KR101807870B1 - Novel organic semiconductor compound and organic electronic device using them - Google Patents

Novel organic semiconductor compound and organic electronic device using them Download PDF

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KR101807870B1
KR101807870B1 KR1020150184735A KR20150184735A KR101807870B1 KR 101807870 B1 KR101807870 B1 KR 101807870B1 KR 1020150184735 A KR1020150184735 A KR 1020150184735A KR 20150184735 A KR20150184735 A KR 20150184735A KR 101807870 B1 KR101807870 B1 KR 101807870B1
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문상진
이상규
이종철
신원석
송창은
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한국화학연구원
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
    • C07D407/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems
    • H01L51/0071—
    • H01L51/0073—
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

The present invention provides a novel monomolecular organic semiconductor compound and an organic electronic device employing the same. The monomolecular organic semiconductor compound of the present invention includes two or more benzodithiophene skeletons and has a high molecular weight, And the organic electronic device employing the organic electronic device has high efficiency.

Description

TECHNICAL FIELD [0001] The present invention relates to a novel organic semiconductor compound and an organic electronic device using the organic semiconductor compound.

The present invention relates to a novel organic semiconductor compound, a method for producing the same, and an organic electronic device including the organic semiconductor compound. More particularly, the present invention relates to a novel organic semiconductor compound having at least two benzodithiophene derivatives introduced therein, Device.

Organic thin film solar cell is a photoactive layer that uses donor material and acceptor material together. It is a thin film with thickness less than several hundred nm and relatively inexpensive photoactive layer, Recently, many researches have been made on the advantage of being able to fabricate a flexible device that can bend freely.

The efficiency of the organic thin film solar cell is determined by the open-circuit voltage (Voc), the short-circuit current (Jsc), and the fill factor (FF). The open-circuit voltage is determined by the energy levels of the donor material that absorbs the light and the acceptor that accepts the excited electrons, and the short-circuit current is deeply related to the absorption spectrum of the donor material that absorbs the light. The fill factor is determined by the morphology of the mixed film of the donor material and the acceptor material. In order to increase the efficiency of the organic thin film solar cell, it is required to study the optical characteristics of the donor material due to the change of the donor material and the electrooptical characteristics of the photovoltaic device.

Donor materials used in organic thin film solar cells can be distinguished from polymers and monomolecules. Single molecules can increase purity compared to polymers, and are easier to reproduce than polymers and have high hole mobility However, it is disadvantageous in that the film factor is worse than that of the polymer due to the problem that the film is inferior to the polymer in the film formation. Currently, the structure of monomolecules that increase the high efficiency is generally studied as ADA type which is in the form of electron acceptor (A) - electron donor (D) - electron acceptor (A), but it can improve the fill factor by increasing hole mobility A new type of monomolecular structure is required.

International Patent Publication No. WO 2010-058692

The present invention provides an organic semiconductor compound having a monomolecular structure with high efficiency by improving the fill factor.

The present invention also provides a method for producing a novel organic semiconductor compound of the present invention and an organic electronic device employing the novel organic semiconductor compound of the present invention.

The present invention provides an organic semiconductor compound represented by the following general formula (1), which has a high fill factor even though it is a single molecule.

[Chemical Formula 1]

Figure 112015126254965-pat00001

[In the above formula (1)

Z 1 and Z 2 are independently of each other O, S, or Se;

R 1 and R 2 are independently of each other hydrogen, halogen, (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy, (C 6 -C 20) aryl or (C 3 -C 20) heteroaryl;

The A 1 group A 3 and B 1 to B 3 are each independently (C6-C20) arylene or (C3-C20) heteroarylene,

R 3 or R 4 independently from each other are hydrogen, (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl, (C 3 -C 20) heterocycloalkyl, (C 6 -C 20) aryl, (C6-C20) ar (C1-C10) alkyl or

Figure 112015126254965-pat00002
Y 1 and Y 2 are independently of each other O, S, Se or CR a R b , and R a and R b is independently from each other cyano, (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy or (C 1 -C 20) alkoxycarbonyl and R 'is (C 1 -C 20) alkyl;

n or o is an integer from 1 to 3;

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

x is an integer from 2 to 5;

The alkyl, alkoxy, aryl or heteroaryl of R 1 and R 2 , the arylene or heteroarylene of A 1 and A 1 to A 3 and B 1 to B 3 are independently selected from the group consisting of a (C 1 -C 20) alkyl group, a (C 2 -C 20) May be further substituted with one or more substituents selected from the group consisting of halogen, (C2-C20) alkynyl, (C1-C20) alkoxy, amino group, hydroxyl group, halogen group, cyano group, nitro group, trifluoromethyl group and silyl group .]

The novel organic semiconductor compound of the present invention includes two or more benzodithiophene skeletons to improve the pore-packing in the solid phase to minimize the phase transition, thereby enhancing the hole mobility and thereby improving the fill factor.

Therefore, the organic semiconductor compound having a monomolecular structure can be improved while maintaining the advantages of the organic semiconductor compound while improving the efficiency of the organic electronic device employing the same.

Preferably, in Formula 1 according to an embodiment of the present invention, Z 1 and Z 2 are S; R 1 and R 2 are, independently of each other, (C 6 -C 20) aryl or (C 3 -C 20) heteroaryl; The aryl or heteroaryl of R 1 and R 2 may be substituted with a substituent selected from the group consisting of a (C1-C20) alkyl group, a (C1-C20) alkoxy group, an amino group, a hydroxyl group, a halogen group, a cyano group, a nitro group, a trifluoromethyl group, May be further substituted with one or more substituents selected.

 Preferably, Formula 1 according to an embodiment of the present invention may be represented by Formula 2 below.

(2)

Figure 112015126254965-pat00003

[In the formula (2)

Z 1 and Z 2 are independently of each other O, S, or Se;

R 1 and R 2 are, independently of each other, (C3-C20) heteroaryl;

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

Y 1 and Y 2 independently of one another are O, S, Se or CR a R b , R a and R b is independently from each other a cyano, carboxyl group, (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy or (C 1 -C 20) alkoxycarbonyl;

R 'is (C1-C20) alkyl;

n or o is an integer from 1 to 3;

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

x is an integer from 2 to 5;

The heteroaryl of R 1 and R 2, the arylene or heteroarylene of A 1 -terminal A 3 and B 1 -B 3 may be substituted with a (C1-C20) alkyl group, a (C2-C20) Which may be further substituted with one or more substituents selected from the group consisting of halogen, (C1-C60) alkoxy, amino, hydroxyl, halogen, cyano, nitro, trifluoromethyl and silyl.

In formulas (1) and (2) according to an embodiment of the present invention, A 1 to A 3 and B 1 to B 3 may be (C3-C20) heteroarylene, and may be specifically selected from the following structures.

Figure 112015126254965-pat00004

[In the above formula,

Z is independently from each other O, S or Se;

D is, independently of each other O, S, N (R 51 ), C (R 52) (R 53) , or Si (R 54) (R 55 ), R 51 to R < 55 > is hydrogen or (C1-C20) alkyl;

R 11 to R 37 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;

R 41 to R 43 independently represent hydrogen, (C 1 -C 20) alkyl 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;

and c is an integer of 1 to 3.]

Preferably, Y 1 is S or O in formulas (1) and (2) according to an embodiment of the present invention; Y 2 is O or CR a R b , R a and R b are independently of each other a cyano, carboxyl group, (C 1 -C 20) alkyl or (C 1 -C 20) alkoxycarbonyl; R 1 and R 2 are each independently (C 3 -C 20) heteroaryl, and the heteroaryl of R 1 and R 2 may be further substituted with (C 1 -C 20) alkyl; A 1 to A 3 and B 1 to B 3 may be independently selected from the following structures.

Figure 112015126254965-pat00005

[In the above formula,

Z is independently from each other O, S or Se;

D is, independently of each other O, S, N (R 51 ), C (R 52) (R 53) , or Si (R 54) (R 55 ), R 51 to R < 55 > is hydrogen or (C1-C20) alkyl;

R 11 to R 21 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 20) alkyl;

a is an integer of 1 to 4;

and b is an integer of 1 to 2.]

Preferably, R 1 and R 2 in formula (2) according to an embodiment of the present invention may independently be heteroaryl having the following skeleton.

Figure 112015126254965-pat00006

[Wherein G 1 to G 2 are independently of each other S, O or N]

Specifically, the organic semiconductor compound according to an embodiment of the present invention may be selected from the following structures, but is not limited thereto.

Figure 112015126254965-pat00007

Figure 112015126254965-pat00008

Figure 112015126254965-pat00009

Figure 112015126254965-pat00010

Figure 112015126254965-pat00011

Figure 112015126254965-pat00012

Figure 112015126254965-pat00013

Figure 112015126254965-pat00014

The substituents comprising the "alkyl", "alkoxy", and other "alkyl" moieties described in the present invention as described in the present invention include both linear and branched forms and are those having 1 to 20 carbon atoms, preferably 1 to 15, Preferably 1 to 10 carbon atoms.

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.

The term " alkenyl ", alone or as part of another group described herein, means a straight, branched or cyclic hydrocarbon radical containing from 2 to 20 carbon atoms and at least one carbon to carbon double bond. More preferred alkenyl radicals are lower alkenyl radicals having from 2 to about 15 carbon atoms. The most preferred lower alkenyl radical is a radical having from 2 to about 10 carbon atoms. The alkenyl group may also be substituted at any available point of attachment. Examples of alkenyl radicals include ethenyl, propenyl, allyl, propenyl, butenyl, and 4-methylbutenyl. The terms alkenyl and lower alkenyl include cis and trans orientation, or alternatively, radicals having an E and Z orientation.

The term " alkynyl ", alone or as part of another group described herein, means a straight, branched or cyclic hydrocarbon radical containing from 2 to 20 carbon atoms and at least one carbon to carbon triple bond. More preferred alkynyl radicals are lower alkynyl radicals having from 2 to about 15 carbon atoms. Most preferred is a lower alkynyl radical having from 2 to about 10 carbon atoms. Examples of such radicals include propargyl, butynyl, and the like. The alkynyl group may also be substituted at any available attachment point.

The present invention also provides a process for preparing the novel organic semiconductor compounds of the present invention.

A method for preparing an organic semiconductor compound represented by the following formula (1) of the present invention comprises reacting a compound represented by the following formula (3) with a compound represented by the following formula (4) and a compound represented by the following formula (5) ; ≪ / RTI >

[Chemical Formula 1]

Figure 112015126254965-pat00015

(3)

Figure 112015126254965-pat00016

[Chemical Formula 4]

Figure 112015126254965-pat00017

[Chemical Formula 5]

Figure 112015126254965-pat00018

[In the above formulas (1), (3) and (4)

Z 1 and Z 2 are independently of each other O, S, or Se;

R 1 and R 2 are independently of each other hydrogen, halogen, (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy, (C 6 -C 20) aryl or (C 3 -C 20) heteroaryl;

The A 1 group A 3 and B 1 to B 3 are each independently (C6-C20) arylene or (C3-C20) heteroarylene,

R 3 or R 4 independently from each other are hydrogen, (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl, (C 3 -C 20) heterocycloalkyl, (C 6 -C 20) aryl, (C6-C20) aryl (C1-C10) alkyl;

n or o is an integer from 1 to 3;

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

x is an integer from 2 to 5;

T is Sn (R 61 ) (R 62 ) (R 63 ), R 61 to R 63 is (C1-C10) alkyl;

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

The alkyl, alkoxy, aryl or heteroaryl of R 1 and R 2 , the arylene or heteroarylene of A 1 and A 1 to A 3 and B 1 to B 3 are independently selected from the group consisting of a (C 1 -C 20) alkyl group, a (C 2 -C 20) May be further substituted with one or more substituents selected from the group consisting of halogen, (C2-C20) alkynyl, (C1-C20) alkoxy, amino group, hydroxyl group, halogen group, cyano group, nitro group, trifluoromethyl group and silyl group .]

The present invention also relates to a process for the preparation of a compound represented by the following formula (7) by reacting a compound represented by the following formula (3) with a compound represented by the following formula (6-1) and a compound represented by the following formula To prepare an organic semiconductor compound represented by the following formula (2).

(2)

Figure 112015126254965-pat00019

(3)

Figure 112015126254965-pat00020

[Formula 6-1]

Figure 112015126254965-pat00021

[Formula 6-2]

Figure 112015126254965-pat00022

(7)

Figure 112015126254965-pat00023

[Chemical Formula 8]

Figure 112015126254965-pat00024

[In the above Chemical Formulas 2, 3, 6-1, 6-2, 7 and 8,

Z 1 and Z 2 are independently of each other O, S, or Se;

R 1 and R 2 are, independently of each other, (C3-C20) heteroaryl;

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

Y 1 and Y 2 independently of one another are O, S, Se or CR a R b , R a and R b is independently from each other a cyano, carboxyl group, (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy or (C 1 -C 20) alkoxycarbonyl;

R 'is (C1-C20) alkyl;

n or o is an integer from 1 to 3;

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

x is an integer from 2 to 5;

T is Sn (R 61 ) (R 62 ) (R 63 ), R 61 to R 63 is (C1-C10) alkyl;

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

The heteroaryl of R 1 and R 2, the arylene or heteroarylene of A 1 -terminal A 3 and B 1 -B 3 may be substituted with a (C1-C20) alkyl group, a (C2-C20) Which may be further substituted with one or more substituents selected from the group consisting of halogen, (C1-C60) alkoxy, amino, hydroxyl, halogen, cyano, nitro, trifluoromethyl and silyl.

The compound of formula (3) according to an embodiment of the present invention may be prepared by reacting a compound of formula (9) with a compound of formula (10) or a compound of formula (11).

[Chemical Formula 9]

Figure 112015126254965-pat00025

[Chemical formula 10]

(X 3) Sn (R 61 ) (R 62) (R 63)

(11)

(R 64) (R 65) (R 66) Sn-Sn (R 61) (R 62) (R 63)

[In the above formulas (9) to (10)

Z 1 and Z 2 are independently of each other O, S, or Se;

R 1 and R 2 are independently of each other hydrogen, halogen, (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy, (C 6 -C 20) aryl or (C 3 -C 20) heteroaryl;

x is an integer from 2 to 5;

R 61 to R 66 independently from each other are (C 1 -C 20) alkyl;

X 3 is halogen;

The alkyl group, alkoxy, aryl or heteroaryl of R 1 and R 2 may be substituted with a substituent selected from the group consisting of a (C1-C20) alkyl group, (C2-C20) alkenyl, (C2- A halogen atom, a cyano group, a nitro group, a trifluoromethyl group, and a silyl group.

The formula (9) according to an embodiment of the present invention may be prepared by reacting a compound of the following formula (12) with a compound of the following formula (13).

[Chemical Formula 12]

Figure 112015126254965-pat00026

[Chemical Formula 13]

Figure 112015126254965-pat00027

[In the formulas (12) and (13)

Z 1 and Z 2 are independently of each other O, S, or Se;

R 1 and R 2 are independently of each other hydrogen, halogen, (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy, (C 6 -C 20) aryl or (C 3 -C 20) heteroaryl;

x is an integer from 2 to 5;

T 1 is Sn (R 71 ) (R 72 ) (R 73 ), and R 71 to R 73 is (C1-C10) alkyl;

when x is 2, A is hydrogen, and when x is 2 or more, A is T 1 ;

X < 4 > is halogen;

The alkyl, alkoxy, aryl or heteroaryl of R 1 and R 2 , the arylene or heteroarylene of A 1 and A 1 to A 3 and B 1 to B 3 are independently selected from the group consisting of a (C 1 -C 20) alkyl group, a (C 2 -C 20) May be further substituted with one or more substituents selected from the group consisting of halogen, (C2-C20) alkynyl, (C1-C20) alkoxy, amino group, hydroxyl group, halogen group, cyano group, nitro group, trifluoromethyl group and silyl group .]

The solvent used in the process for preparing an organic semiconductor compound of the present invention may be any conventional organic solvent, but may be chlorobenzene, toluene, dichloromethane (DCM), dichloroethane (DCE), toluene (Toluene) (1) selected from the group consisting of MeCN, Nitromethan, tetrahydrofuran (THF), N, N -dimethylformamide (DMF), acetic acid and N, N -dimethylacetamide It is preferable to use more than species.

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 electronic device containing the organic semiconductor compound according to the present invention.

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

The organic semiconductor compound of the present invention can provide a compound having a higher purity than that of a polymer as a single molecule, and thus the electrochemical characteristics of the organic electronic device employing the organic semiconductor compound can be improved and an organic electronic device having excellent efficiency can be manufactured.

In addition, the organic semiconductor compound of the present invention improves pi-pile stacking in a solid phase to enhance hole mobility, thereby improving a low p factor value of a monomolecular organic semiconductor compound.

Further, the organic semiconductor compound of the present invention can be easily applied to a solution process by introducing various functional groups into benzodithiophene as a central skeleton to improve solubility.

Therefore, the organic electronic device containing the novel organic semiconductor compound of the present invention can have high efficiency.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, it should be understood that the following examples are for illustrative purposes only and are not intended to limit the scope of the invention. .

[Example 1] Production of monomolecular organic semiconductor compound 1

Synthesis of 2-Bromo-4,8-bis (5- (2-ethylhexyl) thiophene-2-yl) benzo [1,2-b: 4,5-b '] dithiophene

Figure 112015126254965-pat00028

Synthesis of 4- (5- (2-ethylhexyl) thiophen-2-yl) -8- ] Dithiophene (2.00 g, 3.25 mmol) was dissolved in 30 mL of THF, and the temperature was lowered to -78 ° C to add n-butyllithium slowly. After stirring at -78 ° C for 1 hour, the mixture was warmed to room temperature, stirred for 1 hour, cooled again to -78 ° C, and carbon tetrabromide (1.21 mL, 3.79 mmol) was added. After further stirring at room temperature for 15 hours, the reaction was terminated with cold water, and water was removed with MgSO 4. The solvent was distilled off under reduced pressure and then separated by column to obtain 1.69 g (74%) of the title compound.

1 H-NMR (300 MHz, CDCl 3): δ 7.61 (d, 1H), 7.60 (s, 1H), 7.47 (d, 2H), 7.25 (d, 1H), 6.88 (d, 2H), 2.86 ( d, 4H), 1.69 (m, 2H), 1.45-1.33 (m, 16H), 0.94-0.88 (m, 12H).

(8- (5- (2-Ethylhexyl) thiophene-2-yl) -4- (5- (2- ethylpentyl) thiophene-2-yl) benzo [1,2- b, 4,5- b '] dithiophene -2-yl) trimethylstannane

Figure 112015126254965-pat00029

Synthesis of 4- (5- (2-ethylhexyl) thiophen-2-yl) -8- ] Dithiophene (2.00 g, 3.25 mmol) was dissolved in 30 mL of THF, and the temperature was lowered to -78 ° C to add n-butyllithium slowly. After stirring at -78 ° C for 1 hour, the mixture was stirred at room temperature for 1 hour, then cooled to -78 ° C and trimethyltin chloride (3.50 mL, 3.50 mmol) was added. After stirring for 15 hours at room temperature, the reaction was terminated with cold water. The reaction mixture was extracted with diethyl ether, and water was removed with MgSO 4. The solvent was distilled off under reduced pressure to obtain 2.16 g (81%) of the title compound.

1 H-NMR (300 MHz, CDCl 3): δ 7.68 (s, 1H), 7.64 (d, 1H), 7.43 (t, 1H), 7.3 (d, 2H), 6.89 (d, 2H), 2.85 ( d, 4H), 1.68 (m, 2H), 1.46-1.34 (m, 16H), 0.94-0.88 (m, 12H), 0.43 (t, 9H).

Synthesis of 4,4'8,8'-Tetrakis (5- (2-ethylhexyl) thiophen-2-yl) -2,2'-bibenzo [1,2- b: 4,5-b '] dithiophene.

Figure 112015126254965-pat00030

(1.0 g, 1.5 mmol) and (8-bromo-4,8-bis (5- (2-ethylhexyl) thiophene- (5- (2-ethylhexyl) thiophene-2-yl) -4- (5- (2- ethylpentyl) thiophen- Pd 2 (dba) 3 (0.068 g, 0.075 mmol) and tri (ortho-tolyl) phosphine (0.045 g, 0.15 mmol) were added to a toluene solution of triethylstannane (1.2 g, 1.7 mmol) Lt ; 0 > C. After the reaction was terminated with water, the reaction mixture was extracted with dichloromethane, and water was removed with MgSO 4. The solvent was distilled off under reduced pressure and then separated by column to obtain 1.2 g (71%) of the title compound.

1 H-NMR (300 MHz, CDCl 3): δ 7.76 (s, 2H), 7.61 (d, 2H), 7.46 (d, 2H), 7.29 (d, 4H), 6.9 (d, 4H), 2.87 ( d, 8H), 1.69 (m, 4H), 1.48-1.32 (m, 32H), 0.98-0.89 (m, 24H).

(4,4'8,8'-Tetrakis (5- (2-ethylhexyl) thiophen-2-yl) - [2,2'-bibenzo [1,2- b: 4,5- b '] dithiophene] 6,6'-dily) bis (trimethylstannane).

Figure 112015126254965-pat00031

4, 4'8,8'-Tetrakis (5- (2-ethylhexyl) thiophen-2-yl) -2,2'- bibenzo [1,2- b: 4,5- b '] dithiophene (1.0 g, 0.88 mmol) was dissolved in 25 mL of THF, and the temperature was lowered to -78 ° C to slowly add n-butyllithium. After stirring at -78 ° C for 1 hour, the mixture was stirred at room temperature for 1 hour, then cooled to -78 ° C and trimethyltin chloride (2.0 mL, 2.0 mmol) was added. After further stirring at room temperature for 15 hours, the reaction was terminated with cold water, extracted with diethyl ether, and water was removed with MgSO 4. The solvent was distilled off under reduced pressure to obtain 0.65 g (51%) of the title compound.

1 H-NMR (300 MHz, CDCl 3 ):? 7.74 (s, 2H), 7.64 (s, 2H), 7.30 m, 4H), 1.48-1.33 (m, 32H), 0.98-0.89 (m, 24H), 0.39 (t, 18H).

5 '', 5 '' - (4,4 ', 8,8'-tetrakis (5- (2-ethylhexyl) thiophen-2-yl) - [2,2'- b: 4,5-b '] dithiophene] -6,6'-diyl) bis (3,3'-dioctyl- [2,2': 5 ', 2 "-terthiophene] -5-carbaldehyde) Synthesis .

Figure 112015126254965-pat00032

(4,4 ', 8,8'-Tetrakis (5- (2-ethylhexyl) thiophen-2-yl) - [2,2'- bibenzo [1,2- b: 4,5- b'] dithiophene] -Bromo-3 ', 3 "4-trihexyl-2,2', 5 ', 2" -trithiophene-5-carbaldehyde (0.200 g, 0.137 mmol) (0.200 g, 0.34 mmol) of dissolved toluene: DMF mixture solution (5 mL, 4: 1, v / v) to put the Pd (PPh 3) 4 (0.017 g, 0.013 mmol) under an argon atmosphere for 16 hours 110 o The reaction was terminated with water and water was removed with MgSO 4 , and then the solvent was distilled off under reduced pressure and then separated by column to obtain 1.9 g (66%) of the title compound.

1 H-NMR (300 MHz, CDCl 3): δ 9.81 (s, 2H), 7.66 (s, 2H), 7.57 (s, 4H), 7.30 (t, 4H), 7.25 (d, 2H), 7.09 ( (d, 2H), 7.07 (s, 2H), 6.94 (d, 4H), 2.91 (m, 16H), 1.75-1.63 (m, 12H), 1.48-1.35 32H), 0.99 (t, 12H), 0.95-0.91 (m, 12H), 0.87 (t, 12H).

Preparation of monomolecular organic semiconductor compound 1

Figure 112015126254965-pat00033

5 '', 5 '' - (4,4 ', 8,8'-Tetrakis (5- (2-ethylhexyl) thiophen-2-yl) - [2,2'- b: 4,5-b '] dithiophene] -6,6'-diyl) bis (3,3'-dioctyl- [2,2': 5 ', 2'-terthiophene] -5-carbaldehyde) 0.220 g, 0.100 mmol), 3 -ethylrhodanine (0.083 g, 0.50 mmol), NH 4 OAc (0.084 mg, 1.1 mmol) the dissolved chloro-benzene was heated under reflux for 13 hours acetic acid mixture solution was raised in an argon atmosphere, cooled to room temperature . When the reaction solution was dropped into a methanol solvent, a precipitate was formed and the resulting precipitate was filtered, again dissolved with a minimum amount of chloroform, and precipitated again with methanol. The organic layer was separated by column to obtain 0.160 g (63%) of the title compound as an organic semiconductor compound 1.

1 H-NMR (300 MHz, CDCl 3): δ 7.49 (s, 2H), 7.41 (s, 2H), 7.30 (d, 2H), 7.28 (d, 2H), 7.10 (s, 2H), 7.08 ( 2H), 6.97 (d, 2H), 6.94 (d, 4H), 6.91 (s, 2H), 4.15 , 4H), 1.80-1.74 (m, 4H), 1.66-1.59 (m, 8H), 1.52-1.50 (m, 10H), 1.43-1.39 (t, 12H), 0.96 (t, 12H), 0.88 (t, 12H).

[Example 2] Production of monomolecular organic semiconductor compound 2

4,4 ', 4 ", 8,8', 8" -hexakis (5- (2-ethylhexyl) thiophen-2-yl) -2,2 ' 2-b: 4,5-b '] dithiophene.

Figure 112015126254965-pat00034

(2-ethylhexyl) thiophene-2-yl) benzo [1,2-b: 4,5-b '] dithiophene (2.0 g, 3.0 mmol) Bis (5- (2-ethylhexyl) thiophen-2-yl) benzo [1,2-b: 4,5-b '] dithiophene-2,6-diyl bis (trimethylstannane) Pd 2 (dba) 3 (0.068 g, 0.075 mmol) and tri (ortho-tolyl) phosphine (0.045 g, 0.15 mmol) were added to the toluene solution in an argon atmosphere and the mixture was stirred at 110 ° C for 24 hours. After the reaction was terminated with water, the reaction mixture was extracted with dichloromethane, and water was removed with MgSO 4. The solvent was distilled off under reduced pressure and then separated by column to obtain 1.2 g (71%) of the title compound.

1 H-NMR (300 MHz, CDCl 3): δ 7.75 (s, 2H), 7.71 (s, 2H), 7.60 (d, 2H), 7.45 (d, 2H), 7.30 (d, 6H), 6.93 ( m, 6H), 2.90 (m, 12H), 1.74-1.63 (m, 6H), 1.48-1.33 (m, 48H), 0.98-0.89 (m, 36H).

(4,4 ', 4 ", 8,8', 8" -hexakis (5- (2-ethylhexyl) thiophen-2-yl) - [2,2 ' 1,2-b: 4,5-b '] dithiophene] -6,6' '- diyl) bis (trimethylstannane).

Figure 112015126254965-pat00035

4,4 ', 4 ", 8,8', 8" -hexakis (5- (2-ethylhexyl) thiophen-2-yl) -2,2 ' 2-b: 4,5-b '] dithiophene (0.70 g, 0.40 mmol) was dissolved in 25 mL of THF and the temperature was lowered to -78 ° C to slowly add n-butyllithium. After stirring at -78 ° C for 1 hour, the reaction mixture was warmed to room temperature and stirred for 1 hour, then cooled to -78 ° C, and then trimethyltin chloride (0.96 mL, 0.96 mmol) was added. After stirring for 15 hours at room temperature, the reaction was terminated with cold water. The reaction mixture was extracted with diethyl ether, and water was removed with MgSO 4. The solvent was distilled off under reduced pressure to obtain 0.68 g (82%) of the title compound.

1 H-NMR (300 MHz, CDCl 3): δ 7.76 (s, 2H), 7.71 (s, 2H), 7.64 (t, 2H), 7.31 (m, 6H), 6.92 (m, 6H), 2.89 ( d, 12H), 1.72 (m, 6H), 1.54-1.33 (m, 48H), 0.99-0.89 (m, 36H), 0.39 (t, 18H).

5 '', 5 '' - (4,4 ', 4' ', 8,8', 8 '' - hexakis (5- (2-ethylhexyl) thiophen- Bis (3,3'-dioctyl- [2,2 '] bipyridyl) -6,6', 2'- : 5 ', 2 "-terthiophene] -5-carbaldehyde).

Figure 112015126254965-pat00036

(4,4 ', 4 ", 8,8', 8" -hexakis (5- (2-ethylhexyl) thiophen-2-yl) - [2,2 ' Bis (trimethylstannane) (0.426 g, 0.200 mmol) and 5 "-bromo-3 ', 3" 4-trihexyl- Pd (PPh 3 ) was added to a toluene: DMF mixed solution (5 mL, 4: 1, v / v) in which 2,2 ', 5', 2 "-trithiophene-5-carbaldehyde (0.235 g, 0.400 mmol) ) 4 (0.023 g, 0.020 mmol) was added thereto and stirred for 16 hours at 110 ° C. The reaction was terminated by water and water was removed with MgSO 4 , the solvent was distilled off under reduced pressure, and the obtained product was separated by column to obtain 0.38 g %).

1 H-NMR (300 MHz, CDCl 3): δ 9.76 (s, 2H), 7.51 (s, 2H), 7.48 (s, 4H), 7.41 (s, 2H), 7.29 (t, 6H), 7.13 ( (d, 2H), 6.96 (d, 2H), 6.92 (d, 6H), 6.88 , 6H), 1.64 (m, 8H), 1.51-1.38 (m, 48H), 1.33-1.28 (m, 40H), 1.03 (t, 18H), 0.98-0.92 , 12H).

Preparation of monomolecular organic semiconductor compound 2

Figure 112015126254965-pat00037

5 '', 5 '' - (4,4 ', 8,8'-Tetrakis (5- (2-ethylhexyl) thiophen-2-yl) - [2,2'- b: 4,5-b '] dithiophene] -6,6'-diyl) bis (3,3'-dioctyl- [2,2': 5 ', 2'-terthiophene] -5-carbaldehyde) 0.30 g, 0.11 mmol), 3 -ethylrhodanine (0.088 g, 0.55 mmol), NH 4 OAc (0.077 mg, 1.1 mmol) the dissolved chloro-benzene was heated under reflux for 13 hours acetic acid mixture solution was raised in an argon atmosphere, cooled to room temperature . When the reaction solution was dropped into a methanol solvent, a precipitate was formed and the resulting precipitate was filtered, again dissolved with a minimum amount of chloroform, and precipitated again with methanol. Column separation afforded 0.160 g (63%) of the monomolecular organic semiconductor compound 2, the title compound.

1 H-NMR (300 MHz, CDCl 3): δ 7.57 (s, 2H), 7.37 (d, 4H), 7.30 (s, 2H), 7.28-7.25 (m, 6H), 7.05 (d, 4H), 2H), 4.15 (q, 4H), 2.96 (d, 12H), 2.67 (t, 4H), 2.58 (t, 4H), 1.82-1.78 (m, 6H), 1.61-1.58 (m, 8H), 1.51-1.41 (m, 48H), 1.35-1.25 (m, 46H), 1.08-1.02 (m, 18H), 0.99-0.93 m, 12H).

[Example 3] Production of monomolecular organic semiconductor compound 3

Figure 112015126254965-pat00038

2-Bromo-3-hexylthiophene ( 20g, 80.90mmol) and Ni (dppp) 2 Cl 2 ( 2.192, 4.104mmol) was dissolved the 2-Ethylhexylmagnesium bromide (113.2 ml, 113.2 mmol) to 0 o C condition here in 300mL THF Lt; / RTI > The reaction solution was heated to 70 ° C. and allowed to react for 2 hours. The reaction solution was cooled to room temperature, and 10% HCl (50 ml) was added thereto, followed by stirring for 30 minutes. The mixed solution was extracted with diethyl ether (100 x 3), concentrated, and then distilled to obtain the title compound (2) as yellow. (13.1 g, 57.7%)

1 H-NMR (300MHz, CDCl 3): δ 7.02-7.01 (d, 1H, J = 5.09Hz), 6.81-6.79 (d, 1H, J = 5.09Hz), 2.65-2.62 (d, 2H, J = (M, 3H), 1.39-1.23 (m, 14H), 0.90-0.85 (m, 9H)

Figure 112015126254965-pat00039

The solution of compound 2 (10.2 g, 36.3 mmol) in 300 mL of THF was cooled to -78 ° C. and butyl lithium (18.1 mL, 45.4 mmol) was added. The reaction solution was stirred at -78 ° C. for 30 minutes, After stirring for a time, the reaction temperature was lowered again to -78 ° C, and then Compound 3 (2 g, 9.9 mmol) was added. The reaction solution was stirred at room temperature for 12 hours, then SnCl 2 .2H 2 O (10.25 g, 45.45 mmol) and 10% HCl (100 ml) were added and stirred for 4 hours. The mixed solution was extracted with CH 2 Cl 2 (100 ml × 3), concentrated, and purified by column chromatography (hexane) to obtain the title compound (4) (2.5 gm, 48.1%) as a pale green solid.

1 H-NMR (300MHz, CDCl 3): δ 7.68-7.66 (d, 2H, J = 5.63), 7.44-7.42 (d, 2H, J = 5.63), 7.21 (s, 2H), 2.75-2.73 (d , 4H, J = 7.12 Hz), 2.62-2.57 (t, 4H, J = 15.56 Hz), 1.67-1.62 (m, 6H) 1.46-1.25 (m, 28H), 0.96-0.88

Figure 112015126254965-pat00040

A solution of Compound 4 (0.9 g, 1.2 mmol) in 40 mL of THF was cooled to -78 째 C, and butyl lithium (0.52 mL, 1.3 mmol) was added. The mixture was stirred at -78 째 C for 30 minutes and at room temperature for 1 hour. The reaction solution was cooled to -78 ° C, and CBr 4 (0.839 g, 2.53 mmol) was added thereto. The mixture was stirred at room temperature for 1 hour and then water was added thereto and extracted with hexane. The extracted solution was concentrated and purified by column chromatography (hexane) to obtain Compound 5 (1.521 g, 80.01%).

1 H-NMR (300MHz, CDCl 3): δ 7.66-7.64 (d, 2H, J = 5.97Hz), 7.64 (s, 1H) 7.47-7.45 (d, 1H, J = 5.69Hz), 7.17 (s, 2H), 2.75-2.73 (d, 4H, J = 6.99Hz), 2.61-2.57 (m, 4H), 1.68-1.60 (m, 6H), 1.45-1.26 18H).

Figure 112015126254965-pat00041

A solution of Compound 4 (1.4 g, 1.87 mmol) in 40 mL of THF was cooled to -78 째 C, and butyl lithium (0.824 mL, 2.06 mmol) was added slowly and the mixture was stirred at -78 째 C for 30 minutes and then at room temperature for 30 minutes. The reaction solution was cooled again to -78 ° C, and (CH 3 ) 3 SnCl (2.06 ml, 2.06 mmol) was slowly added thereto, followed by stirring at room temperature for 12 hours. Water was added to the reaction solution, extracted with hexane and concentrated to obtain the title compound (1.67 g, 98.39%) as a yellow liquid, which was used for the next step without further purification.

Figure 112015126254965-pat00042

Compound 5 (1.5 g, 1.81 mmol) and compound 6 (1.652 g, 1.81 mmol) were dissolved in a mixed solvent of toluene and DMF (25 ml, 9: 1), Pd (0) (0.104 g, 0.09 mmol) The mixture was stirred for 30 minutes and refluxed for 16 hours. Water was added to the reaction solution, and the mixture was extracted with CH 2 Cl 2 (70 ml × 3), concentrated, and purified by column chromatography (hexane) to obtain Compound 7 as a yellow solid (1.9 g, 72.3%).

1 H-NMR (300MHz, CDCl 3): δ 7.82 (s, 2H), 7.63-7.61 (d, 2H, J = 5.88Hz), 7.44-7.42 (d, 2H, J = 5.55Hz), 7.23 (s 2H, 7.20 (s, 2H), 2.77-2.74 (m, 8H), 2.63-2.58 (m, 8H), 1.66-1.65 (m, 12H), 1.43-1.32 m, 36H).

Figure 112015126254965-pat00043

A solution of Compound 7 (1.950 g, 1.3 mmol) in 40 mL of THF was cooled to -78 ° C and butyl lithium (1.09 mL, 2.74 mmol) was slowly added thereto. The mixture was stirred at -78 ° C for 30 minutes and at room temperature for 30 minutes. The reaction solution was cooled again to -78 ° C, and (CH 3 ) 3 SnCl (2.87 ml, 2.87 mmol) was slowly added thereto, followed by stirring at room temperature for 12 hours. Water was added to the reaction solution, extracted with hexane and concentrated to obtain a pale brown liquid compound 8 (2.3 g, 97.8%), which was used for the next step reaction without further purification.

1 H-NMR (300MHz, CDCl 3): δ 7.8 (s, 2H), 7.67 (s, 2H), 7.22-7.21 (d, 4H, J = 2.01Hz), 2.77-2.75 (d, 8H, J = (M, 8H), 1.71-1.62 (m, 12H), 1.49-1.26 (m, 56H), 0.97-0.86 (m, 36H), 0.47-0.33 (t, 18H).

Figure 112015126254965-pat00044

Compound (8) (2.324 g, 1.27 mmol) and compound 9 (1.327 g, 2.55 mmol) were dissolved in a mixed solvent of toluene and DMF (60 ml, 9: 1), Pd (0) (73 mg, 0.06 mmol) After stirring for a minute, the mixture was refluxed for 16 hours. Water was added to the reaction solution, and the mixture was extracted with CH 2 Cl 2 (100 ml × 3), concentrated and purified by column chromatography (hexane: CH 2 Cl 2 (1: 1)) to obtain Compound 7 as a red solid (0.71 g, 56.4% ).

1 H-NMR (300MHz, CDCl 3): δ 9.88 (s, 2H), 7.77 (s, 2H), 7.71-7.70 (d, 2H, J = 3.71Hz), 7.62 (s, 2H), 7.23-7.21 (m, 2H), 7.01 (s, 2H), 2.83-2.75 (m, 16H), 2.65-2.62 (t, 8H, J = 15.67), 1.73-1.64 , 1.51-1.32 (m, 80H), 0.98-0.88 (m, 48H).

Figure 112015126254965-pat00045

Compound 10 (1.7 g, 0.71 mmol) and hexyl rhodanine (1.55 g, 7.1 mmol) were dissolved in chlorobenzene (80 mL), piperidine (10 mol%) was added thereto and stirred at 60 ° C for 12 hours. After the reaction solvent was distilled off under reduced pressure, ethyl acetate (200 mL) and CHCl 3 (5.0 mL) were added to precipitate and purified by column chromatography (40% CH 2 Cl 2 / hexane) to obtain a dark brown compound 11 , 55.47%).

1 H-NMR (300MHz, CDCl 3): δ 7.84 (s, 2H), 7.77 (s, 2H), 7.65 (s, 2H), 7.35-7.34 (d, 2H, J = 3.88), 7.23-7.20 ( (t, 8H, m, 6H), 7.11 (s, 2H), 7.01 (s, 2H), 4.12-4.08 (t, 4H, J = 15.5Hz), 2.84-2.75 J = 15.88 Hz), 1.74-1.64 (m, 24H), 1.49-1.33 (m, 92H), 0.99-0.56 (m, 54H).

[Example 4] Production of monomolecular organic semiconductor compound 4

Figure 112015126254965-pat00046

A solution of Compound 4 (0.5 g, 0.66 mmol) in Example 3 in 20 mL of THF was cooled to -78 ° C., and butyl lithium (0.562 mL, 1.4 mmol) was slowly added thereto. The mixture was stirred at -78 ° C. for 30 minutes, Min. The reaction solution was cooled again to -78 ° C, and (CH 3 ) 3 SnCl (1.47 ml, 1.47 mmol) was slowly added thereto, followed by stirring at room temperature for 12 hours. Water was added to the reaction solution, extracted with hexane and concentrated to obtain a yellow liquid compound 12 (0.63 g, 87.8%), which was used for the next step without further purification.

Figure 112015126254965-pat00047

Pd (O) (0.043 g, 0.03 mmol) was added to a solution of Compound 5 (0.4 g, 0.37 mmol) in Example 5 and Compound 12 (0.77 g, 0.93 mmol) in toluene and DMF mixed solvent (25 ml, 9: ) Was added, stirred for 30 minutes, and refluxed for 16 hours. Water was added to the reaction solution, and the mixture was extracted with CH 2 Cl 2 (70 ml × 3), concentrated, and purified by column chromatography (hexane) to obtain a yellow solid compound 7 (0.32 g, 38.8%).

1 H-NMR (300MHz, CDCl 3): δ 7.82 (s, 2H), 7.77 (s, 2H), 7.63-7.61 (d, 2H, J = 5.79Hz), 7.45-7.43 (d, 2H, J = (M, 12H), 1.71 (s, 2H), 7.22 (s, 2H) 1.59 (m, 18H), 1.49-1.31 (m, 84H), 0.97-0.87 (m, 54H).

Figure 112015126254965-pat00048

A solution of Compound 13 (0.319 g, 0.14 mmol) in 20 mL of THF was cooled to -78 ° C and slowly added with butyl lithium (0.142 mL, 0.35 mmol). The mixture was stirred at -78 ° C for 30 minutes and at room temperature for 30 minutes. The reaction solution was cooled again to -78 ° C, and (CH 3 ) 3 SnCl (0.356 ml, 0.35 mmol) was slowly added thereto, followed by stirring at room temperature for 12 hours. Water was added to the reaction solution, extracted with hexane and concentrated to obtain a yellow liquid (0.437 g, 92.3%). The product was used for the next step reaction without further purification.

1 H-NMR (300MHz, CDCl 3): δ 7.8 (s, 2H), 7.75 (s, 2H), 7.67 (s, 2H), 7.22 (s, 2H), 7.21 (s, 4H), 2.77-2.74 (m, 54H), 1.48-1.25 (m, 84H), 0.97-0.84 (m, 54H) 0.47-0.33 (t, 18H)

Figure 112015126254965-pat00049

Pd (0) (15 mg, 0.003 mmol) was dissolved in a mixed solvent of toluene and DMF (10 ml, 9: 1) and the compound 9 of Example 3 (0.172 g, 0.32 mmol) And the mixture was stirred for 30 minutes and refluxed for 16 hours. Water was added to the reaction solution, and the mixture was extracted with CH 2 Cl 2 (100 ml × 3), followed by concentration and purification through column chromatography (hexane: CH 2 Cl 2 (1: 1)) to obtain red solid compound 15 (0.232 g, 56.5% ).

1 H-NMR (300MHz, CDCl 3): δ 9.88 (s, 2H), 7.78-7.76 (d, 2H, J = 4.86Hz), 7.71-7.70 (d, 2H, J = 3.9Hz), 7.66 (2H 2H), 2.82-2.71 (m, 20H), 2.66-2.61 (m, 12H), 1.73-1.64 (m, 2H), 7.23-7.22 , 26H), 1.49-1.30 (m, 108H), 0.99-0.87 (m, 66H).

Figure 112015126254965-pat00050

Piperidine (10 mol%) was added to a solution of compound 15 (0.23 g, 0.07 mmol) and hexyl rhodanine (0.16 g, 0.73 mmol) in chlorobenzene (80 mL) and the mixture was stirred at 60 ° C for 12 hours. After distillation under reduced pressure of the reaction solvent, ethyl acetate (200mL) and CHCl adding 3 (5.0 mL) to precipitation and column chromatography (40% CH 2 Cl 2 / hexane) was purified via the compound of the dark brown 16 (134mg, 55.4%).

1 H-NMR (300MHz, CDCl 3): δ 7.83 (s, 2H), 7.77-7.76 (d, 4H, J = 5.39Hz), 7.65 (s, 2H), 7.36-7.34 (d, 2H), 7.25 4H, J = 15.74 Hz), 2.83-2.75 (m, 24H), 2.66-2.61 (m, 2H) , 12H), 1.73-1.41 (m, 30H), 1.51-1.28 (m, 120H), 0.99-0.81 (m, 72H).

[Example 5] Production of monomolecular organic semiconductor compound 5

Figure 112015126254965-pat00051

Example 1 was repeated except that 2- (3-ethyl-4-oxothiazolidin-2-ylidene) propanenitrile was used instead of rhodanine (3-ethyl-2-thioxothiazolidin- The monomolecular organic semiconductor compound 5 was prepared in the same manner.

1 H NMR (300MHz, CHCl 3 ): δ 7.64 (s, 2H), 7.41 (s, 2H), 7.37 (s, 2H), 7.22 (d, J = 3.5 Hz, 2H), 7.18 (d, J = (D, J = 4.0 Hz, 2H), 6.80 (d, J = 3.6 Hz, 4H), 6.79 (s, 2H) , 4.14 (q, J = 7.8 Hz, 4H), 2.92 (d, J = 6.74 Hz 8H), 2.70 (t, J = 7.8 Hz, 4H) (m, 4H), 1.64-1.56 (m, 8H), 1.50-1.49 (m, 10H), 1.44-1.37 (m, 26H), 1.32-1.22 (T, J = 6.6 Hz, 12H), 0.95 (t, J =

[Example 6] Production of monomolecular organic semiconductor compound 6

Figure 112015126254965-pat00052

The procedure of Example 2 was repeated except that 2- (3-ethyl-4-oxothiazolidin-2-ylidene) propanenitrile was used instead of rhodanine (3-ethyl-2-thioxothiazolidin- The monomolecular organic semiconductor compound 6 was prepared in the same manner.

1 H NMR (300MHz, CHCl 3 ): δ 7.64 (s, 2H), 7.48 (s, 2H) 7.37 (d, J = 5.6 Hz, 4H), 7.30 (s, 2H), 7.28-7.25 (m, 6H (M, 8H), 6.79 (s, 2H), 4.15 (q, J = 7.8 Hz, 4H), 2.96 (d, J = 6.71 Hz, (M, 6H), 1.61-1.57 (m, 2H), 2.67 (t, J = 7.5 Hz, 4H), 2.55 8H), 1.55-1.43 (m, 48H), 1.35-1.25 (m, 46H), 1.08-1.02 (m, 18H), 0.99-0.93 (m, 18H), 0.90 (m, 12H).

[Example 7] Production of monomolecular organic semiconductor compound 7

Figure 112015126254965-pat00053

Except that 2-cyano-2- (3-ethyl-4-oxothiazolidin-2-ylidene) acetic acid was used in place of rhodanine (3-ethyl-2-thioxothiazolidin-4-one) , And a monomolecular organic semiconductor compound 7 was prepared in the same manner as in Example 1.

1 H NMR (300MHz, CHCl 3 ): δ 7.65 (s, 2H), 7.51 (s, 2H), 7.44 (s, 2H), 7.27 (d, J = 3.5 Hz, 2H), 7.25 (d, J = 2H), 6.91 (d, J = 4.0 Hz, 2H), 6.90 (d, J = 3.6 Hz, 4H) J = 7.8 Hz, 4H), 2.95 (d, J = 6.74 Hz 8H), 2.73 (t, J = 7.8 Hz, 4H) (m, 4H), 1.67-1.55 (m, 8H), 1.54-1.52 (m, 10H), 1.43-1.38 (m, 26H), 1.35-1.24 , 12H), 0.96 (t, J = 6.3 Hz, 12H), 0.88 (t, J = 6.6 Hz, 12H).

[Example 8] Production of monomolecular organic semiconductor compound 8

Figure 112015126254965-pat00054

2-cyano-2- (3-ethyl-4-oxothiazolidin-2-yl) acetic acid was used instead of rhodanine (2-cyano- 2-ylidene) acetic acid was used as a starting material, to thereby prepare a monomolecular organic semiconductor compound 8.

1 H NMR (300MHz, CHCl 3 ): δ 12.52 (s, 2H), 7.60 (s, 2H) 7.47 (d, J = 5.6 Hz, 4H), 7.35 (s, 2H), 7.30-7.28 (m, 6H 2H), 4.14 (q, J = 7.8 Hz, 4H), 2.99 (d, J = 6.72 Hz, , 12H), 2.67 (t, J = 7.5 Hz, 4H), 2.58 (t, J = 7.5 Hz, 4H), 1.82-1.78 (m, 6H), 1.61-1.58 (m, 8H), 1.51-1.41 m, 48H), 1.35-1.25 (m, 46H), 1.08-1.02 (m, 18H), 0.99-0.93 (m, 18H), 0.90 (m, 12H).

[Comparative Example 1]

Figure 112015126254965-pat00055

(4,4 ', 8,8'-Tetrakis (5- (2-ethylhexyl) thiophen-2-yl) - [2,2'-bibenzo [ b] dithiophene] -6,6'-dyl) bis (trimethylstannane) instead of (4,8-bis (5- (2-ethylhexyl) thiophen- bromo-3 ', 3'4-trihexyl-2,2', 5 ', 2'-trithiophene-5-carbaldehyde was prepared by using 4'-b'] dithiophene-2,6-diyl bis (trimethylstannane) The compound of Comparative Example 1 was prepared in the same manner as in Example 1,

1 H NMR (300MHz, CHCl 3 ): δ 7.75 (s, 2H), 7.60 (s, 2H), 7.32 (s, 2H), 7.22 (s, 2H), 7.20 (d, 2H), 7.12 (d, 2H, J = 7.8 Hz, 4H), 2.91 (m, 4H), 2.82 (t, 2H), 1.70 (m, 8H), 1.30 (m, 56H), 0.88 (m, 30H)

Fabrication of organic solar cell device containing monomolecular organic semiconductor compound

The glass substrate coated with ITO (Indium Tin Oxide), which is a positive electrode, was immersed in deionized water containing washing solution, washed with an ultrasonic washing machine for 15 minutes, washed again with deionized water, acetone and IPA three times, Lt; 0 > C for 5 hours. The cleaned ITO glass substrate was subjected to ultraviolet / ozone treatment for 15 minutes, and then a hole transport layer PEDOT: PSS 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 each of Examples 1 to 8 or the compound of Comparative Example 1 and PC 71 BM in a chlorobenzene solvent at the mixing ratios shown in Table 1 below and injecting 0.45 μm (PTFE) syringe Filters were prepared by coating the organic semiconductor solution on a 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 is vacuum 1 × 10 - 6 torr was deposited in a thickness of 100 nm.

The composition ratios of the organic semiconductor solution and the electrical characteristics of the fabricated organic solar cell are shown in Table 1 below.

compound V oc (V) Jsc (mA / cm 2 ) FF (%) PCE (%) Example 1 0.90 12.88 69 8.02 Example 2 0.89 11.54 68 7.03 Example 3 0.98 11.90 74 7.88 Example 4 0.91 10.85 68 6.71 Example 5 0.89 11.38 67 6.79 Example 6 0.89 11.15 67 6.65 Example 7 0.88 11.85 65 6.78 Example 8 0.88 11.46 66 6.66 Comparative Example 1 0.87 12.23 61 6.55

The monomolecular organic semiconductor compounds of the present invention include a structure in which two or three benzodithiophene skeletons are continuously bonded as compared with Comparative Example 1, thereby improving intermolecular pi-pi stacking in a solid phase to minimize phase transition, The fill factor can be improved not only by increasing the degree of crystallinity.

Therefore, the organic semiconductor compound having a monomolecular structure can be improved while maintaining the advantages of the organic semiconductor compound while improving the efficiency of the organic electronic device employing the same. As shown in Table 1, when the characteristics of the device were compared, it was found that the efficiency of each monomolecular derivative was improved by increasing the fill factor of Comparative Example 1.

Claims (9)

delete delete An organic semiconductor compound represented by the following formula (2).
(2)
Figure 112017071288479-pat00058

[In the formula (2)
Z 1 and Z 2 are S;
R 1 and R 2 are independently of each other thiophenyl, wherein said thiophenyl may be further substituted with (C 1 -C 20) alkyl;
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;
Y 1 and Y 2 independently of one another are O, S, Se or CR a R b , R a and R b is independently from each other a cyano, carboxyl group, (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy or (C 1 -C 20) alkoxycarbonyl;
R 'is (C1-C20) alkyl;
n or o is an integer from 1 to 3;
l, m, p and q are each independently an integer of 0 to 3;
x is an integer from 2 to 5;
The arylene or heteroarylene of the A 1 group A 3 and B 1 to B 3 is independently selected from the group consisting of a (C 1 -C 20) alkyl group, a (C 1 -C 20) alkoxy group, an amino group, a hydroxyl group, a halogen group, a cyano group, A nitro group, a trifluoromethyl group, and a silyl group. The method of claim 3,
A 1 to A 3 and B 1 to B 3 are each independently selected from the following structures.
Figure 112017071288479-pat00059

[In the above formula,
Z is independently from each other O, S or Se;
D is, independently of each other O, S, N (R 51 ), C (R 52) (R 53) , or Si (R 54) (R 55 ), R 51 to R < 55 > independently from each other are hydrogen or (C1-C20) alkyl;
R 11 to R 37 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 20) alkyl;
R 41 to R 43 independently represent hydrogen, (C 1 -C 20) alkyl or (C 6 -C 20) aryl (C 1 -C 10) alkyl;
a is an integer of 1 to 4;
b, e and f are independently of each other an integer of 1 to 2;
and c is an integer of 1 to 3.] The method of claim 3,
Y 1 is S or O;
Y 2 is O or CR a R b , R a and R b are independently of each other a cyano, carboxyl group, (C 1 -C 20) alkyl or (C 1 -C 20) alkoxycarbonyl;
A 1 to A 3 and B 1 to B 3 are each independently selected from the following structures.
Figure 112017071288479-pat00060

[In the above formula,
Z is independently from each other O, S or Se;
D is, independently of each other O, S, N (R 51 ), C (R 52) (R 53) , or Si (R 54) (R 55 ), R 51 to R < 55 > independently from each other are hydrogen or (C1-C20) alkyl;
R 11 to R 21 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 20) alkyl;
a is an integer of 1 to 4;
and b is an integer of 1 to 2.] The method of claim 3,
An organic semiconductor compound selected from the following structures.
Figure 112015126254965-pat00061

Figure 112015126254965-pat00062

Figure 112015126254965-pat00063

Figure 112015126254965-pat00064

Figure 112015126254965-pat00065

Figure 112015126254965-pat00066

Figure 112015126254965-pat00067

Figure 112015126254965-pat00068
 delete Reacting a compound represented by the following formula (3) with a compound represented by the following formula (6-1) and a compound represented by the following formula (6-2) to prepare a compound represented by the following formula (7) And then reacting the organic semiconductor compound to form an organic semiconductor compound.
(2)
Figure 112017071288479-pat00073

(3)
Figure 112017071288479-pat00074

[Formula 6-1]
Figure 112017071288479-pat00075

[Formula 6-2]
Figure 112017071288479-pat00076

(7)
Figure 112017071288479-pat00077

[Chemical Formula 8]
Figure 112017071288479-pat00078

[In the above Chemical Formulas 2, 3, 6-1, 6-2, 7 and 8,
Z 1 and Z 2 are S;
R 1 and R 2 are independently of each other thiophenyl, wherein said thiophenyl may be further substituted with (C 1 -C 20) alkyl;
The A 1 group A 3 and B 1 to B 3 independently of one another are (C 6 -C 20) arylene or (C 3 -C 20) heteroarylene;
Y 1 and Y 2 independently of one another are O, S, Se or CR a R b , R a and R b is independently from each other a cyano, carboxyl group, (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy or (C 1 -C 20) alkoxycarbonyl;
R 'is (C1-C20) alkyl;
n or o is an integer from 1 to 3;
l, m, p and q are each independently an integer of 0 to 3;
x is an integer from 2 to 5;
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 arylene or heteroarylene of the A 1 group A 3 and B 1 to B 3 is independently selected from the group consisting of a (C 1 -C 20) alkyl group, a (C 1 -C 20) alkoxy group, an amino group, a hydroxyl group, a halogen group, a cyano group, A nitro group, a trifluoromethyl group, and a silyl group. An organic electronic device comprising the organic semiconductor compound according to any one of claims 3 to 6.
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