KR102093460B1 - 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.

In addition, 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.

The present invention aims to provide an organic solar cell having excellent photoelectric conversion efficiency by employing the compound of the present invention in 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 ₁₁ to R ₁₈ are each independently C1-C30 alkyl, 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 halo C1-C30 alkyl, etc., may be further substituted with one or more substituents;

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 ₁₁ and V ₁₂ 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 ₁₁ to Y ₁₄ 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 ₁₁ and V ₁₂ may be 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 ₁₁ and V ₁₂ may be 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, V ₁₁ and V ₁₂ may be the formula (4). At this time, the R ₁₂ to R ₁₄ of Formula 4 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.

The compound according to an embodiment of the present invention in Formula 1, wherein R ₁₁ , R ₁₂ , R ₁₇ and R ₁₈ are each independently C1-C30 alkyl, and R ₁₃ to R ₁₆ are each independently phenyl, naph Aryl such as butyl and biphenyl, and the aryl may be each independently substituted with one or more substituents selected from C1-C30 alkyl, C1-C30 alkoxy and 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 to use the compound of Formula 1 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 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 formula 1,

R ₁₁ to R ₁₈ are each independently C1-C30 alkyl, 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 halo C1-C30 alkyl, etc., may be further substituted with one or more substituents;

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 ₁₁ and V ₁₂ 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 ₁₁ to Y ₁₄ are each independently O, S or Se;

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

Specifically, the compound of Formula 1 is characterized in that it has a central skeleton having an extended conjugate containing indensenodithiophene or indasenodycelenophene. With such a structural characteristic, the compound of Formula 1 may further improve the planeness of the molecule.

In addition, in order to further improve the interaction between molecules by forming the conjugate of the compound of Formula 1 outside the central skeleton, a fused ring using methylidene as a linker was introduced.

Specifically, the fused ring (eg, V ₁₁ and V ₁₂ ) 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 ₁₁ and V ₁₂ ) 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, in Chemical Formula 4, when Z ₃ is -C (R ₂₃ ) =, it may be connected to R ₁₂ or R ₁₃ to form an aromatic ring.

For example, the fused ring (eg, V ₁₁ and V ₁₂ ) 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 thus high charge mobility can be realized.

In addition, the compound has high crystallinity, and in order to realize high charge mobility, a fused ring (eg, V ₁₁ and V ₁₂ ) 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.

The compound according to an embodiment of the present invention in Formula 1, wherein R ₁₁ , R ₁₂ , R ₁₇ and R ₁₈ are each independently C1-C30 alkyl, and R ₁₃ to R ₁₆ are each independently phenyl, naph Aryl such as butyl and biphenyl, and the aryl may be each independently substituted with one or more substituents selected from C1-C30 alkyl, C1-C30 alkoxy and C1-C30 alkylthio.

Specifically, the compound according to an embodiment of the present invention in Formula 1, wherein R ₁₁ , R ₁₂ , R ₁₇ and R ₁₈ are each independently C1-C7 alkyl, and R ₁₃ to R ₁₆ are each independently It may be a phenyl substituted with one or more substituents selected from C1-C30 alkyl, C1-C30 alkoxy and C1-C30 alkylthio.

More specifically, the compound according to an embodiment of the present invention in the formula (1), the phenyl of R ₁₃ to R ₁₆ may be a substituent described above in the meta-position.

Most specifically, the compound according to an embodiment of the present invention is selected from a compound selected from the following structure in terms of realizing excellent light absorption coefficient and realizing improved photoelectric conversion efficiency with high miscibility with an electron donor It may be at least one, but is not limited to this.

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 present invention provides an organic electronic device comprising the compound of Formula 1 above.

The organic electronic device of the present invention is not limited as long as it is a device in which the compound of Formula 1 can be used, and as a non-limiting example of the organic electronic device, an organic light emitting device, an organic thin film transistor, an organic photosensor or an organic solar cell is Can be lifted.

Specifically, the compound of Formula 1 may be included in the photoactive layer of the organic solar cell.

More specifically, the compound of Formula 1 is an electron acceptor 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 consists of a structure in which a hole transport layer and an electron transport layer are bonded, and when absorbing sunlight, electron-hole pairs are generated in the hole receptor and electrons move to the electron receptor to separate electron-holes. It shows the photoelectric conversion effect through the process.

 Thus, the present invention is to form a two-dimensional structure having a high planarity, and by employing a compound of Formula 1 that can significantly improve the face-on fraction by a de-localized pi-electron system along the central skeleton, in an organic solar cell , It was confirmed that a surprisingly improved photoelectric conversion efficiency can be achieved. In addition, the compound of the present invention 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 of course, 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 formed by applying a transparent electrode material to one surface of the substrate or coated in a film form using sputtering, E-Beam, thermal evaporation, spin coating, screen printing, inkjet printing, doctor blade or gravure printing. do. 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 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 manufacturing examples and 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 (3-bromo-2,2'-bithiophene, 60 g, 0.244698 mol) was dissolved in diethyl ether (500 mL) in a well-dried nitrogen-substituted three-necked flask, cooled to -75 ° C, and then 2.5 M n-butyllithium (n-Butyllithium) (98 mL, 0.244698 mol) was dropped and stirred at -78 ° C for 2 hours. Then, acetone (14.2 g, 0.244698 mol) was slowly dropped and stirred at room temperature. Thereafter, the mixture was extracted with diethyl ether, the organic layer was washed with water, dried over MgSO _4, and then the solvent was removed using a rotary evaporator. Then purified by column chromatography to obtain compound b (30 g, 54.6%).

Step 2.

Compound 1 (30 g, 0.133727 mol) was dissolved in hexane (900 mL) in a well-dried nitrogen-substituted three-necked flask, dissolved, and then Amberlyst 15 (20 g) was added and stirred at room temperature for 30 minutes. Then, sulfuric acid (25 mL) was slowly dropped and stirred. Then, it was extracted with an aqueous sodium hydrogen carbonate solution and dichloromethane (MC), the organic layer was washed with water, dried over MgSO _4, and the solvent was removed using a rotary evaporator. Then, purified by column chromatography to obtain compound c. (13 g, 47.1%).

Step 3.

Compound 2 (5.0 g, 0.02423 mol) was added to THF (100 mL) and dissolved in a well-dried nitrogen-substituted three-necked flask, the temperature was lowered to -78 ° C, and 2.5 M n-butyllithium (9.7 mL) (9.7 mL) , 0.02423 mol) was dropped and stirred at -30 ° C for 30 minutes. Then, the well-dried ZnCl ₂ (3.3 g, 0.02423 mol) was dissolved in THF (40 mL), slowly dropped, and stirred at 0 ° C. for 1 hour. diethyl 2,5-dibromoterephthalate (3.07 g, 0.00807 mol) and Pd (PPh ₃ ) ₄ (4.66 g, 0.00403 mol) was added and refluxed for 12 hours. Thereafter, the mixture was lowered to room temperature, extracted with ethyl acetate, washed with water, dried over MgSO _4, and the solvent was removed using a rotary evaporator. Then purified by column chromatography to obtain compound d (2.65 g, 52%).

 Step 4.

1-bromo-3-((2-ethylhexyl) oxy) benzene, 5.6 g, 0.01981 mol) was added to a well-dried nitrogen-substituted three-necked flask. After melting in THF (60 mL), the temperature was lowered to -78 ° C, and 2.5 M n-Butyllithium (7.9 mL, 0.01981 mol) was dropped and stirred for 1 hour. Then, Compound 3 (2.5 g, 0.00396 mol) was dissolved in THF (80 mL), slowly dropped, and stirred at room temperature for 16 hours. Thereafter, the mixture was extracted with ethyl acetate, and the organic layer was washed with water, dried over MgSO _4, and the solvent was removed using a rotary evaporator. To the well-dried three-necked flask, the solvent-removed reaction intermediate and acetic acid (200 mL) were added and refluxed for 3 hours. Then, after lowering to room temperature, the reaction was poured into ice water to terminate the reaction, extracted with ethyl acetate, washed with water, dried over MgSO _4, and then the solvent was removed using a rotary evaporator. Then purified by column chromatography to obtain compound e. (1.5 g, 30%).

Step 5.

Compound e (1.5 g, 0.00113 mol) and tetramethylethylenediamine (TMEDA, 0.52 g, 0.00452 mol) were dissolved in THF (30 mL) in a well-dried nitrogen-substituted three-necked flask, and the temperature was lowered to -75 ° C. 2.5 M n-butyllithium (n-Butyllithium) (1.8 mL, 0.00452 mol) was dropped and stirred for 1 hour. Then, the well-dried ZnCl ₂ was dissolved in THF (40 mL), slowly dropped, and stirred at 0 ° C. for 1 hour. Then DMF (0.81 g, 0.01129 mol) was injected and stirred for 16 hours.

Then, NaCl aqueous solution (10 mL) was added, stirred for 10 minutes, extracted with chloroform, and the organic layer was washed with water, dried over MgSO ₄ and the solvent was removed using a rotary evaporator. Then purified by column chromatography to obtain compound f (0.6 g, 38.3%).

Step 6.

Acetic acid (20 mL) and sodium acetate (0.1 g, 0.00121 mol), (Z) -2-isocyano-2- (3-oxo-2,3-di) in a well-dried nitrogen-substituted three-necked flask Hydro-1H-inden-1-ylidene) acetonitrile ((Z) -2-isocyano-2- (3-oxo-2,3-dihydro-1H-inden-1-ylidene) acetonitrile, 0.14 g, 0.00075 mol) was added and stirred for 5 minutes, and then compound 5 (0.3 g, 0.00021 mol) was dissolved in toluene (10 mL) and stirred at 100 ^o C for 16 h. After lowering to room temperature, the mixture was poured into ice water to terminate the reaction, extracted with dichloromethane, washed with water, dried over MgSO _4, and the solvent was removed using a rotary evaporator. Then, it was purified by recrystallization to obtain Compound 1 (0.35 g, 92%).

MS (ESI) m / z: 1734.73

¹ H-NMR (300 MHz, CD ₂ Cl ₂ ): 8.88 (s, 2H), 8.68-8.65 (m, 2H), 7.91-7.88 (m, 2H), 7.78-7.74 (m, 4H), 7.59 ( s, 2H), 7.51 (s, 2H), 7.27-7.21 (t, 4H), 6.99-6.93 (m, 8H), 6.88-6.84 (m, 4H), 3.83-3.81 (d, 8H), 1.76- 1.63 (m, 4H), 1.50-1.27 (m, 32H), 1.02 (s, 12H), 0.93-0.88 (m, 24H) δ (ppm)

(Examples 2 to 12)

Each of Compound 2 to Compound ?? was prepared in a similar manner to that of Example 1. MS or ¹ H-NMR of the synthesized compound is shown in Table 1 below.

Example. #
(compound.#) MS or ¹ H-NMR Example 2
(Compound 2) MS (ESI) m / z: 1762..76
¹ H-NMR (300 MHz, CD ₂ Cl ₂ ): 8.88 (s, 2H), 8.67 (s, 2H), 7.78-7.74 (m, 4H), 7.59 (s, 2H), 7.51 (s, 2H) , 7.27-7.21 (t, 4H), 6.99-6.93 (m, 8H), 6.88-6.84 (m, 4H), 3.83-3.81 (d, 8H), 2.42 (s, 6H), 1.76-1.63 (m, 4H), 1.50-1.27 (m, 32H), 1.02 (s, 12H), 0.93-0.88 (m, 24H) δ (ppm) Example 3
(Compound 3) MS (ESI) m / z: 1870.57
¹ H-NMR (300 MHz, CD ₂ Cl ₂ ): 8.88 (s, 2H), 8.67 (s, 2H), 7.76 (s, 2H), 7.59 (s, 2H), 7.51 (s, 2H), 7.27 -7.21 (t, 4H), 6.99-6.93 (m, 8H), 6.88-6.84 (m, 4H), 3.83-3.81 (d, 8H), 1.76-1.63 (m, 4H), 1.50-1.27 (m, 32H), 1.02 (s, 12H), 0.93-0.88 (m, 24H) δ (ppm) Example 4
(Compound 4) MS (ESI) m / z: 1806.69
¹ H-NMR (300 MHz, CD ₂ Cl ₂ ): 8.83 (s, 2H), 8.62 (s, 2H), 7.71 (s, 2H), 7.54 (s, 2H), 7.46 (s, 2H), 7.22 -7.16 (t, 4H), 6.94-6.88 (m, 8H), 6.83-6.79 (m, 4H), 3.78-3.76 (d, 8H), 1.71-1.58 (m, 4H), 1.45-1.22 (m, 32H), 0.97 (s, 12H), 0.88-0.83 (m, 24H) δ (ppm) Example 5
(Compound 5) MS (ESI) m / z: 1794.75
¹ H-NMR (300 MHz, CD ₂ Cl ₂ ): 8.88 (s, 2H), 8.67 (s, 2H), 7.78-7.74 (m, 4H), 7.59 (s, 2H), 7.51 (s, 2H) , 7.27-7.21 (t, 4H), 6.99-6.93 (m, 8H), 6.88-6.84 (m, 4H), 3.83-3.81 (d, 8H), 3.77 (s, 6H), 1.76-1.63 (m, 4H), 1.50-1.27 (m, 32H), 1.02 (s, 12H), 0.93-0.88 (m, 24H) δ (ppm) Example 6
(Compound 6) MS (ESI) m / z: 1774.67
¹ H-NMR (300 MHz, CD ₂ Cl ₂ ): 8.88 (s, 2H), 8.67 (s, 2H), 7.51 (s, 2H), 7.27-7.21 (t, 4H), 6.99-6.93 (m, 8H), 6.88-6.84 (m, 4H), 3.83-3.81 (d, 8H), 2.36 (s, 6H), 1.76-1.63 (m, 4H), 1.50-1.27 (m, 32H), 1.02 (s, 12H), 0.93-0.88 (m, 24H) δ (ppm) Example 7
(Compound 7) MS (ESI) m / z: 1656.74
¹ H-NMR (300 MHz, CD ₂ Cl ₂ ): 8.88 (s, 2H), 8.68-8.65 (m, 2H), 7.91-7.88 (m, 2H), 7.78-7.74 (m, 4H), 7.59 ( s, 2H), 7.51 (s, 2H), 7.27-7.21 (t, 4H), 6.99-6.93 (m, 8H), 6.88-6.84 (m, 4H), 2.60-2.35 (d, 8H), 1.68- 1.54 (m, 4H), 1.45-1.22 (m, 32H), 1.02 (s, 12H), 0.88-0.83 (m, 24H) δ (ppm) Example 8
(Compound 8) MS (ESI) m / z: 1684.77
¹ H-NMR (300 MHz, CD ₂ Cl ₂ ): 8.88 (s, 2H), 8.67 (s, 2H), 7.78-7.74 (m, 4H), 7.59 (s, 2H), 7.51 (s, 2H) , 7.27-7.21 (t, 4H), 6.99-6.93 (m, 8H), 6.88-6.84 (m, 4H), 2.60-2.35 (d, 8H), 2.42 (s, 6H), 1.68-1.54 (m, 4H), 1.45-1.22 (m, 32H), 1.02 (s, 12H), 0.88-0.83 (m, 24H) δ (ppm) Example 9
(Compound 9) MS (ESI) m / z: 1792.58
¹ H-NMR (300 MHz, CD ₂ Cl ₂ ): 8.88 (s, 2H), 8.67 (s, 2H), 7.76 (s, 2H), 7.59 (s, 2H), 7.51 (s, 2H), 7.27 -7.21 (t, 4H), 6.99-6.93 (m, 8H), 6.88-6.84 (m, 4H), 2.60-2.35 (d, 8H), 1.68-1.54 (m, 4H), 1.45-1.22 (m, 32H), 1.02 (s, 12H), 0.88-0.83 (m, 24H) δ (ppm) Example 10
(Compound 10) MS (ESI) m / z: 1728.70
¹ H-NMR (300 MHz, CD ₂ Cl ₂ ): 8.83 (s, 2H), 8.62 (s, 2H), 7.71 (s, 2H), 7.54 (s, 2H), 7.46 (s, 2H), 7.22 -7.16 (t, 4H), 6.94-6.88 (m, 8H), 6.83-6.79 (m, 4H), 2.60-2.35 (d, 8H), 1.68-1.54 (m, 4H), 1.45-1.22 (m, 32H), 1.02 (s, 12H), 0.88-0.83 (m, 24H) δ (ppm) Example 11
(Compound 11) MS (ESI) m / z: 1716.76
¹ H-NMR (300 MHz, CD ₂ Cl ₂ ): 8.88 (s, 2H), 8.67 (s, 2H), 7.78-7.74 (m, 4H), 7.59 (s, 2H), 7.51 (s, 2H) , 7.27-7.21 (t, 4H), 6.99-6.93 (m, 8H), 6.88-6.84 (m, 4H), 3.77 (s, 6H), 2.60-2.35 (d, 8H), 1.68-1.54 (m, 4H), 1.45-1.22 (m, 32H), 1.02 (s, 12H), 0.88-0.83 (m, 24H) δ (ppm) Example 12
(Compound 12) MS (ESI) m / z: 1710.70
¹ H-NMR (300 MHz, CD ₂ Cl ₂ ): 8.88 (s, 2H), 8.67 (s, 2H), 7.51 (s, 2H), 7.27-7.21 (t, 4H), 6.99-6.93 (m, 8H), 6.88-6.84 (m, 4H) ,, 2.60-2.35 (d, 8H), 1.68-1.54 (m, 4H), 1.45-1.22 (m, 32H), 1.02 (s, 12H), 0.88-0.83 (m, 24H) δ (ppm)

(Example 13)

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 Compound 1 (electron acceptor) of the present invention and P3HT (Poly (3-hexylthiophene)) electron donor in a chloroform solvent at a weight ratio of 1: 1 to 0.45 μm (PTFE) syringe filter. 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. 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.

The electrical characteristics of the fabricated organic solar cell, open voltage (Voc), short-circuit current (Jsc), fill factor (Fill Factor, FF) and photoelectric conversion efficiency (Power Conversion Efficiency, PCE) were confirmed.

(Examples 14 to 24)

Fabrication of organic solar cells

In Example 19, the compound 1 used in the photoactive layer Instead, each of the compounds of the present invention of Examples 2 to 18 was used to complete an organic solar cell. Then, the electrical properties of the produced organic solar cell were checked.

(Comparative Example 1)

Fabrication of organic solar cells

PC71BM

PC71BM

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

As a result, 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 6.94% or more. This effect is expected to be due to the introduction of the central skeleton according to the present invention.

When employing the compound according to the present invention described above, it was confirmed that it is possible to realize high short-circuit current (J _sc ) and charge rate (FF) as well as to realize excellent photoelectric conversion efficiency. In addition, the characteristics of the organic solar cell employing the compound according to the present invention as an electron acceptor in a photoactive layer, that is, in photoelectric conversion efficiency, the rate of change at room temperature (25 ° C) as well as high temperature (eg, 110 ° C or higher) was extremely low . Specifically, it has been confirmed that the organic solar cell according to the present invention is capable of realizing stable characteristics up to 2,000 hours even in an environment of harsh conditions, and can secure long-term stability.

This effect corresponds to a significantly improved photoelectric conversion efficiency, short-circuit current and charging rate compared to an organic solar cell using a conventional electron acceptor (PC71BM).

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 ₁₁ , R ₁₂ , R ₁₇ and R ₁₈ are each independently C1-C30 alkyl;
R ₁₃ To R ₁₆ 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 halo. Substituted with one or more substituents selected from C1-C30 alkyl;
V ₁₁ and V ₁₂ 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 ₁₁ to Y ₁₄ 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,
V ₁₁ and V ₁₂ are each independently represented by the following formula (2), 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 ₁₁ and V ₁₂ 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 ₁₁ and V ₁₂ 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 ₁₃ to R ₁₆ are each independently phenyl, naphthyl, or biphenyl aryl, and each aryl is independently substituted with one or more substituents selected from C1-C30 alkyl, C1-C30 alkoxy and C1-C30 alkylthio. Compound. 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 is an organic light emitting device, an organic thin film transistor, an organic photosensor or an organic solar cell, an organic electronic device. 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.