KR20160050223A - Benzothiadiazole derivatives and Solar cell device using this material - Google Patents

Benzothiadiazole derivatives and Solar cell device using this material Download PDF

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KR20160050223A
KR20160050223A KR1020140147913A KR20140147913A KR20160050223A KR 20160050223 A KR20160050223 A KR 20160050223A KR 1020140147913 A KR1020140147913 A KR 1020140147913A KR 20140147913 A KR20140147913 A KR 20140147913A KR 20160050223 A KR20160050223 A KR 20160050223A
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benzothiadiazole
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김윤희
권순기
이기백
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경상대학교산학협력단
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Abstract

The present invention relates to benzothiadiazole derivatives and an organic solar cell using the same. An organic semiconductor compound of the present invention can have excellent oxidation stability and electrical properties by comprising benzothiadiazole which is an electron doner in the molecule. Thus, an organic solar cell comprising the compound as a material for an active layer can have excellent oxidation stability, high open circuit voltage, and high current density. The benzothiadiazole derivatives of the present invention are represented by chemical formula 1.

Description

벤조싸이아다이아졸 유도체 및 이를 이용한 유기태양전지{Benzothiadiazole derivatives and Solar cell device using this material}[0001] The present invention relates to benzothiadiazole derivatives and solar cell devices using the same,

본 발명은 벤조싸이아다이아졸 유도체 및 이를 이용한 유기태양전지에 관한 것이다. 보다 상세하게는 분자내 전자 당김체인 벤조싸이아다이아졸을 포함하는 유기 반도체 화합물 및 이를 이용한 유기태양전지에 관한 것이다.The present invention relates to benzothiadiazole derivatives and organic solar cells using the same. And more particularly, to an organic semiconductor compound containing a benzothiazole as an electron withdrawing group in a molecule and an organic solar cell using the same.

태양전지는 빛에너지를 전기에너지로 직접 변환시켜 주는 소자이다. 이들은 다양한 종류의 재료로 만들어지고 있으나 현재 가장 많이 사용되고 있는 재료는 단결정 Si이다. 그러나 단결정 Si 태양광전지는 제조단가를 더 이상 낮출 수 없는 문제와 생산 및 응용등에 제한이 있어, 최근 들어서는 박막 형태의 태양전지의 개발이 활발히 이루어지고 있다. 이중 유기태양전지는 유연하고 대면적화 할 수 있으며, 가볍고, 값싸게 제작 할 수 있는 장점을 가지고 있어, 이 분야에 많은 연구가 진행되고 있다. 유기태양전지는 크게 양 전극과 광활성층으로 이루어져 있다. 광활성층은 다시 전자 주게 소재와 전자 받게 소재로 구분 할 수 있으며, 전자 주게 소재는 단분자와 고분자로 나뉜다. 단분자 소재의 경우 phthalocyanine계 CuPc, ZnPc 등을 열증착을 통해 차례대로 쌓는 방법으로 제작 되고 있다. 반면 고분자는 PPV (poly(para-phenylene vinylene)), PF (polyfluorene) 계열 물질들이 대표적으로 쓰이고 최근에는 전자주게/받게를 교대로 중합하여 PFDTBT, PCPDTBT 같은 낮은 밴드갭 에너지를 갖는 공중합체 소재들이 연구되고 있으며, 고분자는 단분자 소재와 달리 스핀 코팅, 잉크젯 방식, gravure 인쇄방식 등을 이용하고 있어 상온 공정이 가능하며 간편하게 소자를 제작 할 수 있다.Solar cells are devices that directly convert light energy into electrical energy. They are made of various kinds of materials, but the most widely used material is monocrystalline Si. However, monocrystalline Si solar photovoltaic cells are limited in their production cost and manufacturing cost because they can no longer lower the production cost, and thin film solar cells have been actively developed recently. The dual organic solar cell has advantages such as being flexible, large-sized, light, and inexpensive, and so much research is being conducted in this field. Organic solar cells consist largely of both electrodes and photoactive layer. The photoactive layer can be divided into an electron-emitting material and an electron-receiving material. The electron-emitting material is divided into a single molecule and a polymer. In the case of monomolecular materials, phthalocyanine based CuPc and ZnPc are stacked one after another by thermal deposition. On the other hand, polymers are typically used for PPV (poly (para-phenylene vinylene)) and PF (polyfluorene) materials. In recent years, copolymer materials having low band gap energy such as PFDTBT and PCPDTBT have been studied by alternately polymerizing electron acceptors / Unlike single-molecule materials, polymers use spin coating, ink-jet printing, and gravure printing. They can be easily processed at room temperature.

상기 고분자를 이용한 유기태양전지의 원리는 전자 주게 소재인 고분자가 빛을 흡수하여 엑시톤 (exciton)을 형성하고 엑시톤이 전자 주게/받게 계면에서 분리가 일어나며, 이는 전자와 정공으로 나뉜다. 분리된 전자와 정공은 각각의 전극으로 이동하여 전기를 생산한다. The principle of an organic solar cell using the polymer is that a polymer as an electron-donating material absorbs light to form an exciton, and excitons are separated at an electron-accepting / receiving interface, which is divided into an electron and a hole. The separated electrons and holes move to the respective electrodes to produce electricity.

즉 낮은 밴드갭 에너지를 갖는 소재 개발을 위해 고분자의 방향성을 유지하고, 컨쥬게이션 길이를 늘리는 등의 연구가 진행되고 있으며, 이러한 일례로 한국공개특허공보 제 2011-0098303를 들 수 있다. 그러나 여전히 산화 안정성이 높고 고효율화를 위한 소재의 연구가 요구되고 있는 실정이다.In other words, in order to develop a material having a low band gap energy, studies are underway to maintain the orientation of the polymer and to increase the conjugation length, for example, Korean Patent Publication No. 2011-0098303. However, it is still required to study the material for high oxidation stability and high efficiency.

이에 본 발명자들은 전자 당김체인 벤조싸이아다이아졸을 포함하여, 산화안정성이 우수하고, 전자 이동 특성이 우수한 유기 반도체 화합물과 이를 이용한 고효율의 유기태양전지를 개발하고 본 발명을 완성하였다.Accordingly, the present inventors have developed an organic semiconductor compound having excellent oxidation stability and electron transfer characteristics, including a benzothiazole as an electron withdrawing group, and a highly efficient organic solar cell using the organic semiconductor compound and completed the present invention.

한국공개특허공보 제 2011-0098303호Korean Patent Publication No. 2011-0098303 미국등록특허 제5,609,970호,U. S. Patent No. 5,609, 970, 미국등록특허 제5,571,626호U.S. Patent No. 5,571,626 미국등록특허 제5,414,069호U.S. Patent No. 5,414,069 미국등록특허 제5,376,456호U.S. Patent No. 5,376,456

본 발명의 목적은 분자 내 전자 주게인 벤조싸이아다이아졸을 가짐으로써, 산화 안정성이 우수하고, 전기적 특성이 우수한 유기 반도체 화합물 및 이를 광활성층 재료로 도입한 유기태양전지를 제공하는 것이다.An object of the present invention is to provide an organic semiconductor compound excellent in oxidation stability and excellent in electrical characteristics by having a benzothiazole as an electron donor in a molecule and an organic solar cell into which the organic semiconductor compound is introduced as a photoactive layer material.

본 발명은 하기 화학식 1로 표시되는 벤조싸이아다이아졸 유도체를 포함한다.The present invention includes benzothiadiazole derivatives represented by the following formula (1).

[화학식 1][Chemical Formula 1]

Figure pat00001
Figure pat00001

[상기 화학식 1에서,[In the above formula (1)

상기 V1 및 V2는 각각 독립적으로 수소,

Figure pat00002
,
Figure pat00003
,
Figure pat00004
,
Figure pat00005
,
Figure pat00006
또는
Figure pat00007
이고, 상기 Z는 각각 독립적으로 S, O 또는 Se이며;V 1 and V 2 are each independently hydrogen,
Figure pat00002
,
Figure pat00003
,
Figure pat00004
,
Figure pat00005
,
Figure pat00006
or
Figure pat00007
And each Z is independently S, O or Se;

상기 L1은 단일결합,

Figure pat00008
,
Figure pat00009
,
Figure pat00010
,
Figure pat00011
이고, 상기 Z는 각각 독립적으로 S, O 또는 Se이고, 상기 R 및 R'는 각각 독립적으로 수소 (C1-C30)알킬, (C1-C30)알콕시 또는 (C1-C30)알킬티오이며;L < 1 > is a single bond,
Figure pat00008
,
Figure pat00009
,
Figure pat00010
,
Figure pat00011
(C1-C30) alkoxy or (C1-C30) alkylthio, each of which is independently S, O or Se, and R and R 'are each independently hydrogen (C1-C30) alkyl;

상기 R1, R2, R3 및 R4는 각각 독립적으로 수소, 불소, (C1-C30)알킬, (C1-C30)알콕시 또는 (C1-C30)알킬티오이다.]Each of R 1, R 2, R 3 and R 4 is independently hydrogen, fluorine, (C 1 -C 30) alkyl, (C 1 -C 30) alkoxy or (C 1 -C 30)

본 발명의 일 실시예에 따른 벤조싸이아다이아졸 유도체는 하기 화합물에서 선택될 수 있다.The benzothiadiazole derivatives according to one embodiment of the present invention can be selected from the following compounds.

Figure pat00012
Figure pat00012

본 발명은 상기 벤조싸이아다이아졸 유도체를 포함하는 유기전자소자를 제공한다.The present invention provides an organic electronic device comprising the benzothiadiazole derivative.

본 발명의 일 실시예에 따른 상기 유기전자소자는 유기발광소자, 유기태양전지, 유기트랜지스터, 유기 메모리 또는 유기감광체(OPC)일 수 있다.The organic electronic device according to an exemplary embodiment of the present invention may be an organic light emitting device, an organic solar cell, an organic transistor, an organic memory, or an organic photoconductor (OPC).

본 발명에 따른 화합물은 전자 주게인 벤조싸이아다이아졸을 가짐으로써, 낮은 에너지 밴드갭과 낮은 구동 전압을 가질 뿐 아니라 열에 대한 안정성을 가지며, 이를 채용한 유기전자소자는 높은 전자 밀도로 인해 높은 단락 전류(Jsc)를 가져, 우수한 효율과 장수명 특성을 가질 수 있다. The compound according to the present invention has a low energy band gap and low driving voltage as well as heat stability by having electron-donating benzothiadiazole, and the organic electronic device employing it has high short circuit due to high electron density Current (Jsc), and can have excellent efficiency and long-life characteristics.

본 발명은 높은 전하 이동도, 높은 전자 밀도 및 높은 용해도를 가지는 하기 화학식 1로 표시되는 신규한 유기 반도체 화합물 및 이를 이용한 유기태양전지에 관한 것으로, 본 발명에 따른 유기 반도체 화합물은 용해도가 높아 간편한 용액 공정이 가능하며, 이를 채용한 유기태양전지는 높은 전자 이동도에 의한 높은 단락 전류(Jsc)를 가져 고효율 특성을 가질 수 있으며, 산화안정성이 우수하고, 개방전압(Voc)을 향상시킬 수 있는 특징이 있다. The present invention relates to a novel organic semiconductor compound represented by the following general formula (1) having high charge mobility, high electron density and high solubility, and an organic solar cell using the same. The organic semiconductor compound according to the present invention has high solubility, The organic solar cell employing the organic solar cell can have a high short-circuit current (Jsc) due to high electron mobility and can have a high efficiency characteristic, and is excellent in oxidation stability and can improve the open-circuit voltage (Voc) .

[화학식 1][Chemical Formula 1]

Figure pat00013
Figure pat00013

[상기 화학식 1에서,[In the above formula (1)

상기 V1 및 V2는 각각 독립적으로 수소,

Figure pat00014
,
Figure pat00015
,
Figure pat00016
,
Figure pat00017
,
Figure pat00018
또는
Figure pat00019
이고, 상기 Z는 각각 독립적으로 S, O 또는 Se이며;V 1 and V 2 are each independently hydrogen,
Figure pat00014
,
Figure pat00015
,
Figure pat00016
,
Figure pat00017
,
Figure pat00018
or
Figure pat00019
And each Z is independently S, O or Se;

상기 L1은 단일결합,

Figure pat00020
,
Figure pat00021
,
Figure pat00022
,
Figure pat00023
이고, 상기 Z는 각각 독립적으로 S, O 또는 Se이고, 상기 R 및 R'는 각각 독립적으로 수소, (C1-C30)알킬, (C1-C30)알콕시 또는 (C1-C30)알킬티오이며;L < 1 > is a single bond,
Figure pat00020
,
Figure pat00021
,
Figure pat00022
,
Figure pat00023
(C1-C30) alkyl, (C1-C30) alkoxy or (C1-C30) alkylthio, each of which is independently S, O or Se, and R and R 'are each independently hydrogen,

상기 R1, R2, R3 및 R4는 각각 독립적으로 수소, 불소, (C1-C30)알킬, (C1-C30)알콕시 또는 (C1-C30)알킬티오이다.]Each of R 1, R 2, R 3 and R 4 is independently hydrogen, fluorine, (C 1 -C 30) alkyl, (C 1 -C 30) alkoxy or (C 1 -C 30)

본 발명의 일 실시예에 따른 벤조싸이아다이아졸 유도체는 하기 구조에서 선택될 수 있으나 이에 한정되는 것은 아니다.The benzothiadiazole derivatives according to an embodiment of the present invention may be selected from the following structures, but are not limited thereto.

Figure pat00024
Figure pat00024

또한 본 발명은 상기 벤조싸이아다이아졸 유도체를 포함하는 유기태양전지를 포함한다. 보다 바람직하게는 본 발명에 따른 상기 벤조싸이아다이아졸 유도체를 유기태양전지의 활성층에 포함할 수 있다. The present invention also includes an organic solar cell comprising the benzothiadiazole derivative. More preferably, the benzothiadiazole derivative according to the present invention can be incorporated into an active layer of an organic solar cell.

일반적으로 본 발명에 따른 유기태양전지는 이하 상술하는 방법으로 제조될 수 있으나 이는 일례를 들어 설명하는 것으로 이에 한정이 있는 것은 아니다.In general, the organic solar cell according to the present invention can be manufactured by the method described below, but the present invention is not limited thereto.

본 발명의 바람직한 실시예에 따라 제조된 유기태양전지는 기판, 제1전극, 정공수송층, 활성층, 전자수송층 및 제2전극으로 이루어진다. An organic solar cell manufactured according to a preferred embodiment of the present invention comprises a substrate, a first electrode, a hole transporting layer, an active layer, an electron transporting layer, and a second electrode.

상기 기판은 유리 및 석영판 이외에도 PET(polyethylene terephthalate), PEN(polyethylene naphthelate), PP(polyperopylene), PI(polyimide), PC(polycarbornate), PS(polystylene), POM(polyoxyethlene), AS 수지(acrylonitrile styrene copolymer), ABS 수지(acrylonitrile butadiene styrene copolymer) 및 TAC(Triacetyl cellulose) 등을 포함하는 플라스틱과 같은 유연하고 투명한 물질로 제조될 수 있다. In addition to glass and quartz, the substrate may be made of a material selected from the group consisting of polyethylene terephthalate (PEN), polyperopylene (PEN), polyimide, polyimide, polycarbonate, polystyrene, polyoxyethylenes, such as plastics, including acrylonitrile butadiene styrene copolymer, ABS resin, and TAC (triacetyl cellulose).

또한 상기 제1 전극은 스퍼터링, E-Beam, 열증착, 스핀코팅, 스크린 프린팅, 잉크젯 프린팅, 닥터 블레이드 또는 그라비아 프린팅법을 사용하여 투명전극 물질을 상기 기판의 일면에 도포되거나 필름형태로 코팅됨으로써 형성된다. 제1 전극(120)은 애노드의 기능을 하는 부분으로써, 후술하는 제2 전극(160)에 비해 일함수가 큰 물질로 투명성 및 도전성을 갖는 임의의 물질이 사용될 수 있다. 예를 들면, ITO(indium tin oxide), 금, 은, 플로린이 도핑된 틴 옥사이드(fluorine doped tin oxide; FTO), 알루미늄이 도핑된 징크 옥사이드(aluminium doped zink oxide, AZO), IZO(indium zink oxide), ZnO-Ga2O3, ZnO-Al2O3 및 ATO(antimony tin oxide) 등이 있으며, 바람직하게는 ITO를 사용하는 것이 좋다.The first electrode may be formed by coating a transparent electrode material on one side of the substrate or by coating it with a film using sputtering, E-beam, thermal evaporation, spin coating, screen printing, inkjet printing, doctor blade or gravure printing do. The first electrode 120 functions as an anode and may be made of any material having a higher work function than the second electrode 160 and having transparency and conductivity. For example, there are known indium tin oxide (ITO), gold, silver, fluorine doped tin oxide (FTO), aluminum doped zink oxide (AZO), indium zinc oxide ), ZnO-Ga 2 O 3 , ZnO-Al 2 O 3 and ATO (antimony tin oxide), and it is preferable to use ITO.

상기 제1 전극의 상부에는 정공 수송층이 스핀코팅 또는 딥코팅 등의 방법을 통해 도입되는데, 본 발명에서는 전도성 고분자 용액으로서 폴리리(3,4-에틸렌디옥시티오펜):폴리(4-스티렌설포네이트)[PEDOT:PSS]를 사용하는 것이 바람직하다.A hole transport layer is introduced onto the first electrode through spin coating or dip coating. In the present invention, a poly (3,4-ethylenedioxythiophene): poly (4-styrenesulfonate ) [PEDOT: PSS] is preferably used.

또한 상기 활성층에는 본 발명에 따른 유기 반도체 화합물을 포함할 수 있으며, 이의 배합량은 용도에 따라 적절하게 조절될 수 있다. 또한 상기 유기 반도체 화합물은 유기 용매에 용해시켜, 60 내지 120nm 두께로 활성층에 도입될 수 있다. 이때, 상기 유기용매는 아세톤, 메탄올, THF, 톨루엔, 자일렌, 테트랄린, 클로로포름, 클로로벤젠, 디클로로벤젠 또는 이들의 혼합용매 일 수 있으나, 이에 한정되는 것은 아니다. 또한 본 발명에 따른 유기 반도체 화합물을 포함하는 상기 활성층은 높은 전자 밀도로 인하여, 단락전류밀도(short circuit current density) 및 개방전압(open circuit voltage)이 증가하여 에너지변환효율에 좋다. The active layer may contain the organic semiconductor compound according to the present invention, and the compounding amount thereof may be suitably adjusted according to the use. The organic semiconductor compound may be dissolved in an organic solvent and introduced into the active layer to a thickness of 60 to 120 nm. At this time, the organic solvent may be acetone, methanol, THF, toluene, xylene, tetralin, chloroform, chlorobenzene, dichlorobenzene or a mixture thereof, but is not limited thereto. In addition, the active layer including the organic semiconductor compound according to the present invention has good short-circuit current density and open circuit voltage due to its high electron density, which is good for energy conversion efficiency.

상기 전자수송층은 전자수송층의 모폴로지를 향상시키기 위해 계면활성제(surfactant)를 첨가하여 제조 할 수 있다. 이때, 상기 전자수송층은 친전자성 기능을 가지는 수용성 고분자를 물, 에탄올 또는 이들의 혼합용매에 용해하고, 상기 고분자 용액에 계면활성제를 첨가한 후 여과하여 박막을 형성하는 단계를 포함하여 제조할 수 있다. 이때, 상기 친전자성 기능기를 가지는 수용성 고분자로는 폴리[9,9-비스(6'-디에탄올아미노)헥실)-플루오렌]이 바람직하며, 상기 계면활성제는 2,4,7,9-테트라메틸-5-데킨-4,7-디올인 것이 바람직하지만, 이에 한정되는 것은 아니다. 또한 상기 수용성 고분자 및 계면활성제가 혼합된 용액을 스핀 코팅 등의 방법으로 2 내지 20nm 코팅하여 열처리하는 것이 좋다. 이때, 상기 전자수송층은 스핀코팅의 방법 외에도 딥코팅, 스크린 프린팅, 잉크젯 프린팅, 그라비아 프린팅, 스프레이 코팅, 닥터블레이드 또는 브러쉬 페인팅 등의 방법을 응용할 수 있으며, 본 발명이 이에 제한되는 것은 아니다.The electron transport layer may be prepared by adding a surfactant to improve the morphology of the electron transport layer. At this time, the electron transport layer may be prepared by dissolving a water-soluble polymer having an electrophilic function in water, ethanol or a mixed solvent thereof, adding a surfactant to the polymer solution, and then filtering to form a thin film have. As the water-soluble polymer having the electrophilic functional group, poly [9,9-bis (6'-diethanolamino) hexyl) -fluorene] is preferable, and the surfactant is 2,4,7,9- Tetramethyl-5-decyne-4,7-diol, but is not limited thereto. The solution mixed with the water-soluble polymer and the surfactant may be coated by 2 to 20 nm by a spin coating method and then heat-treated. At this time, the electron transport layer may be applied by dip coating, screen printing, inkjet printing, gravure printing, spray coating, doctor blade, brush painting or the like in addition to the spin coating method, but the present invention is not limited thereto.

또한 상기 제2 전극은 전자수송층이 도입된 상태에서 열증착기를 이용하여 증착될 수 있다. 이때 사용가능한 전극재료로는 불화리튬/알루미늄, 불화리튬/칼슘/알루미늄, 칼슘/알루미늄, 불화바륨/알루미늄, 불화바륨/바륨/알루미늄, 바륨/알루미늄, 알루미늄, 금, 은, 마스네슘:은 및 리튬:알루미늄 중에서 선택될 수 있으며, 바람직하게는 불화바륨/바륨/알루미늄 구조로 제작된 전극을 사용하는 것이 좋다.Also, the second electrode may be deposited using a thermal evaporator in a state in which an electron transport layer is introduced. The electrode material that can be used at this time includes lithium fluoride / aluminum, lithium fluoride / calcium / aluminum, calcium / aluminum, barium fluoride / aluminum, barium fluoride / barium / aluminum, barium / aluminum, aluminum, gold, silver, Lithium, and aluminum. Preferably, an electrode made of a barium / barium / aluminum structure is used.

Claims (4)

하기 화학식 1로 표시되는 벤조싸이아다이아졸 유도체:
[화학식 1]
Figure pat00025

[상기 화학식 1에서,
상기 V1 및 V2는 각각 독립적으로 수소,
Figure pat00026
,
Figure pat00027
,
Figure pat00028
,
Figure pat00029
,
Figure pat00030
또는
Figure pat00031
이고, 상기 Z는 각각 독립적으로 S, O 또는 Se이며;
상기 L1은 단일결합,
Figure pat00032
,
Figure pat00033
,
Figure pat00034
,
Figure pat00035
이고, 상기 Z는 각각 독립적으로 S,O 또는 Se이고, 상기 R 및 R'는 각각 독립적으로 수소, (C1-C30)알킬, (C1-C30)알콕시 또는 (C1-C30)알킬티오이며;
상기 R1, R2, R3 및 R4는 각각 독립적으로 수소, 불소, (C1-C30)알킬, (C1-C30)알콕시 또는 (C1-C30)알킬티오이다.]
A benzothiadiazole derivative represented by the following formula (1): < EMI ID =
[Chemical Formula 1]
Figure pat00025

[In the above formula (1)
V 1 and V 2 are each independently hydrogen,
Figure pat00026
,
Figure pat00027
,
Figure pat00028
,
Figure pat00029
,
Figure pat00030
or
Figure pat00031
And each Z is independently S, O or Se;
L < 1 > is a single bond,
Figure pat00032
,
Figure pat00033
,
Figure pat00034
,
Figure pat00035
(C1-C30) alkyl, (C1-C30) alkoxy or (C1-C30) alkylthio, each of which is independently S, O or Se, and R and R 'are each independently hydrogen,
Each of R 1, R 2, R 3 and R 4 is independently hydrogen, fluorine, (C 1 -C 30) alkyl, (C 1 -C 30) alkoxy or (C 1 -C 30)
제 1항에 있어서,
하기 화합물에서 선택되는 것인 벤조싸이아다이아졸 유도체;
Figure pat00036
The method according to claim 1,
Benzothiadiazole derivatives wherein the benzothiadiazole derivative is selected from the following compounds;
Figure pat00036
제 1항에 따른 벤조싸이아다이아졸 유도체를 포함하는 유기전자소자.An organic electronic device comprising the benzothiazole diazole derivative according to claim 1. 제 3항에 있어서,
상기 유기전자소자는 유기발광소자, 유기태양전지, 유기트랜지스터, 유기 메모리 또는 유기감광체(OPC)인 유기전자소자.
The method of claim 3,
Wherein the organic electronic device is an organic light emitting device, an organic solar cell, an organic transistor, an organic memory or an organic photoconductor (OPC).
KR1020140147913A 2014-10-29 2014-10-29 Benzothiadiazole derivatives and Solar cell device using this material KR20160050223A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115028602A (en) * 2022-08-09 2022-09-09 中国华能集团清洁能源技术研究院有限公司 Star-shaped molecule for hole transport layer and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115028602A (en) * 2022-08-09 2022-09-09 中国华能集团清洁能源技术研究院有限公司 Star-shaped molecule for hole transport layer and preparation method and application thereof
CN115028602B (en) * 2022-08-09 2022-11-15 中国华能集团清洁能源技术研究院有限公司 Star-shaped molecule capable of being used for hole transport layer and preparation method and application thereof

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