KR102093470B1 - Novel compound and organic electronic device using them - Google Patents

Abstract

The present invention relates to a novel compound and an organic electronic device using the same, and the compound of the present invention forms a two-dimensional conjugated structure, has excellent crystallization properties, and can effectively improve the intermolecular stacking of planar molecular sieves. Thus, the organic electronic device employing the compound of the present invention can increase the face-on fraction and ultimately realize high photoelectric conversion efficiency.

Description

Novel compound and organic electronic device using them

The present invention relates to novel compounds and organic electronic devices using the same.

Typical examples of the organic electronic device include an organic light emitting device (OLED), an organic thin film transistor (OTFT), an organic optical sensor (OPD), an organic solar cell (OPV), a photodetector, a memory device, and a logic circuit.

Among them, the organic solar cell uses an electron donor and an acceptor as a photoactive layer at the same time, and the film formation conditions are less demanding than conventional inorganic semiconductor devices, and the thickness is thinner than hundreds of nm and relatively low photoactivity. Many studies have been conducted in recent years due to the advantage of being able to fabricate a flexible device that can be bent at will, especially the material of a layer.

Specifically, the organic solar cell is composed of a junction structure of an electron donor and an electron acceptor, and is a very fast charge transfer phenomenon called a “photoinduced charge transfer (PICT)” between the electron donor and the electron acceptor, Research is being conducted to obtain a high-efficiency organic solar cell by increasing the photoexcitation charge transfer phenomenon.

Currently, many studies have been conducted on compounds used as electron donors in organic solar cells, mainly with p-type conductive polymers. For example, poly para-phenylenevinylene (hereinafter referred to as “PPV”) series Recently, various derivatives mainly based on low bandgap polymers have been used, including high-molecular weight compounds and polythiophene (hereinafter referred to as “PT”) polymer compounds.

Also, as an electron acceptor of an organic solar cell, PCBM ({6} -1- (3- (methoxycarbonyl) propyl), a metanofullerene derivative, published by Fred Wudl Group in 1995)-{ 5} -1-phenyl [5,6] C61 ({6} -1- (3- (methoxy carbonyl) propyl)-{5} -1-phenyl [5,6] C61)), and Other monomolecules include perylene, 3,4,9,10-perylenetetracarboxylic diimide, phthalocyanine, and pentacene. However, since fullerene derivatives, as well as fullerene derivatives represented by PCBM, have low solubility in organic solvents, there is a problem in that phase separation occurs when mixing with a polymer compound used as an electron donor or overall efficiency is low. have. Moreover, solar absorption is weak and energy level manipulation is difficult.

Accordingly, there is an urgent need for research on a compound to replace fullerene.

However, various studies have been conducted on electron donors centered on low-bandgap polymers, but few studies have been conducted on compounds to replace fullerene derivatives used as electron acceptors.

Specifically, as a replaceable compound of the fullerene derivative, it is necessary to study a compound having high electron affinity similar to fullerene and excellent compatibility with the electron donor, high absorption coefficient for sunlight, and excellent photoelectric conversion efficiency.

US Patent Publication No. 2006-0011233

In order to solve the above problems, the present invention aims to provide a novel compound having an extended conjugated structure.

An object of the present invention is to provide an organic electronic device having excellent light efficiency by employing the compound of the present invention.

An object of the present invention is to provide an organic solar cell having significantly improved photoelectric conversion efficiency as the compound of the present invention is employed as an electron acceptor material for a photoactive layer.

For the above-mentioned purposes, the present invention may include the following means.

The compound according to an embodiment of the present invention has a central skeleton extended to a two-dimensional region, and forms a delocalized pi-electron field along the central skeleton, which may be represented by the following Chemical Formula 1.

[Formula 1]

[In the above formula 1,

R ₁ to R ₈ are each independently C6-C20 aryl or C3-C20 heteroaryl, and the aryl or heteroaryl is each independently C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, halogen, cyano And one or more substituents selected from halo C1-C30 alkyl and the like;

로 대체될 수 있으며, 상기 R은 수소, C1-C30알킬, C1-C30알콕시, C1-C30알킬티오, 할로겐, 시아노, 니트로, 히드록시, 할로C1-C30알킬, C1-C30알킬카보닐 또는 C1-C30알킬카보닐옥시이고;V ₁ and V ₂ are each independently a fused ring having methylidene as a linking group, and each of the fused rings is independently C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, halogen, cyano, nitro, and hydro It may be further substituted with one or more substituents selected from hydroxy and halo C1-C30 alkyl, etc., -CH ₂ -of the fused ring is carbonyl, sulfinyl or

Can be replaced by, R is hydrogen, C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, halogen, cyano, nitro, hydroxy, halo C1-C30 alkyl, C1-C30 alkylcarbonyl or C1-C30 alkylcarbonyloxy;

Y ₁ to Y ₄ are each independently O, S or Se;

The heteroaryl includes one or more heteroatoms selected from N, O, S and Se, etc.]

The compound according to an embodiment of the present invention in Formula 1, V ₁ and V ₂ may be each independently represented by the following formula (2).

[Formula 2]

[In the formula 2,

X ₁ and X ₂ are each independently O, S or CR ₂₁ R ₂₂ , and R ₂₁ and R ₂₂ are each independently halogen, cyano, nitro, hydroxy, C1-C30 alkylcarbonyl or C1-C30 alkyl Carbonyloxy;

A is an aromatic fused ring, and the aromatic fused ring is one or more substituents selected from C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, halogen, cyano, nitro, hydroxy and halo C1-C30 alkyl. Can be further substituted.]

The compound according to an embodiment of the present invention in Formula 1, V ₁ and V ₂ may be each independently represented by the following Formula 3 or Formula 4.

[Formula 3]

[Formula 4]

[In the formulas 3 and 4,

X ₁ and X ₂ are each independently O, S or CR ₂₁ R ₂₂ , and R ₂₁ and R ₂₂ are each independently halogen, cyano, nitro, hydroxy, C1-C30 alkylcarbonyl or C1-C30 alkyl Carbonyloxy;

One of Z ₁ and Z ₂ is -CH =, and the other is O, S or Se;

Z ₃ is -C (R ₂₃ ) = or N, and R ₂₃ is hydrogen, C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, halogen, cyano, nitro, hydroxy or halo C1-C30 Can be linked to an alkyl or adjacent substituent R ₁₂ or R ₁₃ to form an aromatic fused ring;

R ₁₁ to R ₁₄ are each independently hydrogen, C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, halogen, cyano, nitro, hydroxy or haloC1-C30 alkyl.]

The compound according to an embodiment of the present invention in Formula 1, wherein R ₁ to R ₈ are each independently aryl such as phenyl, naphthyl and biphenyl; And heteroaryl such as thiophene, thienothiophene, bithiophene, selenophene, selenoselenophene, and biselenophene; the aryl or heteroaryl is independently C1-C30 alkyl, C1-C30 alkoxy, and It may be substituted with one or more substituents selected from C1-C30 alkylthio.

An organic electronic device including the compound of Formula 1 is provided.

The organic electronic device according to an embodiment of the present invention may be an organic light emitting device, an organic thin film transistor, an organic photosensor or an organic solar cell.

The organic electronic device according to an embodiment of the present invention may include the compound of Formula 1 in the photoactive layer of the organic solar cell.

The organic electronic device according to an embodiment of the present invention may be a compound of Formula 1 used as an electron acceptor. Specifically, the compound of Formula 1 may be included as an electron acceptor in the photoactive layer of the organic solar cell.

The compound of the present invention has a low bandgap, has excellent crystallization properties, and implements effective intermolecular stacking of planar molecular sieves. Accordingly, the compound of the present invention has a high absorption coefficient for sunlight and has an absorption spectrum of almost all wavelengths (eg full color) in the visible region.

The organic electronic device employing the compound of the present invention has a high absorption coefficient and can efficiently absorb sunlight, and can realize excellent photoelectric conversion efficiency with high charge transfer characteristics.

Furthermore, the organic electronic device employing the compound of the present invention as an electron acceptor material can lower the driving voltage, improve light efficiency, and improve the life characteristics of the device by thermal stability of the compound.

With such properties, according to the present invention, it is used as a compound that can replace the fullerene derivative widely used as an electron acceptor, so that the stability and photoelectric conversion efficiency of an organic solar cell can be remarkably improved. That is, the compound of the present invention may be highly applicable as a non-fullerene-based electron acceptor.

The novel compound according to the present invention and the organic electronic device using the same will be described below, but unless otherwise defined in the technical terms and scientific terms used at this time, those skilled in the art to which the present invention pertains generally understand Descriptions of well-known functions and configurations that have meaning and that may unnecessarily obscure the subject matter of the present invention are omitted in the following description.

Substituents including the terms, “alkyl”, “alkoxy”, “alkylthio” and other alkyl moieties described herein include both straight-chain or ground forms. In addition, the alkoxy and alkylthio mean a monovalent organic radical represented by "* -O-alkyl" and "* -S-alkyl", respectively.

In addition, the term "aryl" described herein is an aromatic ring monovalent organic radical derived from an aromatic hydrocarbon by removal of one hydrogen, suitably 4 to 7, preferably 5 or 6 carbon atoms in each ring. It includes a single or fused ring system, and includes a form in which multiple aryls are connected by a single bond. Examples include, but are not limited to, phenyl, naphthyl, biphenyl, and the like.

In addition, the term "heteroaryl" described in the present specification is a heteroaromatic ring monovalent organic radical derived from a heteroaromatic ring derived by one hydrogen removal, 1 to 4 selected from N, O, S, Se, etc. It includes heteroatoms, and includes a form in which multiple heteroaryls are connected by a single bond. Examples include, but are not limited to, thiophene, thienothiophene, bithiophene, selenophene, selenoselenophene, and biselenophene.

In addition, the term "carbonyl" described in this name means a divalent organic radical represented by * -C (= O)-*.

In addition, the term "sulfinyl" described in this specification means a divalent organic radical represented by * -C (= S)-*.

Also, the term “halogen” as described herein means a fluorine, chlorine, bromine or iodine atom.

The compound of the present invention has a central skeleton with high planarity, and forms a de-localized pi-electron field along the central skeleton. In addition, the compounds of the present invention can significantly improve the face-on fraction where the unlocalized pi-electron system is arranged to be positioned parallel to the substrate.

That is, the compound of the present invention forms a plate-like two-dimensional structure with high planarity, and the possibility of forming a face-on lamination structure parallel to the substrate is increased by a delocalized pi-electron system along the central skeleton. Accordingly, the effect of increasing the charge mobility in the vertical direction is caused, and the electron density is significantly improved to increase the interaction between molecules as well as the efficiency of charge transport.

In addition, the compound of the present invention has a high absorption coefficient for sunlight, an excellent solubility in an organic solvent and miscibility with an electron donor (eg, a polymer compound such as polythiophene).

Hereinafter, a novel compound according to the present invention will be described.

Compound according to an embodiment of the present invention may be represented by the following formula (1).

[Formula 1]

[In the above formula 1,

R ₁ to R ₈ are each independently C6-C20 aryl or C3-C20 heteroaryl, and the aryl or heteroaryl is each independently C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, halogen, cyano And one or more substituents selected from halo C1-C30 alkyl and the like;

로 대체될 수 있으며, 상기 R은 수소, C1-C30알킬, C1-C30알콕시, C1-C30알킬티오, 할로겐, 시아노, 니트로, 히드록시, 할로C1-C30알킬, C1-C30알킬카르보닐 또는 C1-C30알킬카르보닐옥시이고;V ₁ and V ₂ are each independently a fused ring having methylidene as a linking group, and each of the fused rings is independently C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, halogen, cyano, nitro, and hydro It may be further substituted with one or more substituents selected from hydroxy and halo C1-C30 alkyl, etc., -CH ₂ -of the fused ring is carbonyl, sulfinyl or

Can be replaced by, R is hydrogen, C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, halogen, cyano, nitro, hydroxy, halo C1-C30 alkyl, C1-C30 alkylcarbonyl or C1-C30 alkylcarbonyloxy;

Y ₁ to Y ₄ are each independently O, S or Se;

The heteroaryl includes one or more heteroatoms selected from N, O, S and Se, etc.]

The compound of the present invention introduced a fused ring using methylidene as a linker to further improve the intermolecular interaction by forming an extended conjugate out of the central skeleton.

Specifically, the fused ring (eg, V ₁ and V ₂ ) using the methylidene as a linking group may be represented by the following Chemical Formula 2.

[Formula 2]

[In the formula 2,

X ₁ and X ₂ are each independently O, S or CR ₂₁ R ₂₂ , and R ₂₁ and R ₂₂ are each independently halogen, cyano, nitro, hydroxy, C1-C30 alkylcarbonyl or C1-C30 alkyl Carbonyloxy;

A is an aromatic fused ring, and the aromatic fused ring is one or more substituents selected from C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, halogen, cyano, nitro, hydroxy and halo C1-C30 alkyl. Can be further substituted.]

More specifically, the fused ring (eg, V ₁ and V ₂ ) using the methylidene as a linking group may be represented by the following Chemical Formula 3 or 4.

[Formula 3]

[Formula 4]

[In the formulas 3 and 4,

X ₁ and X ₂ are each independently O, S or CR ₂₁ R ₂₂ , and R ₂₁ and R ₂₂ are each independently halogen, cyano, nitro, hydroxy, C1-C30 alkylcarbonyl or C1-C30 alkyl Carbonyloxy;

One of Z ₁ and Z ₂ is -CH =, and the other is O, S or Se;

Z ₃ is -C (R ₂₃ ) = or N, and R ₂₃ is hydrogen, C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, halogen, cyano, nitro, hydroxy or halo C1-C30 Can be linked to an alkyl or adjacent substituent R ₁₂ or R ₁₃ to form an aromatic fused ring;

R ₁₁ to R ₁₄ are each independently hydrogen, C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, halogen, cyano, nitro, hydroxy or haloC1-C30 alkyl.]

For example, the fused ring (eg, V ₁ and V ₂ ) using the methylidene as a linking group may be selected from the following structures, but is not limited thereto.

The compound according to one embodiment of the present invention minimizes the quenching of the excited state by the vibronic path by the above-described structural characteristics, thereby reducing the energy loss due to absorption of sunlight and thus increasing the absorption coefficient for higher sunlight. Can be implemented.

In addition, the compound has high crystallinity, and in order to realize high charge mobility, a fused ring (eg, V ₁ and V ₂ ) using the methylidene as a linking group is represented by Chemical Formula 4, and R ₁₂ of Chemical Formula 4 To R ₁₄ are each independently hydrogen or halogen; The Z ₃ is -C (R ₂₃ ) =, and the R ₂₃ may be hydrogen, C1-C30 alkyl, C1-C30 alkoxy or C1-C30 alkylthio.

In addition, it is preferable that at least one halogen is substituted on the fused ring using the methylidene as a linking group.

The compound according to an embodiment of the present invention in Formula 1, wherein R ₁ to R ₈ are each independently aryl such as phenyl, naphthyl and biphenyl; And heteroaryl such as thiophene, thienothiophene, bithiophene, selenophene, selenoselenophene, and biselenophene; And aryl or heteroaryl, each independently substituted with one or more substituents selected from C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio and halogen.

Specifically, the compound according to an embodiment of the present invention in Formula 1, wherein R ₁ to R ₄ are each independently selected from one or more substituents selected from C1-C30 alkyl, C1-C30 alkoxy and C1-C30 alkylthio Substituted phenyl; Each of R ₅ to R ₈ may be independently a thiophene substituted with one or more substituents selected from C1-C30 alkyl, C1-C30 alkoxy and C1-C30 alkylthio.

More specifically, in the compound according to an embodiment of the present invention, in Formula 1, the phenyl of R ₁ to R ₄ may be substituted with the above-described substituent at the meta-position.

As described above, the compound of the present invention having structural characteristics can be used as an electron acceptor material. In addition, the compound of the present invention may be used as an electron donor material by changing the form of a substituent.

Hereinafter, an organic electronic device including the novel compound according to the present invention will be described.

The organic electronic device according to an embodiment of the present invention includes the compound of Formula 1, and may be included in the photoactive layer.

The organic electronic device of the present invention is not limited as long as it is an element using an electron acceptor material, an electron donor material, and the like, and the organic electronic device is an organic light emitting device, an organic thin film transistor, an organic light sensor, or an organic solar cell. And the like.

Specifically, the compound of Formula 1 may be included as an electron acceptor of the photoactive layer of the organic solar cell.

More specifically, the compound of Formula 1 is an electron acceptor and is used as an alternative compound of a fullerene derivative conventionally used in an organic solar cell, and the organic solar cell employing this has improved photoelectric conversion efficiency.

Hereinafter, a method of manufacturing an organic solar cell according to the present invention will be described as an example, but is not limited thereto.

The organic solar cell according to an embodiment of the present invention may have a structure in which a hole transport layer and an electron transport layer are bonded. When the organic solar cell absorbs sunlight, an electron-hole pair is generated in the hole acceptor and electrons move to the electron acceptor, thereby exhibiting a photoelectric conversion effect through separation of electron-holes.

 The organic solar cell according to an embodiment of the present invention has a high planarity and forms a plate-like two-dimensional structure, the compound of Formula 1 that can significantly improve the face-on fraction by a delocalized pi-electron system along the central skeleton It has been confirmed that by employing in an organic solar cell, a surprisingly improved photoelectric conversion efficiency can be achieved.

In addition, the compound of Formula 1 has high crystallinity and high charge mobility, so it can be used as a material such as an electron acceptor or an electron donor in a photoactive layer of an organic solar cell to realize high efficiency.

The organic solar cell according to an embodiment of the present invention may include a substrate, a first electrode, a photoactive layer and a second electrode, and may further include a hole transport layer, an electron transport layer, and the like.

In addition, the organic solar cell according to an embodiment of the present invention may be an inverted type organic solar cell.

In addition to the glass and quartz plates, the substrate is PET (polyethylene terephthalate), PEN (polyethylene naphthelate), PP (polyperopylene), PI (polyimide), PC (polycarbornate), PS (polystylene), POM (polyoxyethlene), AS resin (acrylonitrile styrene) copolymer), ABS resin (acrylonitrile butadiene styrene copolymer) and TAC (Triacetyl cellulose).

In addition, the first electrode is coated with a transparent electrode material on one surface of the substrate or coated in a film form by using sputtering, E-Beam, thermal evaporation, spin coating, screen printing, inkjet printing, doctor blade or gravure printing. Is formed. The first electrode is a part that functions as an anode. As a material having a larger work function than the second electrode described later, any material having transparency and conductivity may be used. For example, ITO (indium tin oxide), gold, silver, and fluorine doped tin oxide (FTO), aluminum doped zinc oxide (AZO), IZO (indium zink oxide) ), ZnO-Ga2O3, ZnO-Al2O3, and antimony tin oxide (ATO), and preferably ITO.

In addition, the photoactive layer may include a compound according to the present invention, and the compounding amount thereof may be appropriately adjusted according to the use. In addition, the compound may be dissolved in an organic solvent and used as an electron acceptor material for a photoactive layer with a thickness of 60 to 120 nm. Also, an example of an electron donor is PBDTTT-CT (Poly {[4,8-bis- (2-ethyl-hexyl-thiophene-5-yl) -benzo [1,2-b: 4,5-b '] dithiophene -2,6-diyl] -alt- [2- (2'-ethyl-hexanoyl) -thieno [3,4-b] thiophen-4,6-diyl]}), PBDTTT-CF ( Poly [1- ( 6- {4,8-bis [(2-ethylhexyl) oxy] -6-methylbenzo [1,2- b : 4,5- b ′] dithiophen-2-yl} -3-fluoro-4-methylthieno [3 , 4- b ] thiophen-2-yl) -1-octanone] ), P3HT (Poly (3-hexylthiophene)), PCDTBT ( Poly [ N -9′-heptadecanyl-2,7-carbazole- alt -5,5 - (4 ', 7'' - di-2-thienyl-2'',1'',3''- benzothiadiazole)], Poly [[9- (1- octylnonyl) -9H- carbazole -2,7- diyl] -2,5-thiophenediyl-2,1,3-benzothiadiazole-4,7-diyl-2,5-thiophenediyl] ) and the like. The organic solvent may be acetone, methanol, THF, toluene, xylene, tetralin, chloroform, chlorobenzene, dichlorobenzene, or a mixed solvent thereof, but is not limited thereto. In addition, the photoactive layer containing the compound according to the present invention increases the photoelectric conversion efficiency by increasing short circuit current density and open circuit voltage due to high electron density.

In addition, the second electrode may be deposited using a thermal evaporator while the electron transport layer is introduced. At this time, the usable electrode materials include lithium fluoride / aluminum, lithium fluoride / calcium / aluminum, calcium / aluminum, barium fluoride / aluminum, barium fluoride / barium / aluminum, barium / aluminum, aluminum, gold, silver, magnesium: silver and It may be selected from lithium: aluminum and the like, and preferably, an electrode made of a barium fluoride / barium / aluminum structure is used.

In addition, materials of the electron transport layer and the hole transport layer can be used unlike the general types of electron transport layer and hole transport layer. Examples of the electron transport layer material include TiO _x , ZnO, TiO ₂ , ZrO ₂ , MgO, and HfO ₂ , and examples of the hole transport layer material include NiO, Ta ₂ O ₃ , MoO ₃ , and Ru ₂ O ₃ And metal oxides. In addition, it is of course possible to use the organic conjugated polymer electrolyte having a cation or an anion in addition to the metal oxide described above as an electron transport layer or a hole transport layer material.

Hereinafter, the present invention will be described in detail by examples. However, the following examples are only for illustrating the present invention, and the contents of the present invention are not limited by the following examples. At this time, unless there is another definition in the technical terminology and scientific terminology used, it has a meaning that a person with ordinary knowledge in the technical field to which this invention belongs generally understands. In addition, repeated description of the same technical configuration and operation as the prior art will be omitted.

(Example 1)

Preparation of compound 1

Step 1.

Compound A (4,8-bis (5- (2-ethylhexyl) thiophen-2-yl) benzo [1,2-b: 4,5-b '] dithiophene, 15 under nitrogen stream in a 500 ml flask with moisture removed g, 0.0259 mol) was added, dissolved in 100 ml of tetrahydrofuran (THF), and 10.6 ml of n-BuLi (2.5M in hexane) was slowly added at 0 ° C, followed by stirring at 50 ° C for 1 hour and 30 minutes. After stirring, the solution was cooled to -78 ° C and the dried ZnCl ₂ dissolved in THF was slowly added to the reaction mixture, followed by further stirring at 0 ° C for 1 hour and 30 minutes, with Pd (PPh ₃ ) ₄ (0.59 g, 0.000518 mol). Diethyl 2,5-dibromotetraphthalate (diethyl 2,5-dibromoterephthalate, 3.93 g, 0.010364 mol) was added, followed by reflux and stirring for 12 hours. After completion of the reaction, water and dichloromethane (MC) were extracted, and the organic layer was dried over MgSO ₄ and subjected to column chromatography (Hexane: MC = 2: 1) to obtain Compound B (11.9 g, 84%).

H-NMR (300 MHz, CDCl ₃ ): δ = 7.95 (s, 2H), 7.69-7.67 (d, 2H), 7.63 (s, 2H), 7.51-7.50 (d, 2H), 7.34-7.33 (d , 2H), 7.32-7.30 (d, 2H), 6.93-6.90 (t, 4H), 4.27-4.19 (q, 4H), 2.90-2.87 (m, 8H), 1.71 (br, 4H), 1.38 (br , 32H), 1.12-1.07 (t, 6H), 0.98-0.94 (br, 18H).

Step 2.

1-bromo-3-hexylbenzene (3-bromo-3-hexylbenzene, 3.68 g, 0.01526 mol) was added to a 250 ml flask in which water was removed under nitrogen flow, dissolved in 70 ml of THF, and then cooled to -78 ° C. At -78 ° C, 6.1 ml of n-BuLi (2.5M in hexane) was slowly added for 15 minutes and stirred for 1 hour. Compound B (4.2 g, 0.00305 mol) dissolved in THF was further added at -78 ° C, and slowly heated to room temperature and stirred for 10 hours. After the reaction was completed, poured into cold water, extracted with ethyl acetate (EA), the organic layer was dried with MgSO ₄ and subjected to column chromatography (Hexane: MC = 4: 1) to obtain Compound C, which was used in the next reaction without further purification. Became.

Step 3.

Compound C under nitrogen stream was added to the removed flask, 100 ml of acetic acid was added, and the mixture was refluxed for 3 hours. After the reaction, the mixture was placed in ice water, extracted with methylene chloride, dried with MgSO ₄ , and subjected to column chromatography (Hexane: MC = 10: 1) to obtain Compound D (80%).

¹ H-NMR (300 MHz, CD ₂ Cl ₂ ): δ = 7.45-7.43 (d, 2H), 7.37-7.35 (d, 2H), 7.34-7.33 (d, 2H), 7.24 (s, 2H), 7.02 (br, 12H), 6.90-6.85 (br, 6H), 6.37-6.36 (d, 2H), 5.92-5.91 (d, 2H), 2.95-2.93 (d, 4H), 2.67 (br, 4H), 2.49 (m, 8H), 1.75 (br, 4H), 1.34 (br, 70H), 0.98 (br, 24H), 0.83 (m, 12H).

Step 4.

Compound D (5 g, 0.00263 mol) was added to the flask in which nitrogen was removed under water, dissolved in 150 ml of THF, tetramethylethylenediamine (TMEDA, 0.85 g, 0.00738 mol) was added and stirred. The reaction was cooled to -78 ° C and 6.33 ml of lithium diisopropylamide (LDA, 2.0M in Hexane) was slowly added, followed by stirring for 2 hours. After stirring, N-formylpiperidine (N-formylpiperidine, 1.79 g, 0.0158 mol) was slowly added and slowly heated to terminate the reaction with an aqueous NaCl solution at 5 ° C. Extracted with ethyl acetate (EA), the organic layer was dried with MgSO ₄ and subjected to column chromatography (Hexane: MC = 4: 1) to obtain Compound E (2.57 g, 50%).

¹ H-NMR (300 MHz, CD ₂ Cl ₂ ): δ = 9.95 (s, 2H), 8.15 (s, 2H), 7.38-7.37 (d, 2H), 7.28 (s, 2H), 7.04 (br, 12H), 6.96 (br, 2H), 6.91 (br, 2H), 6.81 (br, 2H), 6.39-6.38 (d, 2H), 5.92-5.91 (d, 2H), 2.96-2.94 (d, 4H) , 2.70 (br, 4H), 2.49 (m, 12H), 1.76 (br, 4H), 1.34 (br, aliphatic CH ₂ ), 0.99 (br, 37H), 0.81 (m, 12H).

Step 5.

Compound E (0.3 g, 0.000154 mol) and sodium acetate (0.126 g, 0.00153 mol) were added to nitrogen-flowed flask in a water-removed flask, dissolved in 40 ml of acetic acid, and stirred. Slowly heated and heated at 50 ° C with 2- (3-oxo-2,3-dihydro-1H-inden-1-ylidene) malononitrile (2- (3-oxo-2,3-dihydro-1H-inden- 1-ylidene) malononitrile, 0.15 g, 0.00077 mol) was added and stirred for 5 hours. After the reaction, the mixture was cooled to room temperature and crystallized using methanol. The resulting solid was filtered, washed three times with methanol, and recrystallized using methylene chloride and acetone. After recrystallization, compound 1 (0.26 g, 74%) was obtained.

¹ H-NMR (300 MHz, CD ₂ Cl ₂ ): δ = 8.78 (s, 2H), 8.70-8.68 (d, 2H), 8.29 (s, 2H), 7.88-7.77 (m, 6H), 7.42 ( d, 2H), 7.30 (s, 2H), 7.05-6.87 (br, 18H), 6.46 (d, 2H), 5.98 (d, 2H), 2.98-2.96 (d, 4H), 2.73 (br, 4H) , 2.5 (m, 8H), 1.78 (br, 2H), 1.40 (br, 40H), 1.24 (br, 24H), 1.02-0.98 (br, 24H), 0.83-0.79 (m, 12H).

¹³ C-NMR (125 MHz, CD ₂ Cl ₂ ): δ = 187.22, 160.21, 160.01, 151.10, 149.85, 149.63, 147.48, 144.44, 142.53, 142.43, 140.93, 140.10,140.01, 139.53, 138.27, 138.05, 137.01 135.61, 135.35, 135.22, 135.07, 134.71, 134.07, 128.89, 128.78, 128.23, 127.99, 127.83, 126.80, 126.45, 125.85, 125.82, 125.21, 124.61, 123.87, 123.60, 116.30, 114.43, 11497, 55.55. 41.51, 41.30, 35.96, 35.91, 34.22, 34.00, 33.91, 32.54, 32.47, 32.36, 31.72, 31.69, 31.33, 31.31, 30.58, 28.94, 28.89, 28.82, 25.72, 25.54, 25.45, 23.13, 23.04, 22.61, 22.61 14.04, 13.96, 13.89, 13.86, 10.74, 10.66.

C ₁₅₀ H ₁₅₈ N ₄ O ₂ S ₈ : MALDI-TOF: calcd .; 2303.0150, found; 2304.9165.

(Example 2)

Preparation of compound 2

Step 1.

Compound a (4,8-bis (5-((2-ethylhexyl) thio) thiophen-2-yl) benzo [1,2-b: 4,5-b '] under nitrogen stream in a 500 ml flask with moisture removed dithiophene, 18 g, 0.0279 mol) was added, dissolved in 120 ml of THF, and then 11.42 ml of n-BuLi (2.5M in hexane) was slowly added at 0 ° C, followed by stirring at 50 ° C for 1 hour and 30 minutes. After stirring, the mixture was cooled to -78 ° C, and a solution of dried ZnCl ₂ (3.81 g, 0.0279 mol) dissolved in THF was added to the reaction mixture, followed by stirring at 0 ° C for 1 hour and 30 minutes, and Pd (PPh ₃ ) ₄ (0.65 g, 0.00056 mol) and diethyl 2,5-dibromoterephthalate (diethyl 2,5-dibromoterephthalate, 4.25 g, 0.011196 mol) were added and stirred under reflux for 12 hours. After the reaction was completed, extraction was performed with water and dichloromethane (MC), dried over MgSO ₄ and subjected to column chromatography (Hexane: MC = 2: 1) to obtain compound b (12.6 g, 74%).

¹ H-NMR (300 MHz, CDCl ₃ ): δ = 7.97 (s, 2H), 7.69-7.66 (d, 2H), 7.62 (s, 2H), 7.61-7.59 (d, 2H), 7.41-7.40 ( d, 2H), 7.39-7.37 (d, 2H), 7.28-7.25 (t, 4H), 4.28-4.21 (q, 4H), 3.0-2.98 (d, 8H), 1.68 (br, 4H), 1.49 ( br, 14H), 1.35 (br, 16H), 1.13 (t, 6H), 0.94-0.91 (br, 24H).

Step 2.

1-bromo-3-hexylbenzene (1-bromo-3-hexylbenzene, 9.8 g, 0.0408 mol) was added to a 500 ml flask in which water was removed under nitrogen flow, dissolved in 150 ml of THF, and then cooled to -78 ° C. . At -78 ° C, 16.351 ml of n-BuLi (2.5M in hexane) was slowly added and stirred for 1 hour. Compound b (12.3 g, 0.00817 mol) dissolved in THF was dissolved in THF, and slowly added to the reaction product at -78 ° C. Then, the mixture was heated to room temperature and stirred for 10 hours. After completion of the reaction, poured into cold water, extracted with ethyl acetate (EA), dried with MgSO ₄ and subjected to column chromatography (Hexane: MC = 4: 1) to obtain compound c, which was used without further purification.

Step 3.

Compound c was added under a nitrogen stream to the dehydrated flask, and 250 ml of acetic acid was added, followed by reflux for 3 hours. After completion of the reaction, the mixture was placed in ice water, extracted with methylene chloride, dried over MgSO ₄ and subjected to column chromatography (Hexane: MC = 10: 1) to obtain compound d (7.8 g, 47%).

¹ H-NMR (300 MHz, CD ₂ Cl ₂ ): δ = 7.44-7.42 (d, 2H), 7.39-7.38 (d, 2H), 7.37-7.36 (d, 2H), 7.29-7.28 (d, 2H) ), 7.24 (s, 2H), 7.05 (br, 10H), 6.88 (br, 6H), 6.63-6.62 (d, 2H), 5.97-5.96 (d, 2H), 3.01-2.99 (d, 4H), 2.79 (br, 4H), 2.52-2.46 (m, 8H), 1.70 (br, 2H), 1.56-1.21 (br, aliphatic CH ₂ ), 0.96 (br, 24H), 0.86 (m, 12H).

Step 4.

Compound d (5 g, 0.00246 mol) was added to the flask in which nitrogen was removed under water, dissolved in 120 ml of THF, tetramethylethylenediamine (TMEDA, 0.80 g, 0.00691 mol) was added and stirred. The reaction was cooled to -78 ° C and lithium diisopropylamide (LDA, 2.0M in Hexane, 5.9 ml) was slowly added thereto, followed by stirring for 2 hours. After stirring, N-formylpiperidine (N-formylpiperidine, 1.67 g, 0.0158 mol) was added and slowly heated to terminate the reaction with an aqueous NaCl solution at 5 ° C. Extracted with ethyl acetate (EA), dried over MgSO ₄ and subjected to column chromatography (Hexane: MC = 4: 1) to obtain compound e (3.8 g, 73%).

¹ H-NMR (300 MHz, CD ₂ Cl ₂ ): δ = 9.95 (s, 2H), 8.13 (s, 2H), 7.42-7.41 (d, 2H), 7.32-7.31 (d, 2H), 7.29 ( s, 2H), 7.07 (br, 10H), 6.86 (br, 6H), 6.65-6.64 (d, 2H), 5.99-5.98 (d, 2H), 3.04-3.02 (d, 2H), 2.82-2.73 ( m, 4H), 2.49 (br, 8H), 1.71 (m, 2H), 1.55-1.20 (br, aliphatic CH ₂ ), 0.96 (br, 26H), 0.79 (m, 12H).

Step 5.

Compound e (1 g, 0.00048 mol) and sodium acetate (0.39 g, 0.00485 mol) were added to a flask with nitrogen gas dissolved in 80 ml of acetic acid and stirred. Slowly heated and heated at 50 ° C with 2- (3-oxo-2,3-dihydro-1H-inden-1-ylidene) malononitrile (2- (3-oxo-2,3-dihydro-1H-inden- 1-ylidene) malononitrile, 0.46 g, 0.0024 mol) was added and stirred for 5 hours.

After the reaction, the mixture was cooled to room temperature and crystallized using methanol. The resulting solid was filtered, washed three times with methanol, and recrystallized using methylene chloride and acetone. After recrystallization, compound 2 (0.86 g, 73%) was obtained.

¹ H-NMR (300 MHz, CD ₂ Cl ₂ ): δ = 8.78 (s, 2H), 8.71-8.69 (d, 2H), 8.28 (s, 2H), 7.91 (d, 2H), 7.86-7.75 ( m, 4H), 7.46 (d, 2H), 7.35-7.34 (d, 2H), 7.32 (s, 2H), 7.13-7.04 (m, 10H), 6.97-6.87 (m, 6H), 6.71-6.70 ( d, 2H), 6.05-6.04 (d, 2H), 3.08-3.05 (d, 4H), 2.86 (m, 4H), 2.56-2.47 (m, 8H), 1.70 (m, 4H), 1.52-1.21 ( br, aliphatic CH ₂ ), 0.96 (br, 24H), 0.85-0.79 (m, 12H).

¹³ C-NMR (125 MHz, CD ₂ Cl ₂ ): δ = 187.21, 160.21, 160.02, 151.54, 149.93, 149.50, 144.42, 142.76, 142.65, 140.26, 140.03, 139.92,139.77, 139.59, 139.35, 138.33, 138.23, 137.99, 136.97, 135.48, 135.45, 135.01, 134.80, 134.05, 132.38, 130.66, 130.24, 129.54, 128.75, 128.69, 128.19, 127.96, 127.51, 126.90, 126.69, 126.24, 126.23, 125.71, 125.62, 125.62, 125.62 116.34, 114.33, 114.05, 71.31, 64.72, 43.42, 43.17, 39.31, 38.96, 35.96, 32.13, 32.09, 31.72, 31.70, 31.38, 31.29, 28.87, 28.73, 28.69, 28.66, 25.40, 25.34, 23.06, 23.03, 22.03 22.64, 22.57, 13.92, 13.88, 10.61, 10.57.

C ₁₅₀ H ₁₅₈ N ₄ O ₂ S ₁₂ : MALDI-TOF: calcd .; 2430.9033, found; 2430.8628.

(Example 3)

Preparation of compound 2-1

In step 5 of Example 2, instead of 2- (3-oxo-2,3-dihydro-1H-inden-1-ylidene) malononitrile (0.00077 mol), 2- (5, corresponding to the same mole number Compound 2-1 (0.25 g, 67%) was obtained using 6-dichloro-3-oxo-2,3-dihydro-1H-inden-1-ylidene) malononitrile.

¹ H-NMR (300 MHz, CD ₂ Cl ₂ ): δ = 8.80 (s, 2H), 8.78 (s, 2H), 8.32 (s, 2H), 7.94 (s, 2H), 7.45-7.44 (d, 2H), 7.34-7.32 (t, 4H), 7.12-7.03 (m, 10H), 6.95-6.88 (br, 6H), 6.71 (d, 2H), 6.04 (d, 2H), 3.07 (d, 4H) , 2.86 (m, 4H), 2.50 (m, 8H), 1.69 (m, 4H), 1.58 (br, 16H), 1.39-1.20 (br, 44H), 1.01-0.95 (br, 25H), 0.85-0.78 (m, 12H).

(Example 4)

Preparation of compound 2-2

In step 5 of Example 2, 2- (3-oxo-2,3-dihydro-1H-inden-1-ylidene) malononitrile (0.00077 mol) instead of 2- (5, corresponding to the same mole number Compound 2-2 (0.25 g, 69%) was obtained using 6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-ylidene) malononitrile.

¹ H-NMR (300 MHz, CD ₂ Cl ₂ ): δ = 8.78 (s, 2H), 8.57-8.52 (t, 2H), 8.29 (s, 2H), 7.70-7.64 (t, 2H), 7.45 ( d, 2H), 7.34-7.31 (t, 4H), 7.13-7.03 (m, 10H), 6.95-6.88 (br, 6H), 6.70 (d, 2H), 6.03 (d, 2H), 3.07 (d, 4H), 2.85 (m, 4H), 2.53 (m, 8H), 1.71 (m, 4H), 1.51 (br, 20H), 1.39-1.20 (br, 47H), 1.00-0.91 (br, 27H), 0.84 -0.78 (m, 12H).

(Example 5)

Preparation of compound 3

Performed in the same manner as in Example 1, the starting material Compound A (4,8-bis (5- (2-ethylhexyl) thiophen-2-yl) benzo [1,2-b: 4,5-b ' ] dithiophene, 0.0259 mol) compound f (4,8-bis (5- (2-ethylhexyloxy) thio) thiophen-2-yl) benzo [1,2-b: 4,5-b ' ] dithiophene) to give compound 3 (0.15 g, 42%).

¹ H-NMR (300 MHz, CD ₂ Cl ₂ ): δ = 8.79 (s, 2H), 8.71 (d, 2H), 8.28 (s, 2H), 7.91-7.78 (m, 6H), 7.46 (d, 2H), 7.37 (s, 2H), 7.34 (d, 2H), 7.13 (m, 4H), 6.78-6.62 (br, 14H), 6.07 (br, 2H), 3.80-3.70 (m, 8H), 3.07 (d, 4H), 2.85 (d, 4H), 1.70 (m, 8H), 1.54-1.27 (br, aliphatic CH ₂ ), 1.01-0.84 (br, aliphatic CH ₂ , CH ₃ ).

(Example 6)

Preparation of compound 3-1

In step 5 of Example 5, 2- (5, corresponding to the same mole number instead of 2- (3-oxo-2,3-dihydro-1H-inden-1-ylidene) malononitrile (0.00077 mol) Compound 3-1 (0.2 g, 49%) was obtained using 6-dichloro-3-oxo-2,3-dihydro-1H-inden-1-ylidene) malononitrile.

¹ H-NMR (300 MHz, CD ₂ Cl ₂ ): δ = 8.81 (s, 2H), 8.78 (d, 2H), 8.33 (s, 2H), 7.95 (s, 2H), 7.46 (d, 2H) , 7.37 (s, 2H), 7.34 (d, 2H), 7.13-7.03 (m, 4H), 6.78-6.62 (m, 14H), 6.07 (br, 2H), 3.79-3.73 (m, 8H), 3.07 (d, 4H), 2.85 (d, 4H), 1.69 (m, 8H), 1.49-1.27 (br, aliphatic CH ₂ ), 1.01-0.84 (br, aliphatic -CH _2- , -CH ₃ ).

(Example 7)

Preparation of compound 3-2

In step 5 of Example 5, 2- (5, corresponding to the same mole number instead of 2- (3-oxo-2,3-dihydro-1H-inden-1-ylidene) malononitrile (0.00077 mol) Compound 3-2 (0.28 g, 77%) was obtained using 6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-ylidene) malononitrile.

¹ H-NMR (300 MHz, CD ₂ Cl ₂ ): δ = 8.79 (s, 2H), 8.57-8.52 (t, 2H), 8.30 (s, 2H), 7.67 (t, 2H), 7.46 (d, 2H), 7.37 (s, 2H), 7.34 (d, 2H), 7.16-7.02 (m, 4H), 6.78-6.62 (m, 14H), 6.06 (br, 2H), 3.79-3.70 (m, 8H) , 3.07 (d, 4H), 2.84 (d, 4H), 1.71 (m, 8H), 1.56-1.26 (br, aliphatic CH 2), 1.00-0.84 (br, aliphatic -CH 2- -, -CH 3) .

(Examples 8 to 14)

Fabrication of organic solar cells

An organic substrate coated with ITO (Indium Tin Oxide), which is an anode transparent electrode (first electrode), is immersed in deionized water containing a cleaning solution, washed for 15 minutes in an ultrasonic cleaner, and again deionized water, acetone, isopropyl alcohol (IPA) ) And washed 3 times, and dried in an oven at 130 ° C for 5 hours. The ITO glass substrate washed as described above was subjected to ultraviolet / ozone treatment for 15 minutes, followed by spin coating ZnO · NPs having a thickness of 30 nm on the ITO substrate. And the substrate coated with ZnO · NPs was heat treated at 100 ° C. for 10 minutes on a hot plate. Then, to apply the photoactive layer, the device was moved to a glove box filled with argon. The photoactive layer is prepared by dissolving the compound (electron acceptor, Examples 1 to 7) of each of the present invention and PBDB-T (electron donor) in a chloroform solvent at a weight ratio of 1: 1 to 0.45 μm (PTFE) syringe filter (syringe). It was prepared by coating on a ZnO layer with a thickness of 100 nm through a spin coating method with an organic semiconductor solution filtered through a filter). An organic solar cell was completed by depositing a 10 nm thick MoO ₃ on the photoactive layer and a 100 nm thick Ag electrode as a top electrode on a photoactive layer under a 3 X 10 ^-6 torr vacuum in a thermal evaporator.

Table 1 shows the electrical characteristics of the produced organic solar cell, such as open voltage (Voc), short circuit current (Jsc), fill factor (Fill Factor), and photoelectric conversion efficiency (PCE).

(Comparative Example 1)

Fabrication of organic solar cells

PC71BM

PC71BM

An organic solar cell was prepared in the same manner as in Example 8 using the existing electron acceptor (PC71BM) instead of the compound of the present invention to confirm its properties.

Example #.
(Acceptor) Donor: Acceptor
(1: 1 ratio, 8mg) Pre-annealing 140 ℃ V _oc
(V) J _sc
(mA / cm ² ) FF PCE
( % ) Example 8
(Example 1) 1000rpm X 0.98 11.07 0.42 4.59 1000rpm O 0.95 12.11 0.41 4.70 1500rpm X 0.98 12.01 0.47 5.52 1500rpm O 0.97 13.10 0.47 5.90 2000rpm X 0.98 12.24 0.49 5.86 2000rpm O 0.96 13.43 0.51 6.57 Example 9
(Example 2)
1000rpm X 0.88 13.57 0.49 5.89 1000rpm O 0.84 14.51 0.50 6.07 1500rpm X 0.87 14.07 0.52 6.34 1500rpm O 0.85 16.25 0.55 7.58 2000rpm X 0.83 14.30 0.54 6.48 2000rpm O 0.86 16.66 0.59 8.46

As shown in Table 1, it was confirmed that the organic solar cell employing the compound according to the present invention as the electron acceptor in the photoactive layer can achieve a photoelectric conversion efficiency of 4.59% or more. In addition, it was confirmed that in the compound, when R ₁ to R ₈ are different substituents from each other, at least one or more heteroatoms are included, remarkably improved photoelectric conversion efficiency (PCE) can be realized. In addition, it was confirmed that a high short-circuit current (J _sc ) and a charging rate (FF) can be realized by the structural characteristics of the compound.

In addition, when the compound according to the present invention has a substituent substituted with at least one halogen, it can be expected to have high crystallinity and to increase the photoelectric conversion efficiency of the organic solar cell employing it by implementing high charge mobility. have.

These effects showed open voltage, short-circuit current, charge rate and photoelectric conversion efficiency that can overcome the disadvantages of the organic solar cell using the existing electron acceptor (PC71BM).

In addition, the optical and electrochemical properties of the compound according to the present invention are analyzed and shown in Table 2 below.

Example #.
(Acceptor) Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 λ _max (Sol.) Chloroform
(nm) 676 711 685 673 707 694 λ _max (Film) @ RT
(nm) 639 (s), 708 762 738 691 750 738 λ _max (Film) @ 100 ℃
(nm) 643 (s), 712 780 763 703 745 753 E _g (optical_film)
(eV) 1.60 1.44 1.48 1.61 1.54 1.48 FWHM Film
(nm) 130 134 148 129 127 150 E _HOMO (eV) -5.53 -5.60 -5.67 -5.64 -5.65 -5.68 E _LUMO (eV) -3.68 -3.68 -4.19 -4.03 -4.11 -4.20

As shown in Table 2, the compound according to the present invention has a low HOMO energy level, and has high photo-oxidation stability. In addition, it can be seen that the compound is an excellent organic electronic device material because it can be seen that the compound is thermally stable and the charge mobility increases when annealed.

In addition, in order to find out the decomposition temperature of the compound according to the present invention, a thermogravimetric analysis (TGA) was performed by heating from 40 ° C to 800 ° C at 10 ° C per minute (min) under a nitrogen atmosphere using a TA instrument TGA Q50. As a result, Examples 2 to 7 confirmed that 5% decomposition occurred at 317 ° C, 343 ° C, 286 ° C, 320 ° C, 331 ° C and 301 ° C.

As described above, although the embodiments of the present invention have been described in detail, those of ordinary skill in the art to which the present invention pertains, without departing from the technical spirit of the present invention as defined in the appended claims The present invention may be implemented in various ways. Therefore, changes in the embodiments of the present invention will not be able to escape the technology of the present invention.

Claims (9)

Compound represented by the formula (1):
[Formula 1]

[In the above formula 1,
R ₁ to R ₄ are each independently C6-C20 aryl, R ₅ to R ₈ are each independently C3-C20 heteroaryl, and the aryl of R ₁ to R ₄ or the heteroaryl of R ₅ to R ₈ is each Independently substituted with one or more substituents selected from C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, halogen, cyano and halo C1-C30 alkyl;
V ₁ and V ₂ are each independently a fused ring having methylidene as a linking group, and each of the fused rings is independently C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, halogen, cyano, nitro, and hydro It may be further substituted with one or more substituents selected from hydroxy and haloC1-C30 alkyl, -CH ₂ -of the fused ring is carbonyl, sulfinyl or

Can be replaced by, R is hydrogen, C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, halogen, cyano, nitro, hydroxy, halo C1-C30 alkyl, C1-C30 alkylcarbonyl or C1-C30 alkylcarbonyloxy;
Y ₁ to Y ₄ are each independently O, S or Se;
The heteroaryl includes one or more heteroatoms selected from N, O, S and Se.] According to claim 1,
Each of V ₁ and V ₂ is independently represented by Formula 2 below, a compound:
[Formula 2]

[In the formula 2,
X ₁ and X ₂ are each independently O, S or CR ₂₁ R ₂₂ , and R ₂₁ and R ₂₂ are each independently halogen, cyano, nitro, hydroxy, C1-C30 alkylcarbonyl or C1-C30 alkyl Carbonyloxy;
A is an aromatic fused ring, and the aromatic fused ring is one or more substituents selected from C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, halogen, cyano, nitro, hydroxy and halo C1-C30 alkyl. Can be further substituted.] According to claim 2,
V ₁ and V ₂ are each independently represented by the following formula (3) or (4):
[Formula 3]

[Formula 4]

[In the formulas 3 and 4,
X ₁ and X ₂ are each independently O, S or CR ₂₁ R ₂₂ , and R ₂₁ and R ₂₂ are each independently halogen, cyano, nitro, hydroxy, C1-C30 alkylcarbonyl or C1-C30 alkyl Carbonyloxy;
One of Z ₁ and Z ₂ is -CH =, and the other is O, S or Se;
Z ₃ is -C (R ₂₃ ) = or N, and R ₂₃ is hydrogen, C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, halogen, cyano, nitro, hydroxy or halo C1-C30 Can be linked to an alkyl or adjacent substituent R ₁₂ or R ₁₃ to form an aromatic fused ring;
R ₁₁ to R ₁₄ are each independently hydrogen, C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, halogen, cyano, nitro, hydroxy or haloC1-C30 alkyl.] According to claim 3,
V ₁ and V ₂ are Chemical Formula 4,
R ₁₂ to R ₁₄ in Formula 4 are each independently hydrogen or halogen; Wherein Z ₃ is -C (R ₂₃ ) =, and R ₂₃ is hydrogen, C1-C30 alkyl, C1-C30 alkoxy or C1-C30 alkylthio. According to claim 1,
R ₁ to R ₄ are each independently selected from aryl of phenyl, naphthyl and biphenyl, and R ₅ to R ₈ are each independently thiophene, thienothiophene, bithiophene, selenophene, selenoselenophen, and Heteroaryl of biselenophen; is selected from the aryl of R ₁ to R ₄ or heteroaryl of R ₅ to R ₈ are each independently selected from C1-C30 alkyl, C1-C30 alkoxy and C1-C30 alkylthio A compound that is substituted with one or more substituents. An organic electronic device comprising a compound according to any one of claims 1 to 5. The method of claim 6,
The organic electronic device,
An organic electronic device, which is an organic light emitting device, an organic thin film transistor, an organic photosensor or an organic solar cell. The method of claim 6,
The compound is included in the photoactive layer of an organic solar cell, an organic electronic device. The method of claim 8,
The compound is used as an electron acceptor, an organic electronic device.