KR101769665B1

KR101769665B1 - Heterocyclic compound and organic solar cell comprising the same

Info

Publication number: KR101769665B1
Application number: KR1020150043557A
Authority: KR
Inventors: 배재순; 이윤구; 조근; 김홍기; 이재철; 이지영; 이행근; 임보규
Original assignee: 주식회사 엘지화학; 재단법인대구경북과학기술원
Priority date: 2014-03-27
Filing date: 2015-03-27
Publication date: 2017-08-21
Also published as: KR20150114418A

Abstract

The present invention provides heterocyclic compounds and organic solar cells containing the same.

Description

HETEROCYCLIC COMPOUND AND ORGANIC SOLAR CELL COMPRISING THE SAME [0002]

The present invention relates to heterocyclic compounds and organic solar cells comprising the same.

This specification claims the benefit of Korean Patent Application No. 10-2014-0035789, filed on March 27, 2014, to the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference.

Organic solar cells are devices that can convert solar energy directly into electric energy by applying photovoltaic effect. Solar cells can be divided into inorganic solar cells and organic solar cells depending on the material constituting the thin film. A typical solar cell is made of p-n junction by doping crystalline silicon (Si), which is an inorganic semiconductor. Electrons and holes generated by absorption of light are diffused to the p-n junction, accelerated by the electric field, and moved to the electrode. The power conversion efficiency of this process is defined as the ratio of the power given to the external circuit to the solar power entering the solar cell, and is achieved up to 24% when measured under the current standardized virtual solar irradiation conditions. However, since conventional inorganic solar cells have already been limited in economic efficiency and supply / demand of materials, organic semiconductor solar cells, which are easy to process, have various functions and are inexpensive, are seen as long-term alternative energy sources.

Solar cells are important to increase efficiency so that they can output as much electrical energy as possible from solar energy. In order to increase the efficiency of such a solar cell, it is also important to generate as much excitons as possible in the semiconductor, but it is also important to draw out generated charges without loss. One of the causes of loss of charge is that the generated electrons and holes are destroyed by recombination. Various methods have been proposed as methods for transferring generated electrons and holes to electrodes without loss, but most of them require additional processing, which may increase the manufacturing cost.

Yu, J. Gao, J. C. Hummelen, F. Wudl, A. J. Heeger, Science, 270, 1789. (1995)).

It is an object of the present invention to provide a heterocyclic compound and an organic solar cell containing the heterocyclic compound.

The present specification provides a heterocyclic compound containing a unit represented by the following general formula (1) or (2).

[Chemical Formula 1]

(2)

In formulas (1) and (2)

L1, L2, L1 'and L2' are the same or different and are each independently a direct bond; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted divalent heterocyclic group.

L and L 'are the same or different and are each independently a substituted or unsubstituted arylene group; Or a substituted or unsubstituted divalent heterocyclic group,

R1, R3, R1 'and R3' are the same or different from each other, and each independently hydrogen; A halogen group; A nitro group; Cyano; A carboxyl group; A hydroxy group; A substituted or unsubstituted carbonyl group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted allyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted ester group; A substituted or unsubstituted amide group; A substituted or unsubstituted ether group; A substituted or unsubstituted sulfonyl group; A substituted or unsubstituted sulfoxy group; A substituted or unsubstituted arylalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

R2, R4, R2 'and R4' are the same or different from each other and are each hydrogen or a halogen group.

Also, the present specification discloses a plasma display panel comprising a first electrode; A second electrode facing the first electrode; And at least one organic layer disposed between the first electrode and the second electrode and including a photoactive layer,

Wherein at least one of the organic material layers comprises the above-described heterocyclic compound.

The heterocyclic compound according to one embodiment of the present disclosure has a regioregular in which the positions at which the units of formula (1) are connected are selected. Heterocyclic compounds having positional regularity according to one embodiment of the present specification are relatively excellent in crystallinity.

The heterocyclic compound according to one embodiment of the present disclosure includes a structure in which two thiophene groups are condensed to thereby induce a high electron density and / or stabilized the resonance structure in the device.

In addition, the heterocyclic compound according to one embodiment of the present disclosure includes a linker of -L 1 -L-L2- between two thiophene group-condensed structures. In this case, the planarity of the molecules is increased, so that absorption of a long wavelength and low band gap are achieved, and a device with high efficiency can be provided.

The heterocyclic compound according to one embodiment of the present invention can be used as an organic material layer of an organic solar cell, and an organic solar cell including the heterocyclic compound can exhibit excellent characteristics in terms of an increase in open-circuit voltage and short-circuit current and / or an increase in efficiency.

The heterocyclic compound according to one embodiment of the present invention can be used alone or in combination with other materials in an organic solar cell, and the lifetime of the device can be expected to be improved by improving the efficiency and the thermal stability of the compound have.

1 is a view illustrating an organic solar cell according to an embodiment of the present invention.
2 is a diagram showing the NMR spectrum of the formula 1-b.
3 is an NMR spectrum showing the formula 1-c.
4 is an NMR spectrum showing the formula 1-e.
5 is an NMR spectrum showing the formula 1-f.
6 is an NMR spectrum showing the formula 1-g.
7 is a diagram showing the NMR spectrum of the formula 1-h.
8 is a diagram showing an NMR spectrum of the formula 3-a.
9 is an NMR spectrum showing the formula 3-b.
10 is a diagram showing the NMR spectrum of the formula 4-c.
11 is a graph showing the MS spectrum of the formula 4-c.
12 shows the NMR spectrum of the formula 6-b.
13 shows the MS spectrum of the formula 6-b.
14 is an NMR spectrum showing the formula 7-b.
15 is a diagram showing an NMR spectrum of the formula 8-a.
16 is a diagram showing the NMR spectrum of the formula 8-b.
17 is a diagram showing the NMR spectrum of the formula 1-1-1.
18 is a graph showing the results of the mass spectrometry of the Maltitol of Formula 1-1-1.
19 is a diagram showing a UV spectrum in a solution state of the formula 1-1-1.
20 is a diagram showing the UV spectrum of the film state of the formula 1-1-1.
FIG. 21 is a graph showing a cyclic voltammetry result of the chemical formula 1-1-1. FIG.
22 is a diagram showing a UV spectrum in a solution state of the formula 1-1-5.
23 is a diagram showing the UV spectrum of the film state of the formula 1-1-5.
24 is a graph showing the current density according to the voltage of the organic solar battery of Experimental Example 1. Fig.
25 is a graph showing the current density according to the voltage of the organic solar battery of Experimental Example 2. Fig.

Hereinafter, the present invention will be described in detail.

As used herein, the term "unit" means a structure contained in a heterocyclic compound, wherein one unit is bonded to a heterocyclic compound by polymerization.

The unit of formula (1) of the heterocyclic compound according to one embodiment of the present specification is optionally provided such that the S atoms of the thienothiophen group are arranged close to each other.

The unit of formula (2) of the heterocyclic compound according to another embodiment is optionally arranged such that the S atoms of the thienothiophen group are spaced apart from each other.

That is, the unit represented by the formula (1) or the formula (2) contained in the heterocyclic compound according to one embodiment of the present invention has a regioregular in a certain direction in the heterocyclic compound. Heterocyclic compounds having positional regularity according to one embodiment of the present specification are relatively excellent in crystallinity.

As used herein, the term " positional regularity " means selectively maintaining the direction in which a structure joins in the compound.

In one embodiment of the present specification, the linker includes two linkers of -L1-L-L2-, including two thienothiophenes, between the two units. In this case, the planarity of the molecules is increased, so that absorption of a long wavelength and low band gap are achieved, and a device with high efficiency can be provided.

In the case of including a linker, the conjugated structure of the intramolecular quinoid structure increases in an easily absorbing visible light region of a long wavelength in the film, as compared with the case where the linker is not included.

Further, the S atom of the thienothiophene or R2 'and R4' may have noncovalent bonds with the hetero atom of the linker. In this case, the planarity of the molecules is increased, the long wavelength can be absorbed, the low band gap is obtained, and a device with high efficiency can be provided.

The substituted or unsubstituted arylene group; Or a substituted or unsubstituted divalent heterocyclic group may be monocyclic or polycyclic, and is not limited thereto.

In one embodiment of the present invention, the formula (1) may be represented by the following formula (1-a).

[Chemical Formula 1-a]

In formula (1-a), R1 to R4, L, L1 and L2 are as defined above, E1 and E2 are the same as or different from each other and are each independently a terminal group of a heterocyclic compound.

In another embodiment, the formula (2) may be represented by the following formula (2-a).

[Chemical Formula 2-a]

In formula (2-a), R1 'to R4', L ', L1' and L2 'are as defined above, E1' and E2 'are the same or different from each other and are each independently a terminal group of a heterocyclic compound .

In one embodiment of the present disclosure, L1, L2, L1 'and L2' are the same as each other and are each independently a direct bond; Or represented by any one of the following structural formulas,

L and L 'are the same as or different from each other, and are each independently represented by any one of the following structural formulas.

In the above structure,

X1 to X6 are the same or different from each other and each independently CRR ', NR, O, SiRR', PR, S, GeRR '

Y1 and Y2 are the same or different and are each independently CR ", N, SiR", P or GeR "

A substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, Substituted or unsubstituted alkyl group, substituted or unsubstituted allyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted ester group, substituted or unsubstituted amide group, A substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, .

In one embodiment of the present specification, R 1 is a substituted or unsubstituted carbonyl group.

In another embodiment, R < 1 > is a substituted or unsubstituted ester group.

In one embodiment of the present invention, R 1 is a carbonyl group substituted with a substituted or unsubstituted alkoxy group.

In one embodiment of the present specification, R 3 is a substituted or unsubstituted carbonyl group.

In another embodiment, R 3 is a substituted or unsubstituted ester group.

In one embodiment of the present specification, R 3 is a carbonyl group substituted with a substituted or unsubstituted alkoxy group.

In one embodiment of the present invention, R 'is a substituted or unsubstituted carbonyl group.

In another embodiment, R < 1 > is a substituted or unsubstituted ester group.

In one embodiment of the present invention, R 'is a carbonyl group substituted with a substituted or unsubstituted alkoxy group.

In one embodiment of the present specification, R3 'is a substituted or unsubstituted carbonyl group.

In another embodiment, R3 'is a substituted or unsubstituted ester group.

In one embodiment of the present invention, R3 'is a carbonyl group substituted with a substituted or unsubstituted alkoxy group.

In one embodiment of the present invention, Formula 1 is represented by Formula 1-1, and Formula 2 is represented by Formula 2-1.

[Formula 1-1]

[Formula 1-2]

In formulas (1-1) and (1-2)

L, L ', L1, L1', L2, L2 ', R2, R4, R2' and R4 '

A1 to A4 are the same or different from each other, and each independently hydrogen; A halogen group; A nitro group; Cyano; A carboxyl group; A hydroxy group; A substituted or unsubstituted carbonyl group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted allyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted ester group; A substituted or unsubstituted amide group; A substituted or unsubstituted ether group; A substituted or unsubstituted sulfonyl group; A substituted or unsubstituted sulfoxy group; A substituted or unsubstituted arylalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In one embodiment of the present invention, E1 and E2 are the same or different from each other, and each independently is represented by the following formula (3).

In the present specification, the term " terminal " means a structure at both ends excluding the unit represented by the formula (1) in the heterocyclic compound.

In one embodiment of the present specification, the terminal group is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In one embodiment of the present invention, the terminal of the heterocyclic compound is represented by the following formula (3).

(3)

In formula (3)

d is an integer of 1 to 5,

X is selected from the group consisting of CRaRb, NRa, O, SiRaRb, PRa, S, GeRaRb, Se and Te,

Ra, Rb, R6 and R7 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; And a substituted or unsubstituted heterocyclic group,

R8 is hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; A substituted or unsubstituted heterocyclic group or a structure represented by the following formula

In the above structure,

Cy is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

R100 and R101 are the same or different from each other, and each independently hydrogen; A halogen group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted haloalkyl group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

Examples of such substituents are described below, but are not limited thereto.

The term "substituted" means that the hydrogen atom bonded to the carbon atom of the compound is replaced with another substituent, and the substituted position is not limited as long as the substituent is a substitutable position, , Two or more substituents may be the same as or different from each other.

As used herein, the term " substituted or unsubstituted " A halogen group; An alkyl group; An alkenyl group; An alkoxy group; Ester group; A carbonyl group; A carboxyl group; A hydroxy group; A cycloalkyl group; Silyl group; An arylalkenyl group; An aryloxy group; An alkyloxy group; An alkylsulfoxy group; Arylsulfoxy group; Boron group; An alkylamine group; An aralkylamine group; An arylamine group; A heterocyclic group; An arylamine group; An aryl group; A nitrile group; A nitro group; A hydroxy group; And a heterocyclic group, or has no substituent group.

The substituents may be substituted or unsubstituted with an additional substituent.

In the present specification, the halogen group may be fluorine, chlorine, bromine or iodine.

In the present specification, a carbonyl group is

. &Lt; / RTI >

Z is hydrogen; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; A substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms; A substituted or unsubstituted arylalkyl group having 7 to 50 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms.

In the present specification, the general formula of the ester group is

or

. &Lt; / RTI > Z is hydrogen; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; A substituted or unsubstituted arylalkyl group having 7 to 50 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms.

In the present specification, the amide group may be mono- or di-substituted by nitrogen of the amide group with hydrogen, a straight-chain, branched-chain or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the ester group may be substituted with oxygen of the ester group by a straight-chain, branched or cyclic alkyl group of 1 to 25 carbon atoms or an aryl group of 6 to 25 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 50. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec- N-pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, n-hexyl, Cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl Heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl and the like.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and specifically includes cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, But are not limited to, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert- butylcyclohexyl, cycloheptyl, Do not.

In the present specification, the alkoxy group may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 20 carbon atoms. Specific examples include methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, N-hexyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, But is not limited thereto.

In the present specification, the alkenyl group may be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, Butenyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, (Diphenyl-1-yl) vinyl-1-yl, stilbenyl, stilenyl, and the like.

In the present specification, the number of carbon atoms of the arylalkyl group is not particularly limited, but in one embodiment of the present specification, the arylalkyl group has 7 to 50 carbon atoms. Specifically, the aryl moiety has 6 to 49 carbon atoms and the alkyl moiety has 1 to 44 carbon atoms. Specific examples thereof include benzyl group, p-methylbenzyl group, m-methylbenzyl group, p-ethylbenzyl group, m-ethylbenzyl group, 3,5-dimethylbenzyl group, Group, an?,? -Methylphenylbenzyl group, a 1-naphthylbenzyl group, a 2-naphthylbenzyl group, a p-fluorobenzyl group, a 3,5-difluorobenzyl group, , p-methoxybenzyl group, m-methoxybenzyl group,? -phenoxybenzyl group,? -benzyloxybenzyl group, naphthylmethyl group, naphthylethyl group, naphthylisopropyl group, pyrrolylmethyl group, But are not limited to, an ethyl group, an aminobenzyl group, a nitrobenzyl group, a cyanobenzyl group, a 1-hydroxy-2-phenylisopropyl group, a 1-chloro-2-phenylisopropyl group and the like.

In the present specification, the aryl group may be a monocyclic aryl group or a polycyclic aryl group, and includes a case where an alkyl group having 1 to 25 carbon atoms or an alkoxy group having 1 to 25 carbon atoms is substituted. In addition, an aryl group in the present specification may mean an aromatic ring.

When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but is preferably 6 to 25 carbon atoms. Specific examples of the monocyclic aryl group include, but are not limited to, a phenyl group, a biphenyl group, a terphenyl group, and a stilbenyl group.

When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. And preferably has 10 to 24 carbon atoms. Specific examples of the polycyclic aryl group include naphthyl, anthracenyl, phenanthryl, pyrenyl, perylenyl, klychenyl, fluorenyl, and the like.

In the present specification, the fluorenyl group may be substituted, and adjacent substituents may be bonded to each other to form a ring.

When the fluorenyl group is substituted,

,

,

And

And the like. However, the present invention is not limited thereto.

In the present specification, the heterocyclic group is a hetero ring group containing at least one of N, O, S and Se atoms as hetero atoms, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furane group, a furyl group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, A pyridazinyl group, a pyrazinopyrazinyl group, an isoquinoline group, an isoquinolinyl group, an isoquinolinyl group, an isoquinolinyl group, an isoquinolinyl group, an isoquinolyl group, A benzothiazole group, a benzothiazole group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group, a phenanthroline group, a thiazolyl group, a thiazolyl group, An isoxazolyl group, an oxadiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but is not limited thereto.

The heterocyclic group may be monocyclic or polycyclic, and may be an aromatic, aliphatic or aromatic and aliphatic condensed ring.

In the present specification, an arylene group means a group having two bonding positions in an aryl group, that is, a divalent group. The description of the aryl group described above can be applied except that each of these is 2 groups.

In one embodiment of the present disclosure, L1 is a direct bond.

In another embodiment of the present disclosure,

to be.

In the present state of implementation, L2 is a direct bond.

In another embodiment of the present disclosure, L2 is

to be.

In one embodiment of the present specification, L is the same or different from each other, and each independently has the following structure.

In one embodiment, L is the same as or different from each other, and each independently has the following structure.

In another embodiment, L is the same as or different from each other, and each independently has the following structure.

In one embodiment of the present specification, the heterocyclic compound is represented by any one of the following formulas (4) to (19).

(4)

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

In Formulas 4 to 19,

d and d 'are the same as or different from each other, each independently an integer of 1 to 5,

When d and d 'are two or more, the structures in parentheses of two or more are the same or different from each other,

a and b are the same as or different from each other, each independently an integer of 0 or 1,

X and X 'are the same or different from each other and each independently selected from the group consisting of CRaRb, NRa, O, SiRaRb, PRa, S, GeRaRb,

X1 to X6, X10 and X11 are the same or different from each other and each independently CRR ', NR, O, SiRR', PR, S, GeRR '

Wherein R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 6, R 6, R 7, A substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted alkylthio group, or a substituted or unsubstituted alkylthio group; A substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted arylthioxy group, a substituted or unsubstituted alkylsulfoxy group, a substituted or unsubstituted arylsulfoxy group, a substituted or unsubstituted alkenyl group, A substituted or unsubstituted alkylamine group, a substituted or unsubstituted aralkylamine group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted heteroarylamine group, a substituted or unsubstituted aryl group, An unsubstituted heterocyclic group,

A1 to A4 are the same or different from each other, and each independently hydrogen; A halogen group; A nitro group; Cyano; A carboxyl group; A hydroxy group; A substituted or unsubstituted carbonyl group; A sulfonyl group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted allyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted ester group; A substituted or unsubstituted amide group; A substituted or unsubstituted ether group; A substituted or unsubstituted sulfonyl group; A substituted or unsubstituted sulfoxy group; A substituted or unsubstituted arylalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

R2, R4, R2 'and R4' are the same or different from each other, and each independently hydrogen; Or a halogen group,

R8 and R8 'are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; A substituted or unsubstituted heterocyclic group or a structure represented by the following formula

In the above structure,

In one embodiment of the present disclosure, a is zero.

In another embodiment, a is 1.

In one embodiment of the present disclosure, b is zero.

In another embodiment, b is 1.

In one embodiment of the present disclosure, S1 is hydrogen.

In another embodiment of the present specification, S 1 is a substituted or unsubstituted alkyl group.

In another embodiment, S 1 is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

In one embodiment, S 1 is a substituted or unsubstituted 2-ethylhexyl group.

In one embodiment, S1 is a 2-ethylhexyl group.

In one embodiment of the present disclosure, S2 is hydrogen.

In another embodiment, S2 is a substituted or unsubstituted alkyl group.

In another embodiment, S2 is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

In another embodiment, S2 is a substituted or unsubstituted octyl group.

In one embodiment of the present invention, S2 is an octyl group.

In one embodiment of the present disclosure, S3 is hydrogen.

In yet another embodiment, S3 is a substituted or unsubstituted alkyl group.

In another embodiment, S3 is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

In another embodiment, S3 is a substituted or unsubstituted octyl group.

In one embodiment of the present specification, S3 is an octyl group.

In one embodiment of the present disclosure, S4 is hydrogen.

In another embodiment of the present specification, S4 is a substituted or unsubstituted alkyl group.

In another embodiment, S4 is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

In one embodiment, S4 is a substituted or unsubstituted 2-ethylhexyl group.

In one embodiment, S4 is a 2-ethylhexyl group.

In one embodiment, R2 is hydrogen.

In another embodiment of the present disclosure, R 2 is a halogen group.

In another embodiment, R2 is fluorine.

In another embodiment, R4 is hydrogen.

In another embodiment of the disclosure, R4 is a halogen group.

In another embodiment, R4 is fluorine.

In one embodiment of the present specification, R8 is a substituted or unsubstituted alkyl group.

In one embodiment of the present specification, R8 is a substituted or unsubstituted hexyl group.

In one embodiment, R8 is a hexyl group.

In one embodiment of the present disclosure,

to be.

In one embodiment of the present specification, R100 is a substituted or unsubstituted alkyl group.

In another embodiment, R100 is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

In one embodiment, R100 is an ethyl group.

In one embodiment of the present invention, A1 is a substituted or unsubstituted alkyl group.

In another embodiment, A1 is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

In one embodiment of the present invention, A1 is a substituted or unsubstituted 2-ethylhexyl group.

In one embodiment, A1 is a 2-ethylhexyl group.

In one embodiment of the present specification, A2 is a substituted or unsubstituted alkyl group.

In another embodiment, A2 is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

In one embodiment of the present invention, A2 is a substituted or unsubstituted 2-ethylhexyl group.

In one embodiment, A2 is a 2-ethylhexyl group.

In one embodiment of the present invention, A3 is a substituted or unsubstituted alkyl group.

In one embodiment of the present specification, A3 is a substituted or unsubstituted 2-ethylhexyl group.

In one embodiment, A3 is a 2-ethylhexyl group.

In one embodiment of the present invention, A4 is a substituted or unsubstituted alkyl group.

In one embodiment of the present specification, A4 is a substituted or unsubstituted 2-ethylhexyl group.

In one embodiment, A4 is a 2-ethylhexyl group.

In one embodiment of the present disclosure, R6 is hydrogen.

In one embodiment, R7 is hydrogen.

In one embodiment, R6 'is hydrogen.

In another embodiment, R7 'is hydrogen.

In one embodiment of the present disclosure, R10 is hydrogen.

In another embodiment of the present specification, R10 is a halogen group.

In another embodiment, R10 is fluorine.

In another embodiment of the disclosure, R11 is hydrogen.

In another embodiment of the present specification, R11 is a halogen group.

In another embodiment, R11 is fluorine.

In one embodiment of the present specification, R12 is hydrogen.

In another embodiment, R13 is hydrogen.

In one embodiment of the present disclosure, d is 2.

In another embodiment of the present disclosure, d is one.

In one embodiment of the present disclosure, d 'is 2.

In another embodiment of the present disclosure, d 'is 1.

In one embodiment of the present disclosure, X is S.

In one embodiment of the present disclosure, X1 is S.

In another embodiment, X2 is S.

In one embodiment of the present disclosure, X2 is CRR '.

In another embodiment, X2 is NR.

In one embodiment, X2 is SiRR '.

In one embodiment of the present disclosure, X3 is S.

In another embodiment X3 is O.

In another embodiment, X3 is NR.

In another embodiment, X3 is CRR '.

In another embodiment X3 is SiRR '.

In another embodiment, X4 is S.

In another embodiment, X4 is CRR '.

In another embodiment, X5 is S.

In one embodiment of the present disclosure, X5 is O.

In one embodiment of the present disclosure, X5 is SiRR '.

In one embodiment of the present disclosure, X6 is CRR '.

In one embodiment of the present disclosure, X6 is SiRR '.

In another embodiment, X6 is O.

In another embodiment, X6 is S.

In one embodiment of the present invention, R and R 'are the same or different and each independently represents a substituted or unsubstituted alkyl group; A substituted or unsubstituted alkoxy group; Or a substituted or unsubstituted aryl group.

In one embodiment of the present invention, R is a substituted or unsubstituted alkyl group.

In one embodiment, R is a linear or branched alkyl group.

In one embodiment, R is a substituted or unsubstituted octyl group.

In another embodiment, R is an octyl group.

In one embodiment of the present specification, R is a substituted or unsubstituted 2-ethylhexyl group.

In one embodiment, R is a 2-ethylhexyl group.

In one embodiment of the present specification, R is a substituted or unsubstituted 3,7-dimethyloctyl group.

In one embodiment of the present specification, R is a 3,7-dimethyloctyl group.

In one embodiment of the present disclosure, R is a substituted or unsubstituted aryl group.

In one embodiment of the present specification, R is a substituted or unsubstituted phenyl group.

In one embodiment of the present specification, R is a phenyl group substituted with a substituted or unsubstituted alkyl group.

In one embodiment of the present disclosure, R is a phenyl group substituted with an alkyl group.

In one embodiment of the present disclosure, R is a phenyl group substituted with a hexyl group.

In one embodiment of the present invention, R 'is a substituted or unsubstituted alkyl group.

In one embodiment, R 'is a linear or branched alkyl group.

In one embodiment, R 'is a substituted or unsubstituted octyl group.

In another embodiment, R 'is an octyl group.

In one embodiment of the present specification, R 'is a substituted or unsubstituted 2-ethylhexyl group.

In one embodiment, R 'is a 2-ethylhexyl group.

In one embodiment of the present specification, R 'is a substituted or unsubstituted 3,7-dimethyloctyl group.

In one embodiment of the present disclosure, R 'is a 3,7-dimethyloctyl group.

In one embodiment of the present disclosure, R 'is a substituted or unsubstituted aryl group.

In one embodiment of the present specification, R 'is a substituted or unsubstituted phenyl group.

In one embodiment of the present specification, R 'is a phenyl group substituted with a substituted or unsubstituted alkyl group.

In one embodiment of the present disclosure, R 'is a phenyl group substituted with an alkyl group.

In one embodiment of the present disclosure, R 'is a phenyl group substituted with a hexyl group.

In one embodiment of the present disclosure, Y1 is CR ".

In one embodiment of the present disclosure, Y1 is N.

In one embodiment of the present disclosure, Y2 is N.

In another embodiment, Y2 is CR ".

In one embodiment of the present specification, R "is a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted heterocyclic group.

In one embodiment of the present specification, R "is a substituted or unsubstituted alkoxy group.

In another embodiment, R "is a substituted or unsubstituted 2-ethylhexyloxy group.

In one embodiment of the present disclosure, R "is a 2-ethylhexyloxy group.

In one embodiment of the present specification, R "is a substituted or unsubstituted hexyloxy group.

In one embodiment, R "is a hexyloxy group.

In one embodiment of the present specification, R "is a substituted or unsubstituted heterocyclic group.

In one embodiment of the present specification, R "is a substituted or unsubstituted heterocyclic group containing at least one S atom.

In one embodiment of the present specification, R "is a substituted or unsubstituted thiophene group.

In one embodiment of the present specification, R "is a thiophene group substituted with a substituted or unsubstituted alkyl group.

In one embodiment of the present specification, R "is a thiophene group substituted by a substituted or unsubstituted 2-ethylhexyl group.

In one embodiment of the present specification, R "is a thiophene group substituted with a 2-ethylhexyl group.

In one embodiment of the present specification, R "is a thiophene group substituted with a substituted or unsubstituted hexyl group.

In one embodiment of the present disclosure, R "is a thiophene group substituted with a hexyl group.

In one embodiment of the present specification, R "is a substituted or unsubstituted heterocyclic group containing at least one Se atom.

In one embodiment of the present specification, R "is a substituted or unsubstituted selenophen group.

In one embodiment of the present specification, R "is a selenophen group substituted with a substituted or unsubstituted alkyl group.

In one embodiment of the present specification, R "is a selenophen group substituted with a substituted or unsubstituted 2-ethylhexyl group.

In one embodiment of the present specification, R "is a selenophene group substituted with a 2-ethylhexyl group.

In one embodiment of the present specification, R "is a selenophen group substituted with a substituted or unsubstituted 2-hexyldecanyl group.

In one embodiment of the present disclosure, R "is a selenophene group substituted with a 2-hexyldecanyl group.

In one embodiment of the present disclosure, X 'is S.

In another embodiment, R8 'is a substituted or unsubstituted alkyl group.

In one embodiment of the present specification, R8 'is a substituted or unsubstituted hexyl group.

In another embodiment, R8 'is a hexyl group.

In one embodiment of the present disclosure, R8 '

to be.

In one embodiment, R100 is an ethyl group.

In one embodiment of the present invention, the heterocyclic compound represented by Formula 1 is represented by any one of the following Formulas 1-1-1 to 1-1-16.

[Formula 1-1-1]

[Formula 1-1-2]

[Formula 1-1-3]

[Formula 1-1-4]

[Formula 1-1-5]

[Formula 1-1-6]

[Formula 1-1-7]

[Formula 1-1-8]

[Formula 1-1-9]

[Formula 1-1-10]

[Formula 1-1-11]

[Formula 1-1-12]

[Formula 1-1-13]

[Formula 1-1-14]

[Formula 1-1-15]

[Formula 1-1-16]

In one embodiment of the present invention, the heterocyclic compound represented by the formula (2) is represented by any one of the following formulas (2-1-1) to (2-1-16).

[Formula 2-1-1]

[Formula 2-1-2]

[Chemical Formula 2-1-3]

[Chemical Formula 2-1-4]

[Formula 2-1-5]

[Formula 2-1-6]

[Formula 2-1-7]

[Formula 2-1-8]

[Formula 2-1-9]

[Formula 2-1-10]

[Chemical Formula 2-1-11]

[Formula 2-1-12]

[Formula 2-1-13]

[Chemical Formula 2-1-14]

[Chemical Formula 2-1-15]

[Chemical Formula 2-1-16]

The heterocyclic compound of the present specification can be produced based on the following production example.

1 equivalent of bromine is reacted with a thienothiophene group substituted by R 1 to brominate the thienothiophene group in the S atom direction and then combine to obtain a compound represented by the general formula Can be prepared.

The heterocyclic compounds according to the present disclosure can be prepared by a multistage chemical reaction. After the monomers are prepared through alkylation, Grignard reaction, Suzuki coupling reaction, and Stille coupling reaction, the monomers are reacted through a carbon-carbon coupling reaction such as a steel coupling reaction, Can be prepared. When the substituent to be introduced is a boronic acid or a boronic ester compound, it can be prepared through a Suzuki coupling reaction. When the substituent to be introduced is tributyltin or trimethyltin ) Compound, it may be prepared through a steel coupling reaction, but the present invention is not limited thereto.

In one embodiment of the present disclosure, the first electrode; A second electrode facing the first electrode; And at least one organic compound layer including a photoactive layer disposed between the first electrode and the second electrode, wherein at least one of the organic compound layers includes the heterocyclic compound.

An organic solar cell according to an embodiment of the present invention includes a first electrode, a photoactive layer, and a second electrode. The organic solar cell may further include a substrate, a hole transporting layer, and / or an electron transporting layer.

In one embodiment of the present invention, when the organic solar cell receives photons from an external light source, electrons and holes are generated between the electron beams and the electron acceptors. The generated holes are transported to the anode through the electron donor layer.

In one embodiment of the present invention, the organic material layer includes a hole transport layer, a hole injection layer, or a layer that simultaneously transports holes and holes, and the hole transport layer, the hole injection layer, And the above heterocyclic compound.

In another embodiment, the organic material layer may include an electron injection layer, an electron transport layer, or a layer that simultaneously performs electron injection and electron transport, and the electron injection layer, the electron transport layer, And the above heterocyclic compound.

FIG. 1 illustrates an organic solar cell according to an embodiment of the present invention, and it is not limited thereto, and may or may not include an additional organic layer. In addition, the above-mentioned compounds may be used in place of the compound of the formula (1-1-1). When a plurality of organic layers are included, the organic layers may be the same or different.

In one embodiment of the present invention, the organic solar cell includes one or more organic layers selected from the group consisting of a hole injecting layer, a hole transporting layer, a hole blocking layer, a charge generating layer, an electron blocking layer, As shown in FIG.

In one embodiment of the present disclosure, the organic solar cell may further include an additional organic layer. The organic solar cell can reduce the number of organic layers by using organic materials having various functions at the same time.

In one embodiment of the present disclosure, the organic solar cell may be arranged in the order of the cathode, the photoactive layer, and the anode, and may be arranged in the order of the anode, the photoactive layer, and the cathode, but is not limited thereto.

In another embodiment, the organic solar cell may be arranged in the order of an anode, a hole transporting layer, a photoactive layer, an electron transporting layer and a cathode, and may be arranged in the order of a cathode, an electron transporting layer, a photoactive layer, a hole transporting layer, , But is not limited thereto.

In one embodiment of the present invention, the organic solar cell is a normal structure.

In one embodiment of the present invention, the organic solar cell is an inverted structure.

In one embodiment of the present invention, the organic solar cell is a tandem structure.

The organic solar cell according to one embodiment of the present disclosure may have one photoactive layer or two or more layers.

In another embodiment, a buffer layer may be provided between the photoactive layer and the hole transporting layer or between the photoactive layer and the electron transporting layer. At this time, a hole injection layer may be further provided between the anode and the hole transport layer. Further, an electron injecting layer may be further provided between the cathode and the electron transporting layer.

In one embodiment of the present invention, the photoactive layer includes one or two or more selected from the group consisting of an electron donor and a donor, and the electron donor includes the heterocyclic compound.

In one embodiment of the present disclosure, the electron acceptor material may be selected from the group consisting of fullerene, fullerene derivatives, vicoprofoins, semiconducting elements, semiconducting compounds, and combinations thereof. Specifically, there can be a _{PC 61 BM (phenyl C 61 -butyric} acid methyl ester) or _{PC 71 BM (phenyl C 71 -butyric} acid methyl ester).

In one embodiment of the present disclosure, the electron donor and the electron acceptor constitute a bulk heterojunction (BHJ).

In one embodiment of the present invention, the photoactive layer is a bilayer structure including an n-type organic layer and a p-type organic layer, and the p-type organic layer includes the heterocyclic compound.

In this specification, the substrate may be a glass substrate or a transparent plastic substrate having excellent transparency, surface smoothness, ease of handling, and waterproofness, but is not limited thereto, and is not limited as long as it is a substrate commonly used in organic solar cells. Specific examples include glass or polyethylene terephthalate, polyethylene naphthalate (PEN), polypropylene (PP), polyimide (PI), and triacetyl cellulose (TAC) But is not limited thereto.

The anode electrode may be a transparent material having excellent conductivity, but is not limited thereto. Metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SNO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline.

The method of forming the anode electrode is not particularly limited and may be applied to one surface of the substrate or may be coated in a film form using, for example, sputtering, E-beam, thermal evaporation, spin coating, screen printing, inkjet printing, doctor blade or gravure printing . &Lt; / RTI >

When the anode electrode is formed on a substrate, it may undergo cleaning, moisture removal and hydrophilic reforming processes.

For example, the patterned ITO substrate is sequentially washed with a cleaning agent, acetone, and isopropyl alcohol (IPA), and then dried on a heating plate at 100 to 150 ° C for 1 to 30 minutes, preferably 120 ° C for 10 minutes , And the substrate surface is hydrophilically reformed when the substrate is completely cleaned.

Through such surface modification, the junction surface potential can be maintained at a level suitable for the surface potential of the photoactive layer. Further, in the modification, the formation of the polymer thin film on the anode electrode is facilitated, and the quality of the thin film may be improved.

The pretreatment techniques for the anode electrode include a) surface oxidation using a parallel plate discharge, b) a method of oxidizing the surface through ozone generated using UV ultraviolet radiation in vacuum, and c) oxygen generated by the plasma And a method of oxidizing using a radical.

One of the above methods can be selected depending on the state of the anode electrode or the substrate. However, whichever method is used, it is preferable to prevent oxygen from escaping from the surface of the anode electrode or the substrate and to suppress the residual of moisture and organic matter as much as possible. At this time, the substantial effect of the preprocessing can be maximized.

As a specific example, a method of oxidizing the surface through ozone generated using UV can be used. At this time, the ITO substrate patterned after the ultrasonic cleaning is dried by baking on a hot plate, and then put into a chamber. Then, by the action of a UV lamp, ozone generated by reaction of oxygen gas with UV light The patterned ITO substrate can be cleaned.

However, the method of modifying the surface of the patterned ITO substrate in the present specification is not particularly limited, and any method may be used as long as it is a method of oxidizing the substrate.

The cathode electrode may be a metal having a small work function, but is not limited thereto. Specifically, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; Layer structure such as LiF / Al, LiO ₂ / Al, LiF / Fe, Al: Li, Al: BaF ₂ and Al: BaF ₂ : Ba.

The cathode electrode may be formed by depositing in a thermal evaporator having a degree of vacuum of 5 x 10 < ^-7 > torr or less, but the method is not limited thereto.

The hole transporting layer and / or the electron transporting layer material efficiently transfer electrons and holes separated from the photoactive layer to the electrode, and the material is not particularly limited.

The hole transport layer material may include poly (3,4-ethylenediocythiophene) doped with poly (styrenesulfonic acid) (PEDOT: PSS), molybdenum oxide (MoO _x ); Vanadium oxide (V ₂ O ₅ ); Nickel oxide (NiO); And tungsten oxide (WO _x ), but the present invention is not limited thereto.

The electron transport layer material may be electron-extracting metal oxides, specifically a metal complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Metal complexes including Liq; LiF; Ca; Titanium oxide (TiO _x ); Zinc oxide (ZnO); And cesium carbonate (Cs ₂ CO ₃ ), but the present invention is not limited thereto.

The photoactive layer can be formed by dissolving a photoactive material such as an electron donor and / or an electron acceptor in an organic solvent, and then applying the solution by spin coating, dip coating, screen printing, spray coating, doctor blade, brush painting, But is not limited to the method.

The heterocyclic compound according to one embodiment of the present invention can be applied to organic electronic devices such as organic light emitting devices and organic transistors.

The production method of the heterocyclic compound and the production of the organic solar cell including the heterocyclic compound will be described in detail in the following Production Examples and Examples. However, the following examples are intended to illustrate the present specification, and the scope of the present specification is not limited thereto.

Example 1. Synthesis of Compound (1-h)

(1) Synthesis of Formula 1-b (4,5-Diethyl-thiophene-2-carboxylic acid methyl ester)

Methyl-2-thiophenecarboxylate (4.00 g, 28.13 mmol) and chloromethyl methyl ether (11.00 g, 136.63 mmol) were added to a 100 ml flask equipped with a nitrogen gas purge tube Titanium tetrachloride (TiCl ₄ ) (8.00 g, 42.20 mmol) was slowly poured into the ice water bath and reacted for 5 hours. After extraction with excess distilled water and methyl chloride (MC), the organic layer was dried with anhydrous sodium sulfate to remove water. The remaining solvent was removed by evaporation, recrystallized with hexane, and the resulting crystals were filtered under reduced pressure to obtain 5.20 g (93.2%) of white crystals. ¹ H NMR (CDCl ₃ ): 3.89 (3H, s), 4.59 (2H, s), 4.78 (2H, s), 7.71 (1H, s).

2 is a diagram showing the NMR spectrum of the formula 1-b.

(2) Synthesis of Formula 1-c (4,6-Dihydro-thieno- [3,4-b] thiophene-2-carboxylic acid methyl ester (4,6-Dihydro-thieno [ -b] thiophene-2-carboxylic acid methyl ester))

Compound 1-b (5.20 g, 21.75 mmol) and 250 ml of methanol were placed in a 500 ml flask equipped with a reflux condenser and heated in a 60-degree water bath. A solution of sodium sulfide (1.87 g, 23.92 mmol) and methanol (150 ml) was slowly added over 1 hour and refluxed for 2 hours. The solid impurities were removed by filtration under reduced pressure, and the solvent was removed using an evaporator, and the remaining residue was removed using distilled water. The remaining residue was separated by column chromatography (MC: Hex = 2: 1) to obtain 1.64 g (31.23%) of white crystals. ¹ H NMR (CDCl ₃ ): 3.87 (3 H, s), 4.05-4.06 (2H, t), 4.18-4.20

3 is an NMR spectrum showing the formula 1-c.

(3) Synthesis of (1-e) (thieno [3,4-b] thiophene-2-carboxylic acid methyl ester)

Ethyl acetate and 1-c compound (1.64 g, 8.19 mmol) were placed in a 250 ml flask equipped with a nitrogen purge tube and then cooled in a dry ice bath. Methachloro peroxybenzoic acid (MCPBA) (2.12 g, 12.28 mmol) dissolved in ethyl acetate was slowly injected and allowed to react overnight. The solvent was removed using an evaporator, and acetic anhydride was added thereto, followed by reaction for 2 hours. The reaction was cooled at room temperature and distilled to remove acetic anhydride. The remaining residue was separated by column chromatography (MC: Hex = 1: 1) to obtain 1.31 g (80.8%) of white crystals. ¹ H NMR (CDCl ₃ ): 3.91 (3H, s), 7.28-7.29 (IH, d), 7.59-7.60

4 is an NMR spectrum showing the formula 1-e.

(4) Synthesis of (1-f) (thieno [3,4-b] thiophene-2-carboxylic acid)

To a 100 ml flask equipped with a reflux condenser was added lithium hydroxide (LiOH) (0.32, 13.21 mmol) dissolved in 30 ml of distilled water and 1-e compound (1.31 g) dissolved in 30 ml of tetrahydrofuran (THF) And refluxed for one day. The solution was acidified with 1N HCl solution and then filtered under reduced pressure to obtain 1.10 g (90.5%) of dark yellow crystals. ¹ H NMR (DMSO): 7.98 (1H, s), 7.73 (2H, s)

5 is an NMR spectrum showing the formula 1-f.

(5) Synthesis of 1-g (thieno [3,4-b] thiophene-2-carboxylic acid 2-ethyl ester -hexyl ester))

A 1-f compound (1.10 g, 5.97 mmol) dissolved in methyl chloride (MC) was added to a 250 ml flask equipped with a nitrogen purging tube and N, N'-dicyclohexylcarbodiimide (DCC) (1.48 g, 7.16 mmol), dimethylaminopyridine (DMAP) (0.26 g, 2.09 mmol) and 2-ethyl-1-hexanol (3.88 g, 29.85 mmol) were added and reacted for one day. After extraction with distilled water and methyl chloride (MC), the organic layer was dehydrated using anhydrous sodium sulfate. The solid impurities were removed by filtration under reduced pressure. The remaining solvent was removed by evaporation, and the residue was separated by column chromatography (MC: Hex = 1) to obtain 1.49 g (83.9%) of a slightly orange-colored transparent oil. ^{_{1 HNMR (CDCl 3): 0.86-0.96}} (6H, m), 1.25-1.50 (8H, m), 1.67-1.74 (1H, m), 4.19-4.27 (2H, m), 7.23-7.24 (1H, d ), 7.54-7.55 (1 H, d), 7.67 (1 H, s)

6 is an NMR spectrum showing the formula 1-g.

(6) Synthesis of (1-h) (6-Bromo-thieno [3,4-b] thiophene-2-carboxylic acid 2-ethyl-hexyl ester 6-Bromo-thieno [3,4- b] thiophene -2-carboxylic acid 2-ethyl-hexyl ester)

A 1-g compound (1.49 g, 5.03 mmol) dissolved in 20 ml of dimethylformamide (DMF) is placed in a 100 ml flask equipped with a nitrogen purge tube. N-bromosuccinimide (NBS) (0.89 g, 5.03 mmol) dissolved in dimethylformamide (DMF) was slowly injected using a syringe and reacted for 20 minutes. After extraction with distilled water and ethyl acetate (EA), the organic layer was dried over anhydrous sodium sulfate and the solid impurities were removed by filtration under reduced pressure. The mixture was separated twice by column chromatography (Methylenechloride: Chloroform: Hexane = 1: 1: 3) to obtain 1.02 g (51.4%) of transparent orange oil. ^{_{1 HNMR (CDCl 3): 0.86-0.96}} (6H, m), 1.25-1.50 (8H, m), 1.67-1.74 (1H, m), 4.20-4.27 (2H, m), 7.22 (1H, d), 7.53 (1 H, d).

7 is a diagram showing the NMR spectrum of the formula 1-h.

Examples 1-2. Synthesis of 2-h

To a 100 ml flask equipped with a nitrogen purge tube were added 3-fluoro-thieno [3,4-b] thiophene-2-carboxylic acid 2-ethyl-hexyl ester dissolved in DMF (10 ml) thieno [3,4-b] thiophene-2-carboxylic acid 2-ethyl-hexyl ester (0.32 g, 1.01 mmol).

After several times extraction with distilled water and ethyl acetate, the organic layer was dried over anhydrous sodium sulfate and the solid impurities were removed by filtration under reduced pressure. The residue was purified by column chromatography (MC: Hexane = 1: 20) to obtain a yellow transparent oil (0.05 g, 12.6%). ^{_{1 HNMR (CDCl 3): 0.86-0.96}} (6H, m), 1.35-1.50 (8H, m), 1.67-1.74 (1H, m), 4.20-4.27 (2H, m), 7.22 (1H, d)

Examples 1-3. Synthesis of Formula 3-b

(1) Synthesis of Formula 3-a

[Formula 3-a]

To a 100 ml flask equipped with a reflux condenser were added 1.02 g (2.72 mmol) of the compound of the formula 1-h and 2,6-bis (trimethyltin) -4,8-bis (2-ethylhexyloxy) benzoate of the formula 4-C [1,2-b: 4,5-b '] 2,6-Bis (trimethyltin) -4,8-bis (2- ethylhexyloxy) benzo [1,2- ] dithiophene (0.84 g, 1.09 mmol) in toluene (15 ml) was refluxed for 24 hours in an oil bath with Pd (PPh ₃ ) ₄ (0.16 g, 0.14 mmol). The reaction mixture was cooled at room temperature, and the remaining solvent was evaporated. The residue was separated by column chromatography (MC: Chloroform: Hexane = 1: 1: 3) to obtain 0.48 g (41.5%) of a red crystal. ¹ H NMR (CDCl ₃ ): 0.83-0.88 (6H, m), 0.90-1.00 (16H, m), 1.07-1.11 (6H, t), 1.36-1.54 ), 1.72-1.77 (4H, m), 1.84-1.87 (2H, m), 4.20-4.22 (4H, d), 4.27-4.29 ), 8.05 (2H, s).

8 is a diagram showing an NMR spectrum of the formula 3-a.

(2) Synthesis of Formula 3-b

[Formula 3-b]

To a 100 ml flask equipped with a nitrogen purge tube was added ₁₅ ml of chloroform (CHCl ₃ ) in which 1-i compound (0.48 g, 0.46 mmol) was dissolved. N-bromosuccinimide (NBS) (0.18, 1.02 mmol) dissolved in chloroform (CHCl ₃ ) was slowly injected using a syringe and reacted in the dark for 4 hours. After extraction with distilled water and methyl chloride (MC), the organic layer was dried over anhydrous sodium sulfate and the solid impurities were removed by filtration under reduced pressure. The product was separated by column chromatography (MC: Hex = 1: 2) to obtain 0.36 g (65.7%) of a dark red crystal. ¹ H NMR (CDCl ₃ ): 0.83-0.88 (6H, m), 0.90-1.00 (16H, m), 1.07-1.11 (6H, t), 1.36-1.54 ), 1.72-1.77 (4H, m), 1.84-1.87 (2H, m), 4.20-4.22 (4H, d), 4.27-4.29 ).

9 is an NMR spectrum showing the formula 3-b.

Examples 1-4. Synthesis of 4-c

(1) Synthesis of formula 4-b

To 60 ml of distilled water (H ₂ O) was added 4,8-dihydrobenzo [1,2-b: 4,5-b '] dithiophene- (5.2 g, 79.6 mmol) and zinc powder (5.2 g, 79.6 mmol) were added to the solution and stirred. Then, sodium hydroxide (NaOH , 24 g) were added, and the mixture was refluxed for 1 hour with stirring. During the reaction, the color of the solution changed from yellow to red to orange. To this solution was added 2-ethylhexylbromide (21.0 g, 108.9 mmol) and tetrabutylammonium bromide (as catalyst), followed by stirring / refluxing for 2 hours. If the color of the solution was red or dark red, zinc powder was added additionally and stirred / refluxed for 6 hours. The solution was poured into cold water, extracted twice with diethyl ether, and then the residue was removed with magnesium sulfate (MgSO ₄ ). The solvent was removed under reduced pressure, and a colorless liquid of the formula 4-b was obtained through a silica column (eluent: Pet ether: MC = 9: 1) (yield: 64.9%).

(2) Synthesis of formula 4-c

The compound 4-b (10.3 g, 23.1 mmol) was dissolved in 50 ml of tetrahydrofuran (THF) and the temperature was lowered to -78 ° C. At this temperature, 1.6M n-BuLi (1.6M n-Butyllithium in hexane, 31.7ml, 50.8mmol) dissolved in hexane was slowly added and stirred for 30 minutes. Thereafter, the temperature was raised to 0 ° C., stirred for 1 hour, cooled again to -78 ° C., and 1M trimethyltinchloride in THF (53.1 ml, 53.1 mmol) dissolved in THF was added The mixture was stirred at room temperature for 12 hours. The solution was poured into ice, extracted twice with diethyl ether, washed twice with water, and the residue was removed with magnesium sulfate (MgSO ₄ ). The solvent was removed under reduced pressure, and the solvent was recrystallized from ethanol to obtain a colorless crystalline solid (yield: 71.4%).

10 is a diagram showing the NMR spectrum of the formula 4-c.

11 is a graph showing the MS spectrum of the formula 4-c.

Examples 1-5. Synthesis of formula 5-c

(1) Synthesis of the compound of the formula 5-b

(0.05 g, 0.13 mmol) and 4,8-bis- [5- (2-ethylhexyl) -thiophen-2-yl] 2,6-trimethylstannyl- 2-yl] -2,6-bis-trimethylstannanyl-1,5-dithia-sindacene (0.047 g, , 0.052 mmol)) in toluene (10 mL) was added with Pd (PPh ₃ ) _4, and the mixture was stirred under reflux in an oil bath for 12 hours. The reaction mixture was cooled at room temperature, and the remaining solvent was removed by vacuum distillation. The solvent was separated by column chromatography (MC: Hexane = 1: 1.5) to obtain an orange solid 5-b compound. ^{1 HNMR (CDCl3): 0.90-1.00 (} 24H, m), 1.30-1.54 (32H, m), 1.71-1.74 (4H, m), 2.91-2.93 (4H, m), 4.26-4.28 (4H, m) , 6.97-6.98 (2H, d), 7.38-7.39 (2H, d), 7.62 (2H, s), 7.76 (2H, s).

(2) Synthesis of formula 5-c

Compound 5-c was prepared in the same manner as in the preparation of Compound 1-3-2 of Example 1-3, but using Compound 5-b instead of Compound 3-a.

Examples 1-6. Synthesis of 6-d

(1) Synthesis of formula 6-a

2-hexylthiophene (10.0 g, 59.4 mmol) was dissolved in 500 mL of tetrahydrofuran (THF), and the temperature was lowered to -78 ° C. 2.5 M n-BuLi (2.5 M n-Butyllithium in hexane, 24.0 ml, 59.4 mmol) dissolved in hexane was slowly added and stirred for 30 minutes. Thereafter, the temperature was raised to 0 ° C. and the mixture was stirred for 1 hour. Then, 4,8-dehydrobenzo [1,2-b: 4,5-b '] dithiophene- 4,5-b '] dithiophene-4,8-dione, 3.3 g, 14.8 mmol) was added in one portion, and the mixture was stirred at 50 ° C for 3 hours. The solution was cooled to room temperature and added with tin (II) chloride dihydrate (SnCl ₂ .2H ₂ O) (26 g) and 10% HCl (56 ml) Respectively. Ice was added to the solution, extracted twice with diethyl ether, washed twice with water, and the residue was removed with magnesium sulfate (MgSO ₄ ). The solvent was removed from the remaining solution under reduced pressure, and a yellow, dense liquid was obtained through a silica column (eluent; Petroleum) (yield: 64%).

(2) Synthesis of formula 6-b

6-a (3.9 g, 7.43 mmol) was dissolved in 100 mL of tetrahydrofuran (THF) and the temperature was lowered to 0 ° C. At this temperature, 1.6M n-BuLi (1.6M n-Butyllithium in hexane, 10.4ml, 16.7mmol) dissolved in hexane was slowly added and stirred at room temperature for 1 hour. 1M Trimethyltinchloride in THF (22.7 ml, 22.7 mmol) dissolved in tetrahydrofuran (THF) was added to the reaction solution in one portion, followed by stirring for 2 hours. Water was poured into this solution, extracted twice with diethyl ether, washed twice with water, and the residue was removed with magnesium sulfate (MgSO ₄ ). The solvent was removed under reduced pressure, and the solvent was recrystallized from ethanol to obtain a pale yellow crystalline solid (yield: 87%).

12 shows the NMR spectrum of the formula 6-b.

13 shows the MS spectrum of the formula 6-b.

(3) Synthesis of formula 6-c

Compound 6-c was prepared in the same manner as in the preparation of the compound of the formula 1-3-1 of Example 1-3, except that the compound of the formula 6-b was used instead of the compound of the formula 4-c.

(4) Synthesis of formula 6-d

Compound 6-d was prepared using Compound 6-c instead of Compound 3-a in the preparation of Compound 1-3-2 of Example 1-3.

Examples 1-7. Synthesis of Formula 7-d

(1) Synthesis of Formula 7-a

2- (2-ethylhexyl) thiophene (10.0 g, 59.4 mmol) was dissolved in 500 ml of tetrahydrofuran (THF) and the temperature was lowered to -78 ° C. At this temperature, 2.5 M n-BuLi (2.5 M n-Butyllithium in hexane, 24.0 ml, 59.4 mmol) dissolved in hexane was slowly added and stirred for 30 minutes. Thereafter, the temperature was raised to 0 ° C and stirred for 1 hour in this state. After that, 4,8-dehydrobenzo [1,2-b: 4,5-b '] dithiophene-4,8- -dehydrobenzo [l, 2-b: 4,5-b '] dithiophene-4,8-dione, 3.3 g, 14.8 mmol) was added in one portion and stirred at 50 ° C for 3 hours. The solution was cooled to room temperature and added with tin (II) chloride dihydrate (SnCl ₂ .2H ₂ O) (26 g) and 10% HCl (56 ml) and stirred for an additional 3 hours. Ice was poured into this solution, extracted twice with diethyl ether, washed twice with water, and the residue was removed with magnesium sulfate (MgSO ₄ ). The solvent was removed from the remaining solution under reduced pressure, and a yellow, dense liquid was obtained through a silica column (eluent; Petroleum) (yield: 64%).

(2) Synthesis of formula 7-b

7-a (3.9 g, 7.59 mmol) was dissolved in 100 ml of tetrahydrofuran (THF) and the temperature was lowered to 0 ° C. At this temperature, 1.6M n-BuLi (1.6M n-Butyllithium in hexane, 10.4ml, 16.7mmol) dissolved in hexane was slowly added and stirred at room temperature for 1 hour. To this solution was added 1M trimethyltinchloride in THF (22.7 ml, 22.7 mmol) dissolved in THF in one portion, followed by stirring for 2 hours. Water was poured into this solution, extracted twice with diethyl ether, washed twice with water, and the residue was removed with magnesium sulfate (MgSO ₄ ). The solvent was removed under reduced pressure, and the solvent was recrystallized from ethanol to obtain a pale yellow crystalline solid (yield: 87%).

14 is an NMR spectrum showing the formula 7-b.

(3) Synthesis of formula 7-c

Compound 7-c was prepared in the same manner as in the preparation of the compound of the formula 1-3-1 of Example 1-3, except that the compound of the formula 7-b was used instead of the compound of the formula 4-c.

(4) Synthesis of formula 7-d

Compound 7-d was prepared in the same manner as in the preparation of Compound 1-3-2 of Example 1-3, but using Compound 7-c instead of Compound 3-a.

Examples 1-8. Synthesis of 8-d

(1) Synthesis of formula 8-a

2- (2-ethylhexyl) selsnophene (5.0 g, 23.2 mmol) was dissolved in 300 ml of tetrahydrofuran (THF) and the temperature was lowered to -78 ° C. 2.5 M n-BuLi (2.5 M n-Butyllithium in hexane, 11.1 ml, 27.9 mmol) dissolved in hexane was added slowly and stirred for 1 hour. Thereafter, the temperature was raised to 0 ° C and the mixture was stirred for 1 hour at the ideal state. Thereafter, 4,8-dehydrobenzo [1,2-b: 4,5- b '] dithiophene- dihydrobenzo [l, 2-b: 4,5-b '] dithiophene-4,8-dione, 2.1 g, 9.28 mmol) was added in one portion and stirred at 50 ° C for 6 hours. The temperature of the solution was lowered to room temperature and then tin (II) chloride dihydrate (SnCl ₂ .2H ₂ O) (tin (II) chloride dehydrate, 15 g) and 10% HCl (30 ml) were added and stirred for further 3 hours. Ice was poured into the solution, extracted with diethyl ether, and the residue was removed with magnesium sulfate (MgSO ₄ ). The solvent was removed from the remaining solution under reduced pressure, and a yellow, dense liquid was obtained through a silica column (eluent; Petroleum) (Yield: 70%).

15 is a diagram showing an NMR spectrum of the formula 8-a.

(2) Synthesis of compound of formula 8-b

Was prepared in the same manner as in Example 1-6-2, except that 2- (2-ethylhexyl) selenophene was used instead of 2- (2-ethylhexyl) selenophene.

3 (2.0 g, 3.24 mmol) was dissolved in 100 ml of tetrahydrofuran (THF) and the temperature was lowered to 0 ° C. 1.6 M n-BuLi (1.6 M n-Butyllithium in hexane, 7.1 ml, 11.3 mmol) dissolved in hexane was added slowly and stirred at room temperature for 1 hour. To this solution was added 1M trimethyltinchloride in THF (8.10 ml, 8.10 mmol) dissolved in THF in one portion, followed by stirring for 2 hours. Water was poured into this solution, extracted with hexane, and then the residue was removed with magnesium sulfate (MgSO ₄ ). The solvent was removed under reduced pressure, and the solvent was recrystallized from ethanol to obtain a pale yellow crystalline solid (yield: 85%).

16 is a diagram showing the NMR spectrum of the formula 8-b.

(3) Synthesis of formula 8-c

Compound 8-c was prepared in the same manner as in the preparation of the compound of the formula 1-3-1 of Example 1-3, except that the compound of the formula 8-b was used instead of the compound of the formula 4-c.

(4) Synthesis of Compound (8-4)

Compound 8-d was prepared in the same manner as in the preparation of the compound of the formula 1-3-2 of Example 1-3 except that the compound of the formula 8-c was used instead of the compound of the formula 3-a.

Examples 1-9. Synthesis of 9-b

2,1,3-benzothiadiazole-4,5-bis (boronic acid pinacol ester, 0.33 g, 0.84 mmol) was added to a solution of 2,1,3-benzothiadiazole- _{), Pd (PPh 3) 4} (0.05 g, 0.04 mmol) with the general formula 1-h compound (0.79 g, 2.10 mmol) in toluene (toluene) 20 mL, aqueous potassium carbonate solution 10ml and ethanol (ethanol) into a 10 ml, The mixture was cooled to room temperature and the solvent was removed under vacuum and dried over anhydrous sodium sulfate.The residue was purified by silica column chromatography ¹ H NMR (CDCl ₃ , 400 MHz): 8.11 (2H, s), 8.03 (2H, s), (IH) ), 7.52 (2H, s), 4.27-4.28 (4H, m), 1.64-1.75 (2H, m), 1.30-1.48 (16H, m), 0.88-0.96 (12H, m).

(2) Synthesis of formula 9-b

N-bromosuccinimide (NBS, 0.22 g, 1.21 mmol) was added dropwise to a round-bottomed flask with 10 ml of chloroform in the form of a compound of the formula 9-a (0.40 g, 0.55 mmol) . To this solution was added deionized (DI) water and extracted several times with heptyl acetate. The solvent was removed under vacuum and dried with anhydrous sodium sulfate. The residue was purified via silica column chromatography (methylene chloride and hexane (1: 1)) to give 9-b (0.37 g, 76.2%) as a blue solid. ^{_{1 H NMR (CDCl 3, 400}} MHz): 7.94 (1H, s), 7.68 (1H, s), 4.23-4.31 (4H, m), 1.64-1.75 (2H, m), 1.30-1.48 (16H, m ), 0.88-0.96 (12H, m).

GC / MS (m / z): Calcd for C38H38Br2N2O4S5, 881.98; found, 882.20 [M] ^< ⁺ & gt ^; .

Examples 1-10. Synthesis of formula 10-b

(1) Synthesis of formula 10-a

(1.02 g, 2.72 mmol) and 5'-hexyl- [2,2 'bithiophen] -5-yl) trimethylstannane (5'-hexyl- [2 5-yl) trimethylstannane (3.37 g, 5.4 mmol) was dissolved in toluene (15 ml) and the solution was added with Pd (PPh ₃ ) ₄ (0.16 g, 0.14 mmol) Lt; / RTI > The reaction mixture was cooled at room temperature, and the remaining solvent was evaporated. The residue was separated by column chromatography (MC: Chloroform: Hexane = 1: 1: 6) to obtain 0.37 g of yellow crystals (yield: 23%).

(2) Synthesis of formula 10-b

N-bromosuccinimide (NBS, 0.36 g, 2.07 mmol) was added dropwise to a round-bottom flask with 20 ml of DMF (1.11 g, 2.07 mmol) and stirred for 30 minutes . To this solution was added deionized (DI) water and extracted several times with ethyl acetate. The solvent was removed under vacuum and dried with anhydrous sodium sulfate. The residue was subjected to silica column chromatography (methylene chloride: hexane = 1: 1) to obtain yellow crystal formula 10-b (0.81 g, 64%).

Examples 1-11. Synthesis of Formula 11-b

(1) Synthesis of Formula 11-a

(5-trimethylstannyl) thiophene-2-yl) benzo [c] thiophene was used in place of the compound 4-C in the formula 3-a of Example 1-3. [1,2,5] thiadiazole (5,6-difluoro-4,7-bis (5- (trimethylstannyl) thiophen-2-yl) benzo [c] Compound 11-a was prepared in the same manner except that

(2) Synthesis of compound of formula 11-b

Compound 11-b was prepared in the same manner as Compound 1-3-2 of Example 1-3, except that Compound 11-a was used instead of Compound 3-a.

Examples 1-12. Synthesis of Formula 12-c

(1) Synthesis of the compound of the formula 12-a

(4-2-ethylhexyl) -5- (trimethylstannyl) thiophen-2-yl) - (4-methylphenyl) 5,6-difluorobenzene [c] [1,2,5] thiazole (4,7-bis (4- (2-ethylhexyl) -5- (trimethylstannyl) thiophen- , 6-difluorobenzo [c] [1,2,5] thiadiazole) and compound (1-h) were used.

(2) Synthesis of compound of formula 12-b

Compound 12-b was prepared in the same manner as Compound 1-3-2 in Example 1-3 except that Compound 12-a was used instead of Compound 3-a.

(2) Synthesis of compound of formula 12-c

(5-formylthiophene-4,4'-diamine) instead of 2,1,3-benzothiadiazole-4,5-bis (boronic acid pinacol ester) 2- yl) boronic acid ((5-formylthiophen-2- yl) boronic acid, 0.39 g, 2.52 mmol), Pd (PPh 3) 4 (0.05 g, 0.04 mmol) and (1.38 g compound of formula 12-b, 1.05 mmol) was added to 30 mL of toluene, 4.0 mL of an aqueous solution of potassium carbonate (30 mL) and 10 mL of ethanol, and the compound of the formula 12-c was prepared in the same manner as in the synthesis of the compound 1-9-1.

Examples 1-13. Synthesis of formula 13-c

(1) Synthesis of Formula 13-a

(3,3'-dioctyl- [2,2 ': 5', 2 "-tterthiophene] -5,5 (trifluoromethyl) thiophene was used in place of the compound 4-C in the synthesis of the compound 3- (3,3 '' - dioctyl- [2,2 ': 5', 2 "-terthiophene] -5,5''-diyl) bis (trimethylstannane) -h The compound 13-a was prepared in the same manner except that the compound was used.

(2) Synthesis of the compound of the formula 13-b

Compound 13-b was prepared in the same manner as Compound 1-3-a in Example 1-3 except that Compound 13-a was used instead of Compound 3-a.

(3) Synthesis of compound of formula 13-c

13-c was prepared in the same manner as in the preparation of 1-12-3 of Example 1-12, except that 13-b was used instead of 12-b.

Examples 1-14. Synthesis of 14-b

Compound 14-b was prepared in the same manner except that Compound 14-a was used instead of Compound 3-a in the preparation of Formula 1-3-2 of Example 1-3, instead of 2 equivalents of NBS.

Examples 1-15. Synthesis of Formula 15-c

(1) Synthesis of formula (15-a)

The compound 15-a was prepared in the same manner as the compound 3-a in Example 1-3 except that the compound 7-d was used instead of the compound 4-c, and the compound 2-h was used instead of 1-h.

(2) Synthesis of compound of formula 15-b

Compound 15-b was prepared in the same manner as in the preparation of Compound 1-3-2 of Example 1-3, except that Compound 7-d was used instead of Compound 3-a.

(3) Synthesis of compound of formula 15-c

Examples 1-16. Synthesis of 16-d

(1) Synthesis of compound of formula (16-b)

Compound 16-b was prepared in the same manner as Compound-3-a in Example 1-3 except that Compound 16-a was used in place of Compound 4-C and Compound 2-h was used in place of Compound 1-h. Respectively.

(2) Synthesis of compound of formula 16-c

Compound 16-c was prepared in the same manner as in the preparation of the compound of the formula 1-3-2 of Example 1-3 except that the compound of the formula 16-b was used instead of the compound of the formula 3-a.

(3) Synthesis of compound of formula 16-d

In the same manner as in the preparation of the compound of the formula 1-12-3 of Example 1-12, except that the compound of the formula 12-b was used instead of the compound of the formula 12-b, the compound of the formula 16-d was prepared.

Production Example 1. Preparation of Formula 1-1-1

(0.36 g, 0.30 mmol) and compound tributyl- (5'-hexyl- [2,2 '] bithiophen-5-yl) 5'-hexyl- [2,2 '] bithiophen -5-yl) -stannane) (0.49g, 0.91mmol) to a solution in toluene _{(toluene) 15ml Pd (PPh 3} ) 4 (0.017g, 0.015mmol) And refluxed in an oil bath for 24 hours. After cooling the reaction mixture at room temperature, the remaining solvent was removed by evaporation, and the residue was separated by column chromatography (MC: Hex = 1: 2) to obtain 0.058 g (12.5%) of dark purple crystals. ¹ H NMR (CDCl ₃ ): 0.88-0.95 (18H, m), 0.97-1.00 (10H, t), 1.10-1.13 (6H, t), 1.30-1.34 (12H, m), 1.37-1.44 ), 1.47-1.53 (12H, m), 2.76-2.80 (4H, t), 4.09-4.18 (4H, m), 4.28-4.30 (4H, m), 6.66-6.67 (4H, m), 7.07-7.08 (2H, d), 7.43 (1H, s), 7.99 (1H, s).

17 is a diagram showing the NMR spectrum of the formula 1-1-1.

18 is a graph showing the results of the mass spectrometry of the Maltitol of Formula 1-1-1.

The results of the Malditto mass spectrometry are m / z = 1530.52, found m / z = 1531.65.

19 is a diagram showing a UV spectrum in a solution state of the formula 1-1-1.

20 is a diagram showing the UV spectrum of the film state of the formula 1-1-1.

As can be seen from the UV spectrum of the film state of Formula 1-1-1, the band gap is lowered from 1.39 eV to 1.59 eV, absorbing a lot of light, and has a band gap suitable for use in combination with other organic materials .

When the HOMO (highest occupied molecular orbital) value of Formula 1-1-1 is -5.14 eV and the lowest unoccupied molecular orbital (LUMO) value is -3.59 eV, when used with an acceptor of PCBM series, the electron donating substance electron donor.

FIG. 21 is a graph showing a cyclic voltammetry result of the chemical formula 1-1-1. FIG.

Production example 2. Preparation of formula 1-1-2

Compound 1-1-2 was subjected to silica column chromatography (HEX: MC = 10: 4) in the same manner as in Production Example 1, except that Compound 6-d was used instead of Compound 3-b. I got a dark red solid through. (Yield: 69%).

PREPARATION EXAMPLE 3 Preparation of Formula 1-1-3

Compound 1-1-3 was subjected to silica column chromatography (HEX: MC = 10: 4) to obtain a dark red solid in the same manner as in Production Example 1, except that the compound of Formula 7-d was used.

Production Example 4. Preparation of Formula 1-1-4

Compound 1-1-4 was subjected to silica column chromatography (HEX: MC = 10: 4) in the same manner as in Production Example 1, except that the compound of Formula 8-d was used instead of the compound of Formula 3-b. To obtain a dark red solid.

Production Example 5. Preparation of Formula 1-1-5

Compound 1-1-5 was subjected to silica column chromatography (HEX: MC = 10: 4) in the same manner as in Production Example 1, except that Compound 9-b was used instead of Compound 3-b. I got a dark red solid through.

22 is a diagram showing a UV spectrum in a solution state of the formula 1-1-5. 23 is a diagram showing the UV spectrum of the film state of the formula 1-1-5.

Preparation Example 6. Preparation of Formulas 1-1-6

After dissolving 1.19 g of 12-c (0.87 mmol, 1.0 equiv) and 1.4 g of 3-ethylrhodanine (8.7 mmol, 10 equiv) in 30 mL of anhydrous chloroform, catalytic amount of piperidine. The reaction mixture was stirred at 70 < 0 > C for 12 hours. After the reaction mixture was cooled to room temperature, Compound 1-1-6 was obtained through silica gel chromatography using chloroform. (865 mg, yield = 60%).

Production Example 7. Preparation of Formula 1-1-7

In the same manner as in Production Example 6, except for using the compound of the formula 13-c instead of the compound of the formula 12-c, the compound 1-1-7 was reacted through a silica column (HEX: MC = 10: 4) A dark red solid was obtained.

Preparation Example 8. Preparation of Formula 1-1-8

In the same manner as in Production Example 6 except for using the compound of the formula 16-d instead of the compound of the formula 12-c, the compound 1-1-8 was reacted through a silica column (HEX: MC = 10: 4) A dark red solid was obtained.

Preparation Example 9. Preparation of the formula (II-6)

In the same manner as in Production Example 6 except for using the compound of the formula 16-d instead of the compound of the formula 12-c, the compound 2-1-6 was reacted via a silica column (HEX: MC = 10: 4) A dark red solid was obtained.

PREPARATION EXAMPLE 10 Preparation of Formula 2-1-9

In the same manner as in Production Example 1 except that the compound of Formula 12-b was used instead of the compound of Formula 3-b, the compound 2-1-9 was reacted with a silica column (HEX: MC = 2: 1) I got a dark red solid through.

Experimental Example 1. Preparation of Organic Solar Cell

The compound of Formula 1-1-1 of Preparation Example 1 was used as an electron donor and PC ₆₀ BM was used as an electron acceptor in a mixing ratio of 7: 3 (w / w ratio), dissolved in chlorobenzene A composite solution was prepared. At this time, the concentration was adjusted to 4.0 wt%, and the organic solar cell had the structure of ITO / PEDOT: PSS / photoactive layer / LiF / Al. The glass substrate coated with ITO was ultrasonically cleaned using distilled water, acetone and 2-propanol, and the ITO surface was ozone-treated for 10 minutes and spin coated with PEDOT: PSS (Baytrom P) to a thickness of 45 nm. Min. In order to coat the photoactive layer, the compound-PCBM composite solution was filtered with a 0.45 μm PP syringe filter, and then spin-coated. Al was deposited to a thickness of 200 nm using a thermal evaporator under a vacuum of 3 × 10 ^-8 torr An organic solar cell device was fabricated.

Experimental Example 2. Preparation of Organic Solar Cell

In Experimental Example 1, instead of the compound of Formula 1-1-1, the compound of Formula 1-1-2 was used as an electron donor, PC ₆₀ BM was used as an electron acceptor, a compounding ratio of 1: 1 (w / w ratio) (CB), and an organic solar cell device was fabricated under the same conditions as Experimental Example 1.

Experimental Example 3. Preparation of Organic Solar Cell

In Experimental Example 1, the compound of Formula 1-1-1 was used instead of the compound of Formula 1-1-1 as an electron donor, and PC ₆₀ BM was used as an electron acceptor in a ratio of 2: 1 (w / w ratio) And a solvent was chlorobenzene (CB), and an organic solar cell device was fabricated under the same conditions as Experimental Example 1.

Experimental Example 4. Preparation of Organic Solar Cell

In Experimental Example 1, instead of the compound of Formula 1-1-1, the compound of Formula 1-1-4 was used as an electron donor, PC ₆₀ BM was used as an electron acceptor, a compounding ratio of 1: 1 (w / w ratio) And a solvent was chlorobenzene (CB), and an organic solar cell device was fabricated under the same conditions as Experimental Example 1.

Experimental Example 5. Preparation of Organic Solar Cell

In Experimental Example 1, instead of the compound of Formula 1-1-1, a compound of Formula 1-1-5 was used as an electron donor, and PC ₆₀ BM was used as an electron acceptor with a mixing ratio of 1: 1 (w / w ratio ) And a solvent was chlorobenzene (CB), and an organic solar cell device was fabricated under the same conditions as Experimental Example 1. [

Experimental Example 6: Manufacture of organic solar cell

In Experimental Example 1, instead of the compound of Formula 1-1-1, the compound of Formula 1-1-6 was used as an electron donor and PC ₆₀ BM was used as an electron acceptor in a mixing ratio of 7: 3 (w / w ratio) And a solvent was chlorobenzene (CB), and an organic solar cell device was fabricated under the same conditions as Experimental Example 1.

Experimental Example 7. Preparation of Organic Solar Cell

In Experimental Example 1, instead of the compound of Formula 1-1-1, a compound of Formula 1-1-7 was used as an electron donor and PC ₆₀ BM was used as an electron acceptor with a compounding ratio of 1: 1 (w / w ratio) And a solvent was chlorobenzene (CB), and an organic solar cell device was fabricated under the same conditions as Experimental Example 1.

Experimental Example 8. Preparation of Organic Solar Cell

In Experimental Example 1, instead of the compound of Formula 1-1-1, a compound of Formula 1-1-8 was used as an electron donor, and PC ₆₀ BM was used as an electron acceptor with a compounding ratio of 1: 2 (w / w ratio ) And a solvent was chlorobenzene (CB), and an organic solar cell device was fabricated under the same conditions as Experimental Example 1. [

Experimental Example 9: Manufacture of organic solar cell

In Experimental Example 1, instead of the compound of Formula 1-1-1, the compound of Formula 2-1-6 was used as an electron donor, and PC ₆₀ BM was used as an electron acceptor in a mixing ratio of 1: 2 (electron donor 4.0 wt / (CB): PC61BM (DIO) / MoO ₃ / Ag, and the organic solar cell was made of ITO / ZnO / Chemical Formula 1-2-1 (CB): PC61BM Structure.

Experimental Example 10. Preparation of Organic Solar Cell

In Experimental Example 1, instead of the compound of Formula 1-1-1, the compound of Formula 2-1-9 was used as an electron donor, PC ₆₀ BM was used as an electron acceptor, a compounding ratio of 1: 1 (w / w ratio) And a solvent was chlorobenzene (CB), and an organic solar cell device was fabricated under the same conditions as Experimental Example 1.

The photoelectric conversion characteristics of the organic solar cell were measured under the condition of 100 mW / cm ² , and the results are shown in Table 1 below.

V _oc (V) J _sc
(mA / cm ² ) FF (%) PCE (%) Experimental Example 1 Formula 1-1-1: PC ₆₁ BM
= 7: 3 0.69 4.01 57.37 1.58 Experimental Example 2 Formula 1-1-2: PC ₆₁ BM
= 1: 1 0.56 0.97 51.4 0.28 Experimental Example 3 Formula 1-1-3: PC ₆₁ BM
= 2: 1 0.73 5.7 52 2.16 Experimental Example 4 Formula 1-1-4: PC ₆₁ BM
= 1: 1 0.74 8.2 51 3.05 Experimental Example 5 Formula 1-1-5: PC ₆₁ BM
= 1: 1 0.73 5.7 56.3 2.34 Experimental Example 6 Formula 1-1-6: PC ₆₁ BM
= 7: 3 0.69 10.1 53.8 3.75 Experimental Example 7 Formula 1-1-7: PC ₆₁ BM
= 1: 1 0.74 10.2 54.4 4.11 Experimental Example 8 Formula 1-1-8: PC ₆₁ BM
= 1: 2 0.69 7.5 54.4 2.82 Experimental Example 9 Formula 2-1-6: PC ₆₁ BM
= 1: 2 0.86 11.1 52 4.96 Experimental Example 10 Formula 2-1-9: PC ₆₁ BM
= 1: 1 0.81 9.7 53.1 4.17

In Table 1, Voc is the open-circuit voltage, Jsc is the short-circuit current, FF is the fill factor, and PCE is the energy conversion efficiency. The open-circuit voltage and the short-circuit current are the X-axis and Y-axis intercepts in the fourth quadrant of the voltage-current density curve, respectively. The higher the two values, the higher the efficiency of the solar cell. The fill factor is the width of the rectangle that can be drawn inside the curve divided by the product of the short-circuit current and the open-circuit voltage. The energy conversion efficiency can be obtained by dividing these three values by the intensity of the irradiated light, and a higher value is preferable.

24 is a graph showing the current density according to the voltage of the organic solar battery of Experimental Example 1. Fig.

25 is a graph showing the current density according to the voltage of the organic solar battery of Experimental Example 2. Fig.

From the results of Table 1, it can be confirmed that the heterocyclic compound according to one embodiment of the present invention can be used as a material for an organic solar cell.

101: first electrode
102: hole transport layer
103: photoactive layer
104: electron transport layer
105: second electrode

Claims

A heterocyclic compound comprising a unit represented by the following formula (1) or (2):
[Chemical Formula 1]

(2)

In formulas (1) and (2)
L1, L2, L1 'and L2' are the same or different and are each independently a direct bond; Or a substituted or unsubstituted divalent heterocyclic group,
L and L 'are the same or different and are each independently a substituted or unsubstituted divalent heterocyclic group,
R1, R3, R1 'and R3' are the same or different and each independently a substituted or unsubstituted ester group,
R2, R4, R2 'and R4' are the same or different from each other and are each hydrogen or a halogen group.

The method according to claim 1,
L1, L2, L1 'and L2' are the same as each other, and are each independently a direct bond; Or represented by any one of the following structural formulas,
L and L 'are the same or different from each other and each independently represents a heterocyclic compound represented by any one of the following formulas:

In the above structure,
X1 to X6 are the same or different from each other and each independently CRR ', NR, O, SiRR', PR, S, GeRR '
Y1 and Y2 are the same or different and are each independently CR ", N, SiR", P or GeR "
A substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, Substituted or unsubstituted alkyl group, substituted or unsubstituted allyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted ester group, substituted or unsubstituted amide group, A substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, .

The method according to claim 1,
(1) is represented by the following general formula (1-1)
Wherein the formula 2 is a heterocyclic compound represented by the following formula 2-1:
[Formula 1-1]

[Formula 1-2]

In formulas (1-1) and (1-2)
L, L ', L1, L1', L2, L2 ', R2, R4, R2' and R4 '
A1 to A4 are the same or different from each other, and each independently hydrogen; A halogen group; A nitro group; Cyano; A carboxyl group; A hydroxy group; A substituted or unsubstituted carbonyl group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted allyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted ester group; A substituted or unsubstituted amide group; A substituted or unsubstituted ether group; A substituted or unsubstituted sulfonyl group; A substituted or unsubstituted sulfoxy group; A substituted or unsubstituted arylalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

The method according to claim 1,
Wherein the terminal of the heterocyclic compound is represented by the following Formula 3:
(3)

In formula (3)
d is an integer of 1 to 5,
X is selected from the group consisting of CRaRb, NRa, O, SiRaRb, PRa, S, GeRaRb, Se and Te,
Ra, Rb, R6 and R7 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; And a substituted or unsubstituted heterocyclic group,
R8 is hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; A substituted or unsubstituted heterocyclic group or a structure represented by the following formula

In the above structure,
Cy is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
R100 and R101 are the same or different from each other, and each independently hydrogen; A halogen group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted haloalkyl group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

The method according to claim 1,
Wherein the heterocyclic compound represented by Formula 1 or 2 is represented by any one of the following Formulas 4 to 19:
[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

In Formulas 4 to 19,
d and d 'are the same as or different from each other, each independently an integer of 1 to 5,
When d and d 'are two or more, the structures in parentheses of two or more are the same or different from each other,
a and b are the same as or different from each other, each independently an integer of 0 or 1,
X and X 'are the same or different from each other and each independently selected from the group consisting of CRaRb, NRa, O, SiRaRb, PRa, S, GeRaRb,
X1 to X6, X10 and X11 are the same or different from each other and each independently CRR ', NR, O, SiRR', PR, S, GeRR '
Y1 and Y2 are the same or different and are each independently CR ", N, SiR", P or GeR "
Wherein R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 6, R 6, R 7, A substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted alkylthio group, or a substituted or unsubstituted alkylthio group; A substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted arylthioxy group, a substituted or unsubstituted alkylsulfoxy group, a substituted or unsubstituted arylsulfoxy group, a substituted or unsubstituted alkenyl group, A substituted or unsubstituted alkylamine group, a substituted or unsubstituted aralkylamine group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted heteroarylamine group, a substituted or unsubstituted aryl group, An unsubstituted heterocyclic group,
A1 to A4 are the same or different from each other, and each independently hydrogen; A halogen group; A nitro group; Cyano; A carboxyl group; A hydroxy group; A substituted or unsubstituted carbonyl group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted allyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted ester group; A substituted or unsubstituted amide group; A substituted or unsubstituted ether group; A substituted or unsubstituted sulfonyl group; A substituted or unsubstituted sulfoxy group; A substituted or unsubstituted arylalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
R2, R4, R2 'and R4' are the same or different from each other, and each independently hydrogen; Or a halogen group,
R8 and R8 'are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; A substituted or unsubstituted heterocyclic group or a structure represented by the following formula

The method according to claim 1,
Wherein the heterocyclic compound represented by Formula 1 is represented by any one of the following Formulas 1-1-1 to 1-1-16:
[Formula 1-1-1]

[Formula 1-1-2]

[Formula 1-1-3]

[Formula 1-1-4]

[Formula 1-1-5]

[Formula 1-1-6]

[Formula 1-1-7]

[Formula 1-1-8]

[Formula 1-1-9]

[Formula 1-1-10]

[Formula 1-1-11]

[Formula 1-1-12]

[Formula 1-1-13]

[Formula 1-1-14]

[Formula 1-1-15]

[Formula 1-1-16]

The method according to claim 1,
Wherein the heterocyclic compound represented by Formula 2 is represented by any one of the following Formulas 2-1-1 to 2-1-16:
[Formula 2-1-1]

[Formula 2-1-2]

[Chemical Formula 2-1-3]

[Chemical Formula 2-1-4]

[Formula 2-1-5]

[Formula 2-1-6]

[Formula 2-1-7]

[Formula 2-1-8]

[Formula 2-1-9]

[Formula 2-1-10]

[Chemical Formula 2-1-11]

[Formula 2-1-12]

[Formula 2-1-13]

[Chemical Formula 2-1-14]

[Chemical Formula 2-1-15]

[Chemical Formula 2-1-16]

A first electrode; A second electrode facing the first electrode; And at least one organic layer disposed between the first electrode and the second electrode and including a photoactive layer,
Wherein at least one of the organic material layers comprises the heterocyclic compound according to any one of claims 1 to 7.

The method of claim 8,
Wherein the organic material layer includes a hole transporting layer, a hole injecting layer, or a layer simultaneously transporting holes and injecting holes,
Wherein the hole transporting layer, the hole injecting layer, or the layer simultaneously transporting the holes and the hole injecting layer comprises the heterocyclic compound.

The method of claim 8,
Wherein the organic material layer includes an electron injection layer, an electron transport layer, or a layer that simultaneously performs electron injection and electron transport,
Wherein the electron injecting layer, the electron transporting layer, or the layer which simultaneously injects electrons and transports electrons comprises the heterocyclic compound.

The method of claim 8,
Wherein the photoactive layer comprises one or more selected from the group consisting of an electron donor and an electron donor,
Wherein the electron donor comprises the heterocyclic compound.

The method of claim 11,
Wherein the electron acceptor is selected from the group consisting of fullerene, a fullerene derivative, a heterocyclic compound, a semiconductor element, a semiconducting compound, and a combination thereof.

The method of claim 11,
Wherein the electron donor and the electron acceptor constitute bulk heterojunction (BHJ).

The method of claim 8,
The photoactive layer is a bilayer structure including an n-type organic layer and a p-type organic layer,
Wherein the p-type organic compound layer comprises the heterocyclic compound.