b] dithiophene as an orange oil.

_{^{1 H NMR (CDCl 3, 300MHz}} , δppm): 7.59 (d, 1H), 7.54 (d, 1H), 7.43 (d, 1H), 7.40 (d, 1H), 7.22 (d, 1H), 6.86 (d (M, 3H), 1.44-1.31 (m, 16H), 0.96-0.88 (m, 9H) ).

Example 12 Synthesis of bis (trimethyltin) -4- [2- (2-ethylhexyl) thiophene-5-yl] -8-octyloxybenzo [1,2- b; 3,4-b] dithiophene

2.57 g (5.01 mmol) of 4- [2- (2-ethylhexyl) thiophene-5-yl] -8-octyloxybenzo [1,2- b; 3,4- b] dithiophene synthesized in Example 11 was dissolved in an argon atmosphere Was dissolved in 180 ml of anhydrous THF, cooled to -78 ^° C, and 6.9 ml (11.02 mmol) of 1.6 M n-BuLi was added dropwise over 30 minutes. After stirring for 30 minutes at the same temperature, the temperature was gradually raised to room temperature for 30 minutes. After cooling to -78 ^° C again, 11 ml of 1 M trimentyltin chloride dissolved in THF solution (11.02 mmol) was added. The reaction solution was slowly warmed to room temperature and stirred for 1 hour. The reaction was terminated by the addition of methanol and extracted three times with diethyl ether. The organic extracts were dried over MgSO ₄ , the solvent was removed in vacuo and washed several times with ethanol to give 2.50 g (59.5%) of a viscous orange oil.

_{^{1 H NMR (CDCl 3, 300MHz}} , δppm): 7.62 (s, 1H), 7.57 (s, 1H), 7.24 (d, 1H), 6.87 (d, 1H), 4.40 (t, 2H), 2.86 (d 2H), 1.84 (t, 2H), 1.93-1.89 (m, 3H), 1.45-1.22 (m, 16H), 0.96-0.87 (m, 9H), 0.42 (t, 18H).

Example 13 Synthesis of 3- [5- (2,2'-bithiophen-5-yl) thiophen-2-yl] -6- (5-bromothiophen- ) pyrrolo [3,4-c] pyrrolo-1,4-dione

3,4-c] pyrrolo-1,4-dione 4.02 g (5.89 mmol) of 2,2'-bithiophene- 5-boronic acid pinacol ester (1.12 g, 3.84 mmol) and 15 ml of 1 M sodium carbonate were placed in a flask already filled with 100 ml of toluene. After the oxygen in the reaction mixture was removed using an argon bubble, the reaction was carried out in an argon atmosphere at 90 DEG C for 24 hours. The reaction solution was filtered through a silica filter, precipitated in methanol, and filtered to obtain a solid. The solid was subjected to column chromatography using a hexane / chloroform 1: 1 ratio solvent as a mobile phase to give a dark blue solid. The solid was again poured into 300 ml of methanol, stirred, sonicated for 10 minutes and filtered, and then the solid was dried in a vacuum oven at 50 < 0 > C for 24 hours to give 1.05 g (36%) of a dark blue solid.

^{1 H NMR (300 MHz, CDCl} 3): δ (ppm) 8.96 (d, J = 4.2 Hz, 1H); 8.63 (d, J = 4.1 Hz, 1 H); 7.30 (d, J = 4.1 Hz, 1 H); 7.28-7.20 (m, 4H); 7.11 (d, J = 3.7 Hz, 1 H); ^{7.05 (dd, J 1 = 3.6Hz} , J 2 = 1.4Hz, 1H); 4.06-3.93 (m, 4H); 1.88 (m, 2 H); 1.31 (m, 16H); 0.88 (m, 12 H).

¹³ C NMR (125 MHz, CDCl ₃ ):? (Ppm) 161.77, 161.41, 142.95, 140.42, 138.55, 138.41, 137.30, 136.76, 135.11, 134.78, 131.50, 128.19, 128.03, 126.06, 125.32, 124.75, 124.41, 118.60, 108.51, 108.10, 46.13, 39.40, 39.26, 30.51, 30.33, 28.70, 28.48, 23.83, 23.73, 23.26, 23.18, 14.23, 14.16, 10.69, 10.64.

EI-MS m / z calcd for C ₃₈ H ₄₃ BrN ₂ O ₂ S ₄ (M ⁺ ): 766.14; found: 767

Example 14 Synthesis of 2,6-bis {5- {6- [5- (2,2'-bithiophen-5-yl) thiophen-2-yl] -2,5- di (2- ethylhexyl) pyrrolo [ 3,4-c] pyrrolo-1,4-dione-3-yl} thiophen-2-yl} -4-decyl-8-decyloxybenzo [1,2- b: 4,5- '] dithiophene

A 20 ml flask was charged with 98 mg (0.12 mmol) of 2,6-bis (trimethyltin) -4-decyl-8-decyloxybenzo [1,2- b : 4,5- b ' ] dithiophene, 3- [5- , 2'-bithiophen-5-yl) thiophen-2-yl] -6- (5-bromothiophen-2-yl) -2,5-di (2- ethylhexyl) pyrrolo [3,4- c] pyrrolo- , 4-dione (200 mg, 0.26 mmol), toluene (5 ml) and DMF (1 ml) were added and then the oxygen was removed through an argon bubble. To the mixed solution, 6 mg (0.005 mmol) of tetrakis (triphenylphosphine) palladium (0) catalyst was added, followed by argon bubbling. The reaction solution was reacted in an argon atmosphere at 100 ° C for 24 hours, and then the reaction solution was dropped in methanol and filtered. The column was chromatographed on a hexane / chloroform mobile phase solvent at 1/2 to 1/10 ratio to obtain a green solid. The obtained solid was again precipitated in 100 ml of methanol, sonicated for 10 minutes, filtered, washed with hot methanol, acetone, and hexane sequentially, and then dried in a vacuum oven at 50 ° C for 24 hours to obtain 163 mg of 73% A green solid was obtained.

^{1 H NMR (500 MHz, CDCl} 3): δ (ppm) 9.01 (4H, broad); 7.39 (1H, s); 7.24 (3 H, m); 7.20 (2 H, m); 7.13 (4 H, m); 7.06 (2 H, m); 7.01 (2 H, m); 6.97 (2 H, m); 4.33 (2H, t, J = 7.3); 4.02 (8H, broad); 3.00 (2 H, m); 1.94 (6H, m); 1.76 (2 H, m); 1.67 (2 H, m); 1.45-1.30 (58H, broad); 0.97 (30H, m).

Example 15 Preparation of 2,6-bis {5- {6- [5- (2,2'-bithiophen-5-yl) thiophen-2-yl] -2,5- di (2- ethylhexyl) pyrrolo [ 3,4-c] pyrrolo-1,4-dione-3-yl} thiophen-2-yl} -4-decyl-8-decyloxybenzo [1,2- b: 4,5- '] dithiophene

To a 20 ml flask was added 100 mg (0.12 mmol) of bis (trimethyltin) -4- [2- (2-ethylhexyl) thiophene-5-yl] -8-octyloxy benzo [1,2- b; 3,4- b] dithiophene ), 3- [5- (2,2'-bithiophen-5-yl) thiophen-2-yl] -6- (5-bromothiophen- 3,4-c] pyrrolo-1,4-dione (198 mg, 0.26 mmol), toluene (5 ml), and DMF (1 ml) were purged with argon bubbles. To the mixed solution, 7 mg (5 mol%) of tetrakis (triphenylphosphine) palladium (0) catalyst was added and then argon bubbling was conducted again. The reaction solution was reacted in an argon atmosphere at 100 ° C for 24 hours, and then the reaction solution was dropped in methanol and filtered. The column was chromatographed on a hexane / chloroform mobile phase solvent at 1/2 to 1/10 ratio to obtain a green solid. The resulting solid was again precipitated in 100 ml of methanol, sonicated for 10 minutes, filtered, washed with hot methanol, acetone, and then hexane, and then dried in a vacuum oven at 50 ° C for 24 hours to obtain 185 mg of 82% A green solid was obtained.

¹ H NMR (300 MHz, CDCl ₃ ):? (Ppm) 9.01 (4H, broad); 7.43 (1H, s); 7.36 (1H, d); 7.17-7.13 (4 H, m); 7.09-7.06 (4 H, m); 6.98-6.88 (8 H, m); 4.33 (2H, t, J = 7.3); 4.02 (8H, broad); 3.00 (2 H, m); 1.94 (6H, m); 1.76 (2 H, m); 1.67 (2 H, m); 1.45-1.30 (50H, broad); 0.97 (30H, m).

Example 16 Synthesis of (5Z, 5'Z) -5,5 '- (((4-octyl-8- (octyloxy) benzo [1,2- b: 4,5- b'] dithiophene- bis (3 ', 3'', 4-trihexyl- [2,2': 5 ', 2''- terthiophene] -5', 5-diyl) bis (methanylidene) ethyl-2-thioxothiazolidin-4-one) (4)

5 '', 5 '' - (4-octyl-8- (octyloxy) benzo [1,2- b: 4,5- b '] dithiophene-2,6- '', 4-trihexyl- [2,2 ': 5', 2 "-terthiophene] -5-carbaldehyde

5 ', 5'-trithiophene-5-carbaldehyde (250 mg, 0.27 mmol) and 2,6' -bis (trimethyl tin) -4,8-bis (octyloxy) benzo [1,2- b: 4,5- b '] dithiophene (90 mg, 0.12 mmol) in toluene: DMF (10 mL, 9: 1 v / v) was added to the mixed solvent and the addition of _{Pd (PPh 3) 4 (15} mg, 0.012 mmol) here it was stirred at 115 ℃ for 24 hours. After the reaction mixture was diluted with water (25 mL) and extracted with CH ₂ Cl ₂ , the obtained organic layer was washed with water, and the remaining water was removed with Na ₂ SO ₄ , and the residue was purified by column chromatography (dichloromethane: hexane) The following reaction was used without purification.

To a solution of Compound 3 (170 mg, 0.10 mmol), 3-Ethylrhodanine (82 mg, 0.5 mmol) and AcONH ₄ (77 mg, 1.0 mmol) in 10 mL of a mixed solvent of chlorobenzene and acetic acid (1: 1 v / v) Lt; / RTI > 50 mL of methanol was added to the reaction mixture, and the mixture was stirred for 3 hours. The resulting solid was filtered and the residue was washed with methanol. The resulting solid was dissolved again in dichloromethane and the separated and purified by column chromatography (dichloromethane: hexane 2: 3) to give the title compound 4 as a dark brown solid (142 mg, 71% yield).

_{^{1 HNMR (300MHz, CHCl 3)}} : δ 7.93 (s, 2H) 7.46 (s, 1H), 7.37 (s, 1H) 7.13 (s, 1H), 7.12 (s, 1H), 7.06 (s, 2H), J = 7.2 Hz), 3.07 (m, J = 8.2 Hz 2H), 2.82 (m, 12H), 1.92 m, 2H), 1.69 (m, 15H), 1.29 (m, 61H), 0.890 (m, 24H).

Comparative Example 1 Preparation of 2,6-Bis (5- (6 - ([2,2 ': 5', 2 "-terthiophen] -5- 3,4- c ] pyrrole-1,4-dione-3-yl) thiophen-2-yl) -4,8-bis (octyloxyl) benzo [1,2- b : 4,5- b ' ] dithiophene Produce

([2,2 ': 5', 2 "-terthiophen] -5-yl) -6- (5-bromothiophen-2-yl) -2,5-bis 2-ethylhexyl) pyrrolo [3,4- c ] pyrrole-1,4-dione (161mg, 0.21mmol) and 2,6-bis (trimethyltin) -4,8- bis (octyloxy) benzo [1,2- b : 4,5- b '] dithiophene (77 mg, 0.1 mmol) was added thereto, and 10 mL of toluene and 1 mL of N, N-dimethylformamide were added thereto. Tetrakis (triphenylphosphine) palladium (0) (6 mg) was added thereto, followed by stirring at 110 ^° C for 24 hours. After completion of the reaction, methanol was added, filtered, and purified by column chromatography (chloroform) to obtain a deep green solid, which was dissolved in 100 mL of methanol, sonicated for 10 minutes, and filtered. The resulting solid was washed with excess methanol and dried under vacuum at 50 ^° C for 24 hours to give the title compound as a dark green solid, 146 mg (80% yield).

^{1 H NMR (300 MHz, CDCl} 3): δ (ppm) 8.98 (4H), 7.34 (2H), 7.24 (2H), 7.20 (2H), 7.13 (4H), 7.05 (2H), 6.98 (4H), 4.27 (4H), 4.01 (8H), 1.94 (8H), 1.64 (4H), 1.38 (48H), 0.94 (30H).

[Example 17] Fabrication of organic optoelectronic devices

Using a single-molecule organic semiconductor compound prepared in Example 14 as an electron donor and, C ₇₁ -PCBM but the use as an electron acceptor, and the mixing ratio of 1: 1 mixture of the optically active layer material prepared by a 1-chloronaphtalene 0.3 weight ratio The photoactive layer material was dissolved in a chloroform solvent containing a vol% at a weight ratio of 1.5% to prepare a photoactive layer solution.

The photoactive layer solution prepared above was filtered through a 0.45 μm filter on an ITO glass substrate into which PEDOT (poly (3,4-ethylenedioxythiophene) layer (40 to 50 nm) was introduced in an argon atmosphere in a glove box, (0.1 Å / s) and 100 nm (0.1 Å / s) of aluminum in a vacuum chamber with a vacuum of 1 × 10 ^-6 torr, followed by drying for 2 hours. A / s) were successively thermally deposited to fabricate an organic optoelectronic device. The fabricated organic optoelectronic device was confirmed to have JV characteristics in an artificial light simulator under the condition of 100 mA / cm ² (AM 1.5G) Respectively.

[Example 18] Fabrication of organic optoelectronic device

Example 17 was prepared in the same manner as in Example 17, except that the monomolecular organic semiconductor compound prepared in Example 15 was used instead of the monomolecular organic semiconductor compound prepared in Example 14, and the characteristics of the prepared organic optoelectronic device Are shown in Table 1 below.

[Example 19] Fabrication of organic optoelectronic device

Example 17 was prepared in the same manner as in Example 17, except that the monomolecular organic semiconductor compound prepared in Example 16 was used in place of the monomolecular organic semiconductor compound prepared in Example 14. The properties of the produced organic optoelectronic device Are shown in Table 1 below.

[Comparative Example 2] Production of organic optoelectronic device

Example 17 was prepared in the same manner as in Example 17, except that the monomolecular organic semiconductor compound prepared in Comparative Example 1 was used in place of the monomolecular organic semiconductor compound prepared in Example 14. The properties of the prepared organic optoelectronic device Are shown in Table 1 below.

Light development voltage
(Voc)
[V] Short circuit current density (Jsc)
[mA / cm ² ] Phil Fetcher
(FF) Energy conversion efficiency
[%] Example 17 0.68 11.97 0.47 3.57 Example 18 0.61 5.36 0.53 1.71 Example 19 0.90 8.46 0.46 3.54 Comparative Example 2 0.63 2.39 0.45 0.90

As shown in Table 1, the organic optoelectronic device containing the monomolecular organic semiconductor compound of the present invention has remarkably improved efficiency due to an increase in the current density and the filter factor as compared with the device of Comparative Example 1. [

The improvement in the characteristics of the organic electronic device comprising the monomolecular organic semiconductor compound of the present invention in comparison with the device of the comparative example having symmetrical substituents is due to the structural characteristics of the monomolecular organic semiconductor compound of the present invention having an asymmetric substituent .

Claims (10)

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

(3)

[In the above formulas (2) and (3)
Z is S;
R ¹ is (C ¹ -C 20) alkyl or (C 3 -C 20) heteroaryl;
R ² is (C 1 -C 20) alkyl;
R ³ to R ⁶ and R ¹¹ are independently of each other hydrogen or a (C 1 -C 20) alkyl group;
A ² , A ³ , B ² and B ³ are, independently of one another, (C3-C20) heteroarylene;
R ⁷ or R ⁸ independently of one another are hydrogen or

;
l, m, p and q are integers of 0 to 3;
R 'is hydrogen or (C1-C20) alkyl;
The R group or a heteroaryl group, the alkyl of R ^{2 1,} and A ² to A ^3, and Heteroarylene of B ² to B ³ is (C1-C20) alkyl, (C2-C20) alkenyl, (C2-C20) alkynyl, (C1-C20) alkoxy, an amino group, a hydroxyl group, a halogen group, between An amino group, an amino group, an amino group, an amino group, an amino group, an amino group, an amino group, an anion group, a nitro group, a trifluoromethyl group, and a silyl group. Reacting a compound represented by the following formula (4) with a compound represented by the following formula (5) to produce an organic semiconductor compound represented by the following formula (1).
[Chemical Formula 1]

[Chemical Formula 4]

[Chemical Formula 5]

[In the above formulas (1), (4) and (5)
Z is S;
R ¹ is (C ¹ -C 20) alkyl or (C 3 -C 20) heteroaryl;
R ² is (C 1 -C 20) alkyl,
R ⁷ or R ⁸ independently of one another are hydrogen or

;
R 'is hydrogen or (C1-C20) alkyl;
A ¹ to A ³ and B ¹ to B ³ independently of one another are (C3-C20) heteroarylene,
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 ⁵¹ ) (R ⁵² ) (R ⁵³ ), R ⁵¹ to R ⁵³ are (C1-C10) alkyl;
X is halogen;
The R group or a heteroaryl group, the alkyl of R ^{2 1,} and A ¹ to A ^3, and The heteroarylene of B ¹ to B ³ is selected from the group consisting of (C ¹ -C 20) alkyl, (C 2 -C 20) alkenyl, (C 2 -C 20) alkynyl, An amino group, an amino group, an amino group, an amino group, an amino group, an amino group, an amino group, an anion group, a nitro group, a trifluoromethyl group, and a silyl group. Reacting a compound represented by the following formula (4) with a compound represented by the following formula (5-1) to prepare a compound represented by the following formula (5-2), reacting the compound represented by the following formula (5-2) 1. A method for producing an organic semiconductor compound, comprising:
[Chemical Formula 1]

[Chemical Formula 4]

[Formula 5-1]

[Formula 5-2]

[Formula 5-3]
R ^7-1 -H
[In the formulas (1), (4) and (5-1) to (5-3)
Z is S;
R ¹ is (C ¹ -C 20) alkyl or (C 3 -C 20) heteroaryl;
R ² is (C 1 -C 20) alkyl,
R ⁷ or R ⁸ independently of one another

;
R 'is hydrogen or (C1-C20) alkyl;
R ^7-1 is

;
A ¹ to A ³ and B ¹ to B ³ independently of one another are (C3-C20) heteroarylene,
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 ⁵¹ ) (R ⁵² ) (R ⁵³ ), R ⁵¹ to R ⁵³ are (C1-C10) alkyl;
X is halogen;
The R group or a heteroaryl group, the alkyl of R ^{2 1,} and A ¹ to A ^3, and The heteroarylene of B ¹ to B ³ is selected from the group consisting of (C ¹ -C 20) alkyl, (C 2 -C 20) alkenyl, (C 2 -C 20) alkynyl, (C 1 -C 20) alkoxy, A hydroxyl group, a halogen group, a cyano group, a nitro group, a trifluoromethyl group, and a silyl group. 8. The method according to claim 6 or 7,
Wherein the compound of Formula 4 is prepared by reacting a compound of Formula 6 with a compound of Formula 7 or Formula 8.
[Chemical Formula 6]

(7)
(X ¹ ) Sn (R ⁵¹ ) (R ⁵² ) (R ⁵³ )
[Chemical Formula 8]
( ^R57 ) ( ^R56 ) ( ^R56 ) Sn-Sn ( ^R51 ) ( ^R52 ) ( ^R53 )
[In the above Chemical Formulas 6 to 8,
Z is S;
R ¹ is (C ¹ -C 20) alkyl or (C 3 -C 20) heteroaryl;
R ² is (C 1 -C 20) alkyl,
X ¹ is halogen;
R ⁵¹ - R ⁵⁶ is Independently of one another are (C1-C10) alkyl;
Alkyl or heteroaryl, and alkyl of R ² of the R ¹ is a (C1-C20) alkyl, (C2-C20) alkenyl, (C2-C20) alkynyl, (C1-C20) alkoxy, an amino group, a hydroxyl group , A halogen group, a cyano group, a nitro group, a trifluoromethyl group, and a silyl group. 8. The method according to claim 6 or 7,
(6) is prepared by reacting a compound represented by the following formula (9) with the following formula (10) And
And reacting the compound of formula (11) with a compound of formula (12) to produce the compound of formula (6).
[Chemical Formula 9]

[Chemical formula 10]
R ¹ MX ²
(11)

[Chemical Formula 12]
R ² X ³
[In the above formulas (9) to (12)
Z is S;
R ¹ is (C ¹ -C 20) alkyl or (C 3 -C 20) heteroaryl;
R ² is (C 1 -C 20) alkyl,
M is an alkaline earth metal;
X ² or X ³ is halogen;
The alkyl or heteroaryl of R ¹ and the alkyl of R ² may be further substituted with one or more of halogen, (C 1 -C 10) alkyl, (C 1 -C 10) alkoxy, amino, hydroxy or nitro. An organic semiconductor device comprising an organic semiconductor compound according to claim 5.