KR101952815B1 - Compound for photoactive layer additive and method of manufacturing the same, and all-polymer organic solar cell comprising the same - Google Patents
Compound for photoactive layer additive and method of manufacturing the same, and all-polymer organic solar cell comprising the same Download PDFInfo
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- KR101952815B1 KR101952815B1 KR1020170087676A KR20170087676A KR101952815B1 KR 101952815 B1 KR101952815 B1 KR 101952815B1 KR 1020170087676 A KR1020170087676 A KR 1020170087676A KR 20170087676 A KR20170087676 A KR 20170087676A KR 101952815 B1 KR101952815 B1 KR 101952815B1
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- photoactive layer
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
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- H01L51/0035—
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- H01L51/0034—
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- H01L51/0046—
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/451—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising a metal-semiconductor-metal [m-s-m] structure
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
- H10K85/211—Fullerenes, e.g. C60
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L2031/0344—Organic materials
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
본 발명은 하기 구조식 1로 표시되는 광활성층 첨가제용 화합물에 관한 것으로, 본 발명은 전자받개 고분자와 전자주개 고분자와 동시에 분자적 상호작용을 할 수 있는 펜타플루오르벤젠 기반 첨가제를 제조하고, 이를 사용하여 큰 상 분리 없이 균일한 모폴로지를 가지는 유기태양전지 광활성층(photoactive layer)을 형성할 수 있다. 또한, 펜타플루오르벤젠 기반의 첨가제를 포함하는 고분자-고분자 광활성층은 전자받개 고분자와 전자주개 고분자 간의 효율적인 전하 추출 및 전하 이동을 위한 고분자의 배향 및 결정성을 조절하여 광전기적 특성이 우수한 고분자-고분자 태양전지를 구현할 수 있다.
[구조식 1]
Ar1-Y-Ar2 The present invention relates to a compound for a photoactive layer additive represented by the following structural formula 1, wherein a pentafluorobenzene-based additive capable of molecular interaction with an electron acceptor polymer and an electron donor polymer at the same time is prepared, An organic solar cell photoactive layer having a uniform morphology can be formed without a large phase separation. In addition, the polymer-polymer photoactive layer containing the pentafluorobenzene-based additive controls the orientation and crystallinity of the polymer for efficient charge extraction and charge transfer between the electron acceptor polymer and the electron donor polymer, Solar cells can be realized.
[Structural formula 1]
Ar 1 -Y-Ar 2
Description
본 발명은 광활성층 첨가제용 화합물 및 그의 제조방법과 이를 포함하는 고분자-고분자 태양전지에 관한 것으로, 보다 상세하게는 전자주개 고분자 및 전자받개 고분자를 포함하는 유기태양전지의 광활성층에 펜타플루오르페닐기와 페닐기로 구성된 첨가제용 화합물을 첨가하여 고분자-고분자 태양전지의 효율을 향상시키는 기술에 관한 것이다.The present invention relates to a compound for a photoactive layer additive, a process for producing the same, and a polymer-polymer solar cell comprising the same, and more particularly, to a photoactive layer of an organic solar cell comprising an electron donor polymer and an electron acceptor polymer, To a technique for improving the efficiency of a polymer-polymer solar cell by adding a compound for an additive composed of a phenyl group.
태양 전지는 무한하고 재생 가능하며 환경친화적인 전기 에너지원으로서 주목받고 있다. 현재 태양전지는 무기물을 이용한 (가장 대표적인 주원료인 실리콘 결정형 태양전지) 1세대 결정형 태양전지가 태양광 발전 시장의 90%를 차지하고 있다. 그러나 석탄이나 석유, 가스에 비해 발전 단가가 5~20배나 높아 비용 측면에서 효율성이 낮은 문제가 있었으며, 이로 인해 2세대 기술이 대안으로 대두되었다.Solar cells are attracting attention as an endless, renewable and environmentally friendly source of electrical energy. Currently, solar cell uses inorganic materials (silicon crystal type solar cell, which is the most representative raw material). The first generation crystalline solar cell accounts for 90% of the solar power generation market. However, compared to coal, oil, and gas, the cost of power generation was 5 to 20 times higher than that of coal, petroleum, and gas, resulting in low efficiency and second generation technology as an alternative.
한편, 2세대 박막 태양전지 시장 점유율은 실리콘(5.2%), (4.7%), COGS (0.5%)등이 전체 시장의 10%를 차지하고 있으나 아직은 미미한 상태이고, 2세대 태양전지 기술은 제작 공정이 까다롭고 고가의 장비가 필요하여 단가가 높다는 문제점이 있었다. 비용 상승의 주요 요인은 주로 진공 및 고온 하에서 반도체 박막을 제공하는 공정에 기인한다. 따라서, 저온 용액 공정에 의해 생산 단가를 획기적으로 낮출 수 있는 유기 고분자 태양 전지가 새로운 대안으로 주목받고 있는 실정이다.Meanwhile, the second-generation thin-film solar cell market share of silicon (5.2%), (4.7%) and COGS (0.5%) accounts for 10% of the total market, but is still insignificant. There is a problem that the unit price is high due to the necessity of expensive and expensive equipment. The main reasons for the cost increase are mainly due to the process of providing the semiconductor thin film under vacuum and high temperature. Therefore, an organic polymer solar cell capable of drastically lowering a production cost by a low temperature solution process is attracting attention as a new alternative.
현재 고분자를 이용한 에너지 소재의 경우 무기 소재에 비해 소자 제작의 용이성, 기계적 유연성, 분자 디자인의 용이성, 가격 등 유기 재료가 갖는 다양한 장점으로 인해 그 중요성이 점차 부각되고 있다. 그러나 유기태양전지가 이러한 여러 가지 장점을 가지고 있음에도, 에너지 전환 효율 측면에서 낮다는 문제점이 있었다. In the case of energy materials using polymers, the importance of organic materials is increasingly emphasized due to various advantages of inorganic materials such as ease of production, mechanical flexibility, ease of molecular design and price. However, although the organic solar cell has various advantages, it has a problem in that it is low in energy conversion efficiency.
대표적인 유기 태양전지인 고분자 태양전지의 경우에도 효율 문제를 개선하기 위한 많은 연구가 이루어지고 있는데, 예를 들어 고분자 태양전지의 흡광 능력을 향상시키기 위하여 낮은 밴드 격차(band gap)를 가지는 D-A 타입의 고분자를 개발하기 위한 다양한 시도가 이루어졌고, 그 결과 고분자와 플러렌(fullerene)을 포함하는 이중 혼합물(binary blend)이 벌크-이종접합(Bulk Heterojunction, BHJ)을 이루는 고분자 태양전지 (Polymer Solar Cell, PSC)의 경우 광 전환 효율(Power Conversion Efficiency, PCE)이 9~11% 수준까지 개선되고 있는 상황이다.In order to improve the efficiency of a polymer solar cell, for example, a DA type polymer having a low band gap (band gap) The results show that a binary blend containing polymer and fullerene is a polymer solar cell (PSC) that forms a bulk heterogeneous junction (BHJ) The power conversion efficiency (PCE) is improving to 9 ~ 11%.
반면, 전자받개 고분자 (polymer acceptor) 및 전자주개 고분자 (polymer donor)의 이중 혼합물(binary blends)을 구성되는 고분자-고분자 태양전지(all-Polymer Solar Cells)는 상기 고분자/플러렌 태양전지에 비해 분자 에너지 준위를 손쉽게 조절할 수 있고, 전자받개 고분자와 전자주개 고분자가 동시에 태양광 흡수가 가능하며, 또한 기계적 및 열적 특성이 뛰어난 장점이 있어 많은 관심을 받고 있다. 그러나 고분자-고분자 태양전지는 여전히 5-6% 정도의 상대적으로 낮은 광 전환 효율을 보여 주고 있어, 이를 개선하기 위한 해결 방안이 요구되고 있다.On the other hand, all-polymer solar cells constituting binary blends of an electronic acceptor and an electron donor polymer have higher molecular energy than the polymer / fullerene solar cell, And the electron-accepting polymer and the electron-donating polymer can absorb the solar light at the same time, and the excellent mechanical and thermal characteristics are attracting much attention. However, the polymer-polymer solar cell still shows a relatively low light conversion efficiency of 5-6%, and a solution is needed to improve it.
이와 같은 고분자-고분자 태양전지의 낮은 광 전환 효율의 중요한 원인으로는 낮은 단락 전류 밀도(short-circuit current density, Jsc)와 낮은 필 펙터(fill factor, FF)인데, 이는 전자주개 고분자와 전자받개 고분자의 혼합(blending)이 열역학적으로 엔트로피 기여(entropic contribution)를 크게 저하해 고분자/고분자 도메인 사이즈가 큰 상 분리(large-scale phase separation)를 야기하고, 이는 고분자-고분자 태양전지가 필요로 하는 수십 나노 크기의 도메인을 가지는 벌크 이종 접합을 형성할 수 없게 한다. 즉, 전자주개 고분자와 전자받개 고분자 간의 이상적인 혼합이 고분자-고분자 태양전지의 효율을 상승시킬 수 있는 요인으로, 고분자간의 이상적인 혼합이 형성될 수 있는 방법이 요구되고 있다.The short-circuit current density (Jsc) and the low fill factor (FF) are important factors in the low-light conversion efficiency of the polymer-polymer solar cell. This is because the electron-donating polymer and the electron- Blending of the polymers greatly reduces the entropic contribution thermodynamically resulting in a large-scale phase separation of the polymer / polymer domain size, which results in a large number of nano- Lt; RTI ID = 0.0 > domains. ≪ / RTI > That is, an ideal mixing between the electron donor polymer and the electron acceptor polymer is a factor that can increase the efficiency of the polymer-polymer solar cell, and a method of forming an ideal mixture between the polymers is required.
또한, 유기태양전지의 광활성층에 포함된 전자받개 고분자의 전자 이동도(electron mobility)는 기존의 고분자 유기태양전지에 사용되는 플러렌보다 낮기 때문에, 고분자-고분자 태양전지의 효율적인 전하 추출 및 전하 이동을 위해 고분자-고분자 간의 상 분리를 완화시키고 안정된 모폴로지를 형성하여, 전자주개 고분자 및 전자받개 고분자 계면간의 전하 이동도가 높은 유기태양전지의 개발이 요구되고 있다. In addition, since electron mobility of the electron acceptor polymer contained in the photoactive layer of the organic solar cell is lower than that of the conventional fullerene used in the polymer organic solar cell, efficient charge extraction and charge transfer of the polymer- It is required to develop an organic solar cell having a high charge mobility between an electron donor polymer and an electron acceptor polymer interface by alleviating the phase separation between the polymer and the polymer and forming a stable morphology.
본 발명의 목적은 상기 문제점을 해결하기 위한 것으로, 전자주개 고분자와 전자받개 고분자 간의 혼합뿐만 아니라, 고분자의 배향 및 결정성을 제어할 수 있는 광활성층 첨가제용 화합물을 제공한다.An object of the present invention is to provide a compound for a photoactive layer additive capable of controlling the orientation and crystallinity of a polymer as well as mixing between an electron donor polymer and an electron acceptor polymer.
또한, 상기 첨가제용 화합물이 전자받개 고분자 및 전자주개 고분자와 동시에 분자적 상호작용을 함으로써 큰 상 분리 없이 균일한 모폴로지를 가지는 광활성층(photoactive layer)을 형성하고, 이를 포함하는 고분자-고분자 유기태양전지를 제공한다.Further, the additive compound forms a photoactive layer having homogeneous morphology without large phase separation by molecular interaction with the electron-accepting polymer and the electron-donating polymer at the same time, and a polymer- Lt; / RTI >
본 발명의 하나의 측면에 따르면, 하기 구조식 1로 표시되는 광활성층 첨가제용 화합물을 제공한다.According to one aspect of the present invention, there is provided a compound for a photoactive layer additive represented by the following structural formula (1).
[구조식 1][Structural formula 1]
Ar1-Y-Ar2 Ar 1 -Y-Ar 2
상기 구조식 1에서,In the above formula 1,
Ar1은 치환 또는 비치환된 C6 내지 C20의 다륜성 방향족 탄화수소(polycyclic aromatic hydrocarbon)이고, 상기 치환에 해당하는 치환기는 수소원자 또는 할로겐원자이고, 상기 치환기 중 적어도 하나는 할로겐 원자이고,Ar 1 is a substituted or unsubstituted C6 to C20 polycyclic aromatic hydrocarbon, the substituent corresponding to the substitution is a hydrogen atom or a halogen atom, at least one of the substituents is a halogen atom,
Ar2은 치환 또는 비치환된 C6 내지 C20의 다륜성 방향족 탄화수소(polycyclic aromatic hydrocarbon)이고 상기 치환에 해당하는 기는 수소원자 또는 C1 내지 C5의 직쇄형 또는 분쇄형의 알킬기이고,Ar 2 is a substituted or unsubstituted C6 to C20 polycyclic aromatic hydrocarbon, and the group corresponding to the substitution is a hydrogen atom or a straight-chain or branched alkyl group having from 1 to 5 carbon atoms,
Y는 산소(O), 황(S) 및 셀레늄(Se) 중에서 선택된 어느 하나이다.Y is any one selected from oxygen (O), sulfur (S) and selenium (Se).
Ar1은 할로겐 원자로 치환된 C6 내지 C20의 다륜성 방향족 탄화수소(polycyclic aromatic hydrocarbon)이고,Ar 1 is a C6 to C20 polycyclic aromatic hydrocarbon substituted with a halogen atom,
Ar2은 C6 내지 C20의 다륜성 방향족 탄화수소(polycyclic aromatic hydrocarbon)이고,Ar 2 is a C6 to C20 polycyclic aromatic hydrocarbon,
Y는 산소(O)일 수 있다.Y may be oxygen (O).
상기 할로겐 원자가 플루오린(F)일 수 있다.The halogen atom may be fluorine (F).
상기 광활성층 첨가제용 화합물이 하기 구조식 2로 표시되는 화합물일 수 있다.The compound for the photoactive layer additive may be a compound represented by the following structural formula (2).
[구조식 2][Structural formula 2]
상기 구조식 2에서,In the above formula 2,
X1 내지 X5가 서로 같거나 다르고, X1 내지 X5가 각각 독립적으로 할로겐 원자이고,X 1 to X 5 are the same or different from each other, X 1 to X 5 are each independently a halogen atom,
R1 내지 R5는 서로 같거나 다르고, R1 내지 R5는 서로 독립적으로, 수소원자, C1 내지 C20 직쇄형 또는 분쇄형 알킬기이고 R 1 to R 5 are the same or different from each other, and R 1 to R 5 are independently of each other a hydrogen atom, a C1 to C20 linear or branched alkyl group
Y는 산소(O), 황(S) 및 셀레늄(Se) 중에서 선택된 어느 하나이다.Y is any one selected from oxygen (O), sulfur (S) and selenium (Se).
상기 X1 내지 X5가 서로 같거나 다르고, X1 내지 X5가 각각 독립적으로 플루오린(F), 염소(Cl), 브로민(Br) 및 아이오딘(I)을 포함할 수 있다.X 1 to X 5 may be the same or different from each other and each of X 1 to X 5 may independently include fluorine (F), chlorine (Cl), bromine (Br) and iodine (I).
상기 구조식 2가 하기 화학식 1로 표시되는 화합물일 수 있다.The compound represented by Formula 2 may be a compound represented by Formula 1 below.
[화학식 1][Chemical Formula 1]
본 발명의 다른 일 측면에 있어서, 하기 구조식 3으로 표시되는 화합물과 하기 구조식 4로 표시되는 화합물을 반응시켜 상기 구조식 1로 표시되는 화합물을 제조하는 것인 광활성층 첨가제용 화합물의 제조방법을 제공한다.In another aspect of the present invention, there is provided a process for preparing a compound for a photoactive layer additive, which comprises reacting a compound represented by the following structural formula 3 with a compound represented by the following
[구조식 3][Structural Formula 3]
Ar1 Ar 1
상기 구조식 3에서,In the above formula 3,
Ar1은 치환 또는 비치환된 C6 내지 C20의 다륜성 방향족 탄화수소(polycyclic aromatic hydrocarbon)이고, 상기 치환에 해당하는 치환기는 수소원자 또는 할로겐원자이고, 상기 치환기 중 적어도 하나는 할로겐 원자이고,Ar 1 is a substituted or unsubstituted C6 to C20 polycyclic aromatic hydrocarbon, the substituent corresponding to the substitution is a hydrogen atom or a halogen atom, at least one of the substituents is a halogen atom,
[구조식 4] [Structural Formula 4]
YH-Ar2 YH-Ar 2
상기 구조식 4에서,In the
Ar2은 치환 또는 비치환된 C6 내지 C20의 다륜성 방향족 탄화수소(polycyclic aromatic hydrocarbon)이고 상기 치환에 해당하는 기는 수소원자 또는 C1 내지 C5의 직쇄형 또는 분쇄형의 알킬기이고,Ar 2 is a substituted or unsubstituted C6 to C20 polycyclic aromatic hydrocarbon, and the group corresponding to the substitution is a hydrogen atom or a straight-chain or branched alkyl group having from 1 to 5 carbon atoms,
Y는 산소(O), 황(S) 및 셀레늄(Se) 중에서 선택된 어느 하나이다.Y is any one selected from oxygen (O), sulfur (S) and selenium (Se).
상기 구조식 3이 하기 구조식 5로 표시되는 화합물을 포함하고, 상기 구조식 4가 하기 구조식 6으로 표시되는 화합물을 포함할 수 있다.The structural formula 3 may include a compound represented by the following
[구조식 5][Structural Formula 5]
상기 구조식 5에서,In the
X1 내지 X6이 서로 같거나 다르고, X1 내지 X6이 각각 독립적으로 할로겐 원자이고,X 1 to X 6 are the same or different from each other, each of X 1 to X 6 is independently a halogen atom,
[구조식 6][Structural Formula 6]
상기 구조식 6에서,In the
R1 내지 R5는 서로 같거나 다르고, R1 내지 R5는 서로 독립적으로, 수소원자, C1 내지 C20 직쇄형 또는 분쇄형 알킬기이고,R 1 to R 5 are the same or different from one another and each of R 1 to R 5 independently represents a hydrogen atom, a C1 to C20 linear or branched alkyl group,
Y는 산소(O), 황(S) 및 셀레늄(Se) 중에서 선택된 어느 하나이다.Y is any one selected from oxygen (O), sulfur (S) and selenium (Se).
상기 구조식 5가 하기 화학식 2로 표시되는 화합물을 포함하고, 상기 구조식 6이 하기 화학식 3으로 표시되는 화합물을 포함할 수 있다.The compound represented by Formula 5 may include a compound represented by Formula 2, and the compound represented by Formula 6 may be represented by Formula 3 below.
[화학식 2](2)
[화학식 3] (3)
본 발명의 또 다른 일 측면에 있어서, 제 1전극; 상기 제 1전극 상에 형성된 전자수송층; 상기 전자수송층 상에 형성되고, 제1항의 광활성층 첨가제용 화합물, 전자주개 고분자 및 전자받개 고분자를 포함하는 광활성층; 상기 광활성층 상에 형성된 정공수송층; 및 상기 정공수송층 상에 형성된 제 2전극; 을 포함하는 유기태양전지를 제공한다.According to another aspect of the present invention, there is provided a plasma display panel comprising: a first electrode; An electron transport layer formed on the first electrode; A photoactive layer formed on the electron transporting layer and comprising the compound for a photoactive layer additive of claim 1, an electron donating polymer, and an electron acceptor polymer; A hole transport layer formed on the photoactive layer; And a second electrode formed on the hole transport layer; An organic solar cell.
상기 전자수송층이 ZnO, LiF, TiOx, TiO2, CsCO3 및 Ca 중에서 선택된 1종 이상을 포함할 수 있다.Wherein the electron transport layer may include at least one selected from ZnO, LiF, TiOx, TiO 2 , CsCO 3 and Ca.
상기 전자받개 고분자가 플러렌(fullerene), 6,6-페닐-C61-부틸릭엑시드메틸에스터(PCBM(C61)), PCBM(C60), PCBM(C70), PCBM(C71), PCBM(C76), PCBM(C80), PCBM(C82), indene-C60 bisadduct(ICBA) 및 6,6-페닐-C61-부틸릭엑시드콜레스테릴에스터(PCBCR) 중에서 선택되는 플러렌 유도체, 폴리벤지미다졸(polybenzimidazole), 페릴렌(perylene), poly[[N,N'-bis(2-octyldodecyl)-napthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)](NDI2OD-T2), naphthalene diimide(NDI)-selenophene copolymer(PNDIS-HD), poly[(E)-2,7-bis(2-decyltetradecyl)-4-methyl-9-(5-(2-(5-methylthiophen-2-yl)vinyl)thiophen-2-yl)benzo[lmn][3,8] phenanthroline-1,3,6,8(2H, 7H)-tetraone] (PNDI-TVT) 및 poly[[N,N′-bis(2-hexyldecyl)naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5′-thiophene] (PNDI2HD-T) 중에서 선택된 1종 이상을 포함할 수 있다.Wherein the electron acceptor polymer is selected from the group consisting of fullerene, 6,6-phenyl-C61-butylic acid methyl ester (PCBM (C61)), PCBM (C60), PCBM (C70), PCBM (C71) A fullerene derivative selected from PCBM (C80), PCBM (C82), indene-C60 bisadduct (ICBA) and 6,6-phenyl-C61-butylic acid cholesteryl ester (PCBCR), polybenzimidazole, Perylene, poly [[N, N'-bis (2-octyldodecyl) -napthalene-1,4,5,8-bis (dicarboximide) (2,2'-bithiophene)] (NDI2OD -T2), naphthalene diimide (NDI) -selenophene copolymer (PNDIS-HD), poly [(E) -2,7-bis (2-decyltetradecyl) -4-methyl- 9- (5- (2- (5- methylthiophen-2-yl) vinyl) thiophen-2-yl) benzo [lmn] [3,8] phenanthroline-1,3,6,8 (2 H, 7 H) -tetraone] (PNDI-TVT) and poly [[N, N'-bis (2-hexyldecyl) naphthalene-1,4,5,8-bis (dicarboximide) '-Thiophene] (PNDI2HD-T).
상기 전자주개 고분자가 Poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl]](PTB73), Poly[3,6-bis(5-thiophen-2-yl)-2,5-bis(2-octyldodecyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione- 2,2'-diyl-alt- thieno[3,2-b]thiophen-2,5-diyl]( PDPP2T-TT), Poly(3-octylthiophene-2,5-diyl) (P3OT), Poly(p-phenylene vinylene)(PPV), Poly(dioctyl fluorene), Poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene](MEHPPV), Poly[2-methoxy-5-(3',7′'-dimethyloctyloxy)-1,4-phenylenevinylene](MDMO-PPV), Poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']dithiophene)-alt-4,7(2,1,3-benzothiadiazole)](PCPDTBT), poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)-benzo[1,2-b:4,5-b′]dithiophene-alt-5-octyl-4H-thieno[3,4-c] pyrrole-4,6(5H)-dione] (PBDTTTPD), poly[(2,5-bis(2-hexyldecyloxy)phenylene)-alt-(5,6-difluoro-4,7-di(thiophen-2-yl)benzo-[c][1,2,5]thiadiazole)] (PPDT2FBT), poly(3-hexylthiophene) (P3HT), poly{1-(5-(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)-6-methylbenzo[1,2-b:4, 5-b']-dithiophen-2-yl)thiophen-2-yl)-5,7-bis(2-ethylhexyl)-3-(5-methylthiophen-2-yl)benzo-[1,2-c:4,5-c′']dithiophene-4,8-dione} (PBDTBDD-T) 및 이들의 유도체 중에서 선택된 1종 이상을 포함할 수 있다.Wherein the electron donor polymer is selected from the group consisting of Poly [[4,8-bis [(2-ethylhexyl) oxy] benzo [1,2-b: 4,5- b '] dithiophene-2,6-diyl] - [(2-ethylhexyl) carbonyl] thieno [3,4-b] thiophenediyl]] (PTB73), Poly [3,6-bis (5-thiophen- pyrrolo [3,4-c] pyrrole-1,4 (2H, 5H) -dione-2,2'-diyl-thieno [3,2-b] thiophen-2,5-diyl] (PDPP2T- TT), Poly (3-octylthiophene-2,5-diyl) (P3OT), Poly (p-phenylene vinylene) (PPV), Poly (dioctyl fluorene) 1,4-phenylenevinylene] (MEHPPV), Poly [2-methoxy-5- (3 ', 7'-dimethyloctyloxy) -1,4- 4-bis (2-ethylhexyl) -4H-cyclopenta [2,1-b; 3,4-b '] dithiophene) [4,8-bis (5- (2-ethylhexyl) thiophen-2-yl) -benzo [1,2- b: 4,5- b '] dithiophene-5-octyl- 4-c] pyrrole-4,6 (5H) -dione (PBDTTTPD), poly [(2,5-bis (2-hexyldecyloxy) phenylene) (3-hexylthiophene) (P3HT), poly {1- (5- (4,8-b) thiophen-2-yl) benzo [c] [1,2,5] thiadiazole)] (PPDT2FBT) 2-yl) thiophen-2-yl) -6- methylbenzo [1,2-b: 4,5-biphenyl- -bis (2-ethylhexyl) -3- (5-methylthiophen-2-yl) benzo [1,2- c: 4,5-c "dithiophene-4,8-dione} (PBDTBDD- And derivatives thereof.
상기 전자받개 고분자와 전자주개 고분자가 혼합된 벌크 헤테로 접합(bulk hetero junction) 구조일 수 있다.And may be a bulk heterojunction structure in which the electron acceptor polymer and the electron donor polymer are mixed.
상기 광활성층 첨가제용 화합물이 상기 광활성층에 포함된 고분자의 배향 및 결정성을 제어할 수 있다.The compound for the photoactive layer additive can control the orientation and crystallinity of the polymer contained in the photoactive layer.
상기 정공수송층이 몰리브데늄옥사이드(Molybdenum oxide, MoO2, MoO3), 피닷피에스에스(PEDOT:PSS, poly(3,4-ethylenedioxythiophene) polystyrene sulfonate), 텅스텐옥사이드(WO3), 니켈옥사이드(Nickel oxide) 및 세륨 도핑된 텅스텐옥사이드(CeWO3) 중에서 선택된 1종 이상을 포함할 수 있다.The hole transport layer may include at least one of molybdenum oxide, MoO 2 , MoO 3 , PEDOT, poly (3,4-ethylenedioxythiophene) polystyrene sulfonate, tungsten oxide (WO 3 ), nickel oxide oxide and cerium-doped tungsten oxide (CeWO 3 ).
상기 제1 전극이 인듐 틴 옥사이드(ITO), 플루오린 틴 옥사이드(FTO), 은 나노와이어(Ag nanowires) 및 은 나노메쉬(nanomesh) 중에서 선택된 1종 이상을 포함할 수 있다.The first electrode may include at least one selected from indium tin oxide (ITO), fluorine tin oxide (FTO), silver nanowires, and silver nanomesh.
상기 제2 전극이 Au, Fe, Ag, Cu, Cr, W, Al, Mo, Zn, Ni, Pt, Pd, Co, In, Mn, Si, Ta, Ti, Sn, Pb, V, Ru, Ir, Zr, Rh 및 Mg 중에서 선택된 1종 이상을 포함할 수 있다.Wherein the second electrode is made of Au, Fe, Ag, Cu, Cr, W, Al, Mo, Zn, Ni, Pt, Pd, Co, In, Mn, Si, Ta, Ti, Sn, Pb, , Zr, Rh, and Mg.
본 발명의 광활성층 첨가제용 화합물은 전자주개 고분자와 전자받개 고분자 간의 혼합뿐만 아니라, 고분자의 배향 및 결정성을 제어할 수 있는 효과가 있다.The compound for the photoactive layer additive of the present invention has an effect of controlling not only the mixing of the electron donor polymer and the electron acceptor polymer but also the orientation and crystallinity of the polymer.
또한, 상기 첨가제용 화합물이 전자받개 고분자 및 전자주개 고분자와 동시에 분자적 상호작용을 함으로써 큰 상분리 없이 균일한 모폴로지를 가지는 광활성층(photoactive layer)을 형성하고, 광전지 특성이 우수한 고분자-고분자 유기태양전지를 구현할 수 있다.In addition, the additive compound forms a photoactive layer having homogeneous morphology without large phase separation by performing molecular interaction with the electron acceptor polymer and the electron donor polymer at the same time, and the polymer-polymer organic solar cell Can be implemented.
도 1은 본 발명의 광활성층 첨가제용 화합물 구조 및 고분자-고분자 태양전지의 소자구조와 고분자 간의 선택적 4극 전자 정역학 상호작용을 나타낸 개략도이다.
도 2는 본 발명의 광활성층 첨가제용 화합물을 포함한 고분자-고분자 필름의 UV-vis 흡수(UV-vis absorption) 결과를 나타낸 그래프이다.
도 3은 본 발명의 광활성층 첨가제용 화합물을 포함한 고분자-고분자 필름 photoluminescence (PL) 스펙트럼 분석 결과를 나타낸 그래프이다.
도 4는 광활성층 첨가제용 화합물을 포함하는 고분자-고분자 필름의 원자력 현미경 이미지를 나타낸 것이다.
도 5는 광활성층 첨가제용 화합물을 포함하는 고분자-고분자 필름의 입사 광각 X-선 산란(Grazing incidence wide-angle X-ray scattering, GIWAXS) 분석 결과를 나타낸 것이다.
도 6 및 도 7은 광활성층 첨가제용 화합물을 포함하는 고분자-고분자 필름을 광활성층에 포함하는 유기태양전지의 광전지특성 결과를 나타낸 것이다.FIG. 1 is a schematic view showing a compound structure for a photoactive layer additive of the present invention and a selective quadrupole electrostatics interaction between a polymer structure and a device structure of a polymer-polymer solar cell.
2 is a graph showing UV-vis absorption (UV-vis absorption) results of a polymer-polymer film including a compound for a photoactive layer additive of the present invention.
3 is a graph showing the results of photoluminescence (PL) spectrometry of a polymer-polymer film including a compound for a photoactive layer additive of the present invention.
4 is an atomic force microscope image of a polymer-polymer film containing a compound for a photoactive layer additive.
FIG. 5 is a graph showing the results of analysis of grazing incidence wide-angle X-ray scattering (GIWAXS) of a polymer-polymer film including a compound for a photoactive layer additive.
6 and 7 show photovoltaic cell characteristics of an organic solar cell including a polymer-polymer film including a compound for a photoactive layer additive in a photoactive layer.
이하, 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 첨부된 도면을 참조하여 본 발명의 실시예를 상세히 설명하도록 한다. Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention.
그러나 이하의 설명은 본 발명을 특정한 실시 형태에 대해 한정하려는 것이 아니며, 본 발명을 설명함에 있어서 관련된 공지 기술에 대한 구체적인 설명이 본 발명의 요지를 흐릴 수 있다고 판단되는 경우 그 상세한 설명을 생략한다.However, the following description does not limit the present invention to specific embodiments. In the following description of the present invention, detailed description of known related arts will be omitted if it is determined that the gist of the present invention may be blurred.
본원에서 사용한 용어는 단지 특정한 실시예를 설명하기 위해 사용된 것으로, 본 발명을 한정하려는 의도가 아니다. 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다. 본 출원에서, "포함하다" 또는 "가지다" 등의 용어는 명세서상에 기재된 특징, 숫자, 단계, 동작, 구성요소, 또는 이들을 조합한 것이 존재함을 지정하려는 것이지, 하나 또는 그 이상의 다른 특징들이나 숫자, 단계, 동작, 구성요소, 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다.The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, the terms "comprises ", or" having ", and the like, specify that the presence of stated features, integers, steps, operations, elements, or combinations thereof, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, or combinations thereof.
도 1은 본 발명의 광활성층 첨가제용 화합물의 구조와 전자주개 고분자, 전자받개 고분자 및 광활성층 첨가제용 화합물을 포함하는 광활성층 및 이를 포함하는 고분자-고분자 유기태양전지 소자의 구조를 나타낸 것이다.FIG. 1 shows the structure of a photoactive layer comprising a compound for a photoactive layer additive of the present invention and a compound for an electron donating polymer, an electron acceptor polymer and a photoactive layer additive, and a polymer-polymer organic solar cell device comprising the photoactive layer.
이하, 도 1을 참조하여 본 발명의 광활성층 첨가제용 화합물에 대하여 설명하도록 한다.Hereinafter, the compound for a photoactive layer additive of the present invention will be described with reference to FIG.
본 발명은 하기 구조식 1로 표시되는 광활성층 첨가제용 화합물을 제공한다.The present invention provides a compound for a photoactive layer additive represented by the following structural formula (1).
[구조식 1] [Structural formula 1]
Ar1-Y-Ar2 Ar 1 -Y-Ar 2
상기 구조식 1에서,In the above formula 1,
Ar1은 치환 또는 비치환된 C6 내지 C20의 다륜성 방향족 탄화수소(polycyclic aromatic hydrocarbon)이고, 상기 치환에 해당하는 치환기는 수소원자 또는 할로겐원자이고, 상기 치환기 중 적어도 하나는 할로겐 원자이고,Ar 1 is a substituted or unsubstituted C6 to C20 polycyclic aromatic hydrocarbon, the substituent corresponding to the substitution is a hydrogen atom or a halogen atom, at least one of the substituents is a halogen atom,
Ar2은 치환 또는 비치환된 C6 내지 C20의 다륜성 방향족 탄화수소(polycyclic aromatic hydrocarbon)이고 상기 치환에 해당하는 기는 수소원자 또는 C1 내지 C5의 직쇄형 또는 분쇄형의 알킬기이고,Ar 2 is a substituted or unsubstituted C6 to C20 polycyclic aromatic hydrocarbon, and the group corresponding to the substitution is a hydrogen atom or a straight-chain or branched alkyl group having from 1 to 5 carbon atoms,
Y는 산소(O), 황(S) 및 셀레늄(Se) 중에서 선택된 어느 하나이다.Y is any one selected from oxygen (O), sulfur (S) and selenium (Se).
바람직하게는 Ar1은 할로겐 원자로 치환된 C6 내지 C20의 다륜성 방향족 탄화수소(polycyclic aromatic hydrocarbon)이고, Ar2은 C6 내지 C20의 다륜성 방향족 탄화수소(polycyclic aromatic hydrocarbon)이고, Y는 산소(O)일 수 있으며, 더욱 바람직하게는 할로겐 원자가 플루오린(F)일 수 있다.Preferably Ar 1 is a halogen atom, a substituted C6 to a multi ryunseong aromatic hydrocarbon group (polycyclic aromatic hydrocarbon) of the C20, Ar 2 is a C6 to a multi ryunseong aromatic hydrocarbon group (polycyclic aromatic hydrocarbon) of the C20, Y is oxygen (O) days And more preferably, the halogen atom may be fluorine (F).
상기 첨가제용 화합물은 하기 구조식 2로 표시되는 화합물일 수 있다.The additive compound may be a compound represented by the following structural formula (2).
[구조식 2] [Structural formula 2]
상기 구조식 2에서,In the above formula 2,
X1 내지 X5가 서로 같거나 다르고, X1 내지 X5가 각각 독립적으로 할로겐 원자이고,X 1 to X 5 are the same or different from each other, X 1 to X 5 are each independently a halogen atom,
R1 내지 R5는 서로 같거나 다르고, R1 내지 R5는 서로 독립적으로, 수소원자, C1 내지 C20 직쇄형 또는 분쇄형 알킬기이고, R 1 to R 5 are the same or different from one another and each of R 1 to R 5 independently represents a hydrogen atom, a C1 to C20 linear or branched alkyl group,
Y는 산소(O), 황(S) 및 셀레늄(Se) 중에서 선택된 어느 하나이다.Y is any one selected from oxygen (O), sulfur (S) and selenium (Se).
바람직하게는 X1 내지 X5가 서로 같거나 다르고, X1 내지 X5가 각각 독립적으로 플루오린(F), 염소(Cl), 브로민(Br) 및 아이오딘(I)을 포함할 수 있고, 더욱 바람직하게 X1 내지 X5가 플루오린(F)일 수 있다.Preferably, X 1 to X 5 are the same or different from each other and each of X 1 to X 5 may independently include fluorine (F), chlorine (Cl), bromine (Br) and iodine , More preferably X 1 to X 5 may be fluorine (F).
상기 구조식 2는 하기 화학식 1로 표시되는 화합물일 수 있다.The structural formula 2 may be a compound represented by the following general formula (1).
[화학식 1][Chemical Formula 1]
본 발명은 하기 구조식 3으로 표시되는 화합물과 하기 구조식 4로 표시되는 화합물을 반응시켜 상기 구조식 1로 표시되는 광활성층 첨가제용 화합물의 제조방법을 제공한다.The present invention provides a process for producing a compound for a photoactive layer additive represented by the structural formula 1 by reacting a compound represented by the following structural formula 3 with a compound represented by the following
[구조식 3] [Structural Formula 3]
Ar1 Ar 1
상기 구조식 3에서,In the above formula 3,
Ar1은 치환 또는 비치환된 C6 내지 C20의 다륜성 방향족 탄화수소(polycyclic aromatic hydrocarbon)이고, 상기 치환에 해당하는 치환기는 수소원자 또는 할로겐원자이고, 상기 치환기 중 적어도 하나는 할로겐 원자이고,Ar 1 is a substituted or unsubstituted C6 to C20 polycyclic aromatic hydrocarbon, the substituent corresponding to the substitution is a hydrogen atom or a halogen atom, at least one of the substituents is a halogen atom,
[구조식 4][Structural Formula 4]
YH-Ar2 YH-Ar 2
상기 구조식 4에서,In the
Ar2은 치환 또는 비치환된 C6 내지 C20의 다륜성 방향족 탄화수소(polycyclic aromatic hydrocarbon)이고 상기 치환에 해당하는 기는 수소원자 또는 C1 내지 C5의 직쇄형 또는 분쇄형의 알킬기이고,Ar 2 is a substituted or unsubstituted C6 to C20 polycyclic aromatic hydrocarbon, and the group corresponding to the substitution is a hydrogen atom or a straight-chain or branched alkyl group having from 1 to 5 carbon atoms,
Y는 산소(O), 황(S) 및 셀레늄(Se) 중에서 선택된 어느 하나이다.Y is any one selected from oxygen (O), sulfur (S) and selenium (Se).
바람직하게는 상기 구조식 3이 하기 구조식 5로 표시되는 화합물을 포함하고, 상기 구조식 4가 하기 구조식 6으로 표시되는 화합물을 포함할 수 있다.Preferably, Formula 3 includes a compound represented by
[구조식 5] [Structural Formula 5]
상기 구조식 5에서, In the
X1 내지 X6이 서로 같거나 다르고, X1 내지 X6이 각각 독립적으로 할로겐 원자이고,X 1 to X 6 are the same or different from each other, each of X 1 to X 6 is independently a halogen atom,
[구조식 6] [Structural Formula 6]
상기 구조식 6에서,In the
R1 내지 R5는 서로 같거나 다르고, R1 내지 R5는 서로 독립적으로, 수소원자, C1 내지 C20 직쇄형 또는 분쇄형 알킬기이고,R 1 to R 5 are the same or different from one another and each of R 1 to R 5 independently represents a hydrogen atom, a C1 to C20 linear or branched alkyl group,
Y는 산소(O), 황(S) 및 셀레늄(Se) 중에서 선택된 어느 하나이다.Y is any one selected from oxygen (O), sulfur (S) and selenium (Se).
더욱 바람직하게는 상기 구조식 5가 하기 화학식 2로 표시되는 화합물을 포함하고, 상기 구조식 6이 하기 화학식 3으로 표시되는 화합물을 포함할 수 있다.More preferably, the compound represented by
[화학식 2](2)
[화학식 3] (3)
이하, 도 1을 참조하여 본 발명의 광활성층 첨가제용 화합물을 광활성층에 포함하는 고분자-고분자 유기태양전지에 대하여 설명하도록 한다.Hereinafter, the polymer-polymer organic solar cell including the photoactive layer additive compound of the present invention in the photoactive layer will be described with reference to FIG.
본 발명은 제 1전극; 상기 제 1전극 상에 형성된 전자수송층; 상기 전자수송층 상에 형성되고, 제1항의 광활성층 첨가제용 화합물, 전자주개 고분자 및 전자받개 고분자를 포함하는 광활성층; 상기 광활성층 상에 형성된 정공수송층; 및 상기 정공수송층 상에 형성된 제 2전극; 을 포함하는 유기태양전지를 제공한다.The present invention relates to a plasma display panel comprising a first electrode; An electron transport layer formed on the first electrode; A photoactive layer formed on the electron transporting layer and comprising the compound for a photoactive layer additive of claim 1, an electron donating polymer, and an electron acceptor polymer; A hole transport layer formed on the photoactive layer; And a second electrode formed on the hole transport layer; An organic solar cell.
상기 전자수송층은 ZnO, LiF, TiOx, TiO2, CsCO3, Ca, 등을 사용할 수 있으며, 바람직하게는 ZnO을 사용할 수 있다.The electron transport layer can be used for ZnO, LiF, TiOx, TiO 2, CsCO 3, Ca, etc., it can be preferably used for ZnO.
상기 광활성층 첨가제용 화합물은 고분자-고분자 간의 상분리 현상을 완화시키는 동시에 수평적 배향(face-on)을 가지는 파이-파이 스태킹(π-π stacking)을 강화시키는 모폴로지를 형성하여, 전자주개 고분자와 전자받개 고분자 계면 간의 전하 추출 및 전하 이동을 향상시키는 역할을 한다.The compound for the photoactive layer additive modifies the phase separation phenomenon between the polymer and the polymer and forms a morphology which strengthens the pi-pi stacking with a horizontal face-on, And serves to improve charge extraction and charge transfer between the polymer interface.
또한, 상기 광활성층 첨가제용 화합물은 펜타플루오르페닐 그룹과 페닐 그룹으로 구성된 것을 특징으로 하며, 펜타플루오르페닐은 전자 밀도가 낮은 그룹으로 양의 4극자 모멘트(positive quadrupolar moment)를 가지며, 벤젠은 전자가 풍부한 그룹으로 음의 4극자 모멘트(negative quadrupolar moment)를 가진다. 양의 4극자 모멘트를 가지는 펜타플루오르페닐 그룹은 전자주개 고분자와 4극자 전기적 상호작용(quadrupolar electrostatic interaction)을 형성할 수 있으며, 페닐그룹은 전자받개 고분자와 4극자 전기적 상호작용을 형성할 수 있다. 이러한 선택적 상호작용은 전자받개 고분자와 전자주개 고분자의 혼합을 큰 상분리 없는 균일한 모폴로지를 형성하는 광활성층을 형성할 수 있도록 한다.The compound for the photoactive layer additive is characterized by being composed of a pentafluorophenyl group and a phenyl group. Pentafluorophenyl is a group having a low electron density and has a positive quadrupolar moment. A rich group has a negative quadrupolar moment. A pentafluorophenyl group having positive quadrupole moments can form a quadrupolar electrostatic interaction with an electron donor polymer and a phenyl group can form a quadrupole electrical interaction with an electron acceptor polymer. This selective interaction allows the mixture of the electron acceptor polymer and the electron donor polymer to form a photoactive layer that forms a homogeneous morphology without large phase separation.
또한, 이러한 4극자 전기적 상호작용은 면 대 면으로 (face-on-face) 형성되기 때문에 고분자 간의 면 배향을 가지는 파이-파이 스태킹(π-π stacking)을 향상시킬 수 있으며, 이러한 배향을 갖는 고분자 적층은 유기 태양전지에 유리한 수직적 전하 이동을 향상시켜 고분자-고분자 태양전지의 단락전류밀도를 향상시킨다.In addition, since the quadrupole electrical interaction is formed face-on-face, it is possible to improve pi-pi stacking with plane orientation between polymers, and a polymer having such orientation Lamination improves the vertical charge transfer favorable to organic solar cells and improves the short circuit current density of polymer-polymer solar cells.
상기 전자받개 고분자는 플러렌(fullerene), 6,6-페닐-C61-부틸릭엑시드메틸에스터(PCBM(C61)), PCBM(C60), PCBM(C70), PCBM(C71), PCBM(C76), PCBM(C80), PCBM(C82), indene-C60 bisadduct(ICBA) 및 6,6-페닐-C61-부틸릭엑시드콜레스테릴에스터(PCBCR) 중에서 선택되는 플러렌 유도체, 폴리벤지미다졸(polybenzimidazole), 페릴렌(perylene), poly[[N,N'-bis(2-octyldodecyl)-napthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophe ne)](NDI2OD-T2), naphthalene diimide(NDI)-selenophene copolymer(PNDIS-HD), poly[(E)-2,7-bis(2-decyltetradecyl)-4-methyl-9-(5-(2-(5-methylthiophen-2-yl)vinyl)thiophen-2-yl)benzo[lmn][3,8] phenanthroline-1,3,6,8(2H, 7H)-tetraone] (PNDI-TVT), poly[[N,N′-bis(2-hexyldecyl)naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5′-thiophene] (PNDI2HD-T)등일 수 있으며, 바람직하게는 poly[[N,N'-bis(2-octyldodecyl)-napthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophe ne)](NDI2OD-T2) 및 naphthalene diimide(NDI)-selenophene copolymer(PNDIS-HD) 일 수 있다.The electron acceptor polymer may be selected from the group consisting of fullerene, 6,6-phenyl-C61-butyric acid methyl ester (PCBM (C61)), PCBM (C60), PCBM (C70), PCBM (C71) A fullerene derivative selected from PCBM (C80), PCBM (C82), indene-C60 bisadduct (ICBA) and 6,6-phenyl-C61-butylic acid cholesteryl ester (PCBCR), polybenzimidazole, Perylene, poly [[N, N'-bis (2-octyldodecyl) -napthalene-1,4,5,8-bis (dicarboximide) (2,2'-bithiophe ne)] ( NDI2OD-T2), naphthalene diimide (NDI) -selenophene copolymer (PNDIS-HD), poly [(E) -2,7-bis (2-decyltetradecyl) -4-methyl -9- (5- (2- (5- methylthiophen-2-yl) vinyl) thiophen-2-yl) benzo [lmn] [3,8] phenanthroline-1,3,6,8 (2 H, 7 H ) -tetraone] (PNDI-TVT), poly [[N, N'-bis (2-hexyldecyl) naphthalene- 1,4,5,8-bis (dicarboximide) 5'-thiophene] (PNDI2HD-T) and the like, preferably poly [[N, N'-bis (2-octyldodecyl) -napthalene-1,4,5,8-bis (dicarboximide) -diyl] -alt-5,5 '- (2,2'-bithiophene)] (NDI 2OD-T2) and naphthalene diimide (NDI) -selenophene copolymer (PNDIS-HD).
상기 전자주개 고분자는 Poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl]](PTB73) , Poly[3,6-bis(5-thiophen-2-yl)-2,5-bis(2-octyldodecyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione- 2,2'-diyl-alt- thieno[3,2-b]thiophen-2,5-diyl]( PDPP2T-TT), Poly(3-octylthiophene-2,5-diyl) (P3OT), Poly(p-phenylene vinylene)(PPV), Poly(dioctyl fluorene), Poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene](MEHPPV), Poly[2-methoxy-5-(3',7′'-dimethyloctyloxy)-1,4-phenylenevinylene](MDMO-PPV), Poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta [2,1-b;3,4-b']dithiophene)-alt-4,7(2,1,3-benzothiadiazole)](PCPDTBT), poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)-benzo[1,2-b:4,5-b′]dithiophene-alt-5-octyl-4H-thieno[3,4-c] pyrrole-4,6(5H)-dione] (PBDTTTPD), poly[(2,5-bis(2-hexyldecyloxy)phenylene)-alt-(5,6-difluoro-4,7-di(thiophen-2-yl)benzo-[c][1,2,5]thiadiazole)] (PPDT2FBT), poly(3-hexylthiophene) (P3HT), poly{1-(5-(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)-6-methylbenzo[1,2-b:4, 5-b']-dithiophen-2-yl)thiophen-2-yl)-5,7-bis(2-ethylhexyl)-3-(5-methylthiophen-2-yl)benzo-[1,2-c:4,5-c′']dithiophene-4,8-dione} (PBDTBDD-T) 이들의 유도체 등일 수 있으며, 바람직하게는 Poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl]](PTB73)일 수 있다.The electron donor polymer may be selected from the group consisting of Poly [[4,8-bis [(2-ethylhexyl) oxy] benzo [1,2-b: 4,5-b '] dithiophene-2,6- - [(2-ethylhexyl) carbonyl] thieno [3,4-b] thiophenediyl]] (PTB73), Poly [3,6-bis (5-thiophen- pyrrolo [3,4-c] pyrrole-1,4 (2H, 5H) -dione-2,2'-diyl-thieno [3,2-b] thiophen-2,5-diyl] (PDPP2T- TT), Poly (3-octylthiophene-2,5-diyl) (P3OT), Poly (p-phenylene vinylene) (PPV), Poly (dioctyl fluorene) 1,4-phenylenevinylene] (MEHPPV), Poly [2-methoxy-5- (3 ', 7'-dimethyloctyloxy) -1,4- 4-bis (2-ethylhexyl) -4H-cyclopenta [2,1-b; 3,4-b '] dithiophene) [4,8-bis (5- (2-ethylhexyl) thiophen-2-yl) -benzo [1,2- b: 4,5- b '] dithiophene-5-octyl- 4-c] pyrrole-4,6 (5H) -dione (PBDTTTPD), poly [(2,5-bis (2-hexyldecyloxy) phenylene) poly (3-hexylthiophene) (P3HT), poly {1- (5- (4, 8) thiophen-2- -bis (5- (2-ethylhexyl) thiophen-2-yl) -6-methylbenzo [1,2- b: 4,5- bithidophen-2-yl) thiophen- (2-ethylhexyl) -3- (5-methylthiophen-2-yl) benzo [1,2- c: 4,5- cis dithiophene-4,8-dione} (PBDTBDD- 2,6-diyl] [2, 4-bis [(2-ethylhexyl) oxy] benzo [1,2-b: 4,5-b '] dithiophene- 3-fluoro-2 - [(2-ethylhexyl) carbonyl] thieno [3,4-b] thiophenediyl]] (PTB73).
상기 전자받개 고분자와 전자주개 고분자는 혼합된 벌크 헤테로 접합(bulk hetero junction) 구조일 수 있다.The electron acceptor polymer and the electron donor polymer may be a mixed bulk heterojunction structure.
상기 광활성층 첨가제용 화합물은 상기 광활성층에 포함된 고분자의 배향 및 결정성을 제어할 수 있다.The photoactive layer additive compound can control the orientation and crystallinity of the polymer contained in the photoactive layer.
상기 정공수송층은 몰리브데늄옥사이드(Molybdenum oxide, MoO2, MoO3), 피닷피에스에스(PEDOT:PSS, poly(3,4-ethylenedioxythiophene) polystyrene sulfonate), 텅스텐옥사이드(WO3), 니켈옥사이드(Nickel oxide), 세륨 도핑된 텅스텐옥사이드(CeWO3) 등을 사용할 수 있으며, 바람직하게는 몰리브데늄옥사이드(Molybdenum oxide, MoO2, MoO3)을 사용할 수 있다.The hole transport layer may include at least one of molybdenum oxide, MoO 2 , MoO 3 , PEDOT, poly (3,4-ethylenedioxythiophene) polystyrene sulfonate, tungsten oxide (WO 3 ), nickel oxide oxide, cerium-doped tungsten oxide (CeWO 3 ), and the like, and molybdenum oxide (MoO 2 , MoO 3 ) may be preferably used.
상기 제1 전극은 인듐 틴 옥사이드(ITO), 플루오린 틴 옥사이드(FTO), 은 나노와이어(Ag nanowires), 은 나노메쉬(nanomesh) 등을 사용할 수 있으며, 바람직하게는 인듐 틴 옥사이드(ITO)을 사용할 수 있다.The first electrode may be made of indium tin oxide (ITO), fluorine tin oxide (FTO), silver nanowires, silver nanomesh, or the like, preferably indium tin oxide (ITO) Can be used.
상기 제2 전극은 Au, Fe, Ag, Cu, Cr, W, Al, Mo, Zn, Ni, Pt, Pd, Co, In, Mn, Si, Ta, Ti, Sn, Pb, V, Ru, Ir, Zr, Rh, Mg 등을 사용할 수 있으며, 바람직하게는 Au를 사용할 수 있다.The second electrode may be at least one of Au, Fe, Ag, Cu, Cr, W, Al, Mo, Zn, Ni, Pt, Pd, Co, In, Mn, Si, Ta, Ti, Sn, Pb, , Zr, Rh, Mg and the like can be used, and Au can be preferably used.
[실시예] [Example]
이하, 실시예를 통하여 본 발명을 더욱 구체적으로 설명한다. 그러나, 이는 예시를 위한 것으로서 이에 의하여 본 발명의 범위가 한정되는 것이 아니다.Hereinafter, the present invention will be described more specifically by way of examples. However, this is for illustrative purposes only, and thus the scope of the present invention is not limited thereto.
제조예 1: 전자받개 고분자(PNDIS-HD)Production Example 1: Electronic Receiver Polymer (PNDIS-HD)
반응식 1에서 화합물 1로 표시되는 4,9-Dibromo-2,7-bis(2-hexyldecyl)benzo[lmn][3,8]phenanthroline-1,3,6,8-tetraone(200mg, 0.23mmol)와 화합물 2로 표시되는 2,5- bis(trimethylstannyl)selenophene(104.6mg, 0.23 mmol), tris(dibenzylideneacetone)dipalladium(Pd2(dba)3)(4.2mg, 4.6mol) 및 tri(o-tolyl) phosphine(P(o-tolyl)3)(5.6mg, 18.4μmol)를 콘덴서가 장착된 둥근 플라스크에 넣어 혼합물을 제조하고, 1시간 이상 진공 처리하여 수분 및 산소가 제거된 진공분위기로 만들었다. 상기 혼합물에 5mL의 무수 클로로벤젠(chlorobenzene, CB) 용매를 첨가하고 110에서 48시간 동안 반응하여 혼합용액을 제조하였다. 상기 혼합용액에 2-tributylstannyl thiophene(0.1mL)과 2-bromothiophene(0.1mL)를 첨가하여 앤드-캡핑(end-capping)하였다. 이후, 실온으로 식힌 후 메탄올(methanol)에 침전시키고, 생성된 고분자는 메탄올(methanol), 아세톤(acetone), 헥산(hexane), 디클로로메탄(dichloromethane), 클로로포름(chloroform) 순으로 속슬렛 추출기(soxhlet)로 정제하여 하기 화합물 3으로 표시되는 고분자 PNDIS-HD(Mn = 37kDa, PDI = 2.91)를 제조하였다.3, 8] phenanthroline-1,3,6,8-tetraone (200 mg, 0.23 mmol) represented by the compound 1 in the
[반응식 1][Reaction Scheme 1]
제조예Manufacturing example 2: 2: 전자받개Electronic receiver 고분자 P( Polymer P ( NDIODNDIOD -T2)-T2)
하기 화학식 4로 표시되는 P(NDIOD-T2) (Mn = 75k, PDI = 2.5)는 원머털리어사(1-Material Inc.)의 제품을 구입하여 사용하였다.P (NDIOD-T2) (Mn = 75k, PDI = 2.5) represented by the following
[화학식 4][Chemical Formula 4]
제조예Manufacturing example 3: 3: 전자주개Electronic drill 고분자( Polymers PTB7PTB7 -- ThTh ))
하기 화학식 5로 표시되는 전자주개 고분자(PTB7-Th)(Mn = 42k, PDI = 2.5)는 원머털리어사(1-Material Inc.)의 제품을 구입하여 사용하였다.An electron donor polymer (PTB7-Th) (Mn = 42k, PDI = 2.5) represented by the following general formula (5) was purchased from 1-Material Inc.
[화학식 5][Chemical Formula 5]
실시예 1: 광활성층 첨가제용 화합물(FPE) 제조Example 1: Preparation of compound (FPE) for photoactive layer additive
100ml 둥근 바닥 플라스크에 세슘카보네이트(Cs2CO3)(13.6mmol, 4.4g), 산화구리()(Cu2O)(0.68mmol, 0.1mg) 및 1H-이미다졸-4-카르복실릭에시드(1H-imidazole-4-carboxylic acid, L)(1.4mmol, 0.15g)를 혼합한 혼합물을 제조하고, 진공 분위기를 형성하였다. 상기 혼합물에 아세토나이트릴(acetonitrile)(10mL)를 첨가하고 상온에서 30분 동안 교반하여 혼합하고, 아이오도펜타플루오르벤젠(iodopenta-fluorobenzene) (화합물 a, 6.8mmol, 2g)과 페놀(phenol)(화합물 b, 8.2mmol, 0.8g)을 첨가한 후, 80℃의 온도에서 24시간 동안 환류시켜 반응시킴으로써 혼합물을 제조하였다. 반응이 종결되면 상기 혼합물을 다이클로로메테인(dichloromethane) 용매에 희석시킨 후 셀라이트 패드 (celite pad)를 통해 여과하여 여과된 용액을 농축시키고 컬럼 크로마토그래피로 추출하여 첨가제 FPE (화합물 c, 1.5g, 85%)를 제조하였다.To a 100 ml round-bottom flask was added cesium carbonate (Cs 2 CO 3 ) (13.6 mmol, 4.4 g), copper (Cu 2 O) (0.68 mmol, 0.1 mg) and 1 H- imidazole-4-carboxylic acid 1H-imidazole-4-carboxylic acid, L) (1.4 mmol, 0.15 g) was prepared and a vacuum atmosphere was formed. To the mixture was added acetonitrile (10 mL), and the mixture was stirred at room temperature for 30 minutes, and iodopenta-fluorobenzene (compound a, 6.8 mmol, 2 g) and phenol ( Compound b, 8.2 mmol, 0.8 g), and the mixture was refluxed for 24 hours at a temperature of 80 占 폚 to prepare a mixture. After the reaction was completed, the mixture was diluted with dichloromethane solvent and filtered through a celite pad. The filtrate was concentrated and extracted by column chromatography to obtain 1.5 g of the additive FPE (compound c, 1.5 g , 85%).
상기 광활성층 첨가제용 화합물(FPE)의 반응은 아래에 표시된 반응식 1과 같다.The reaction of the photoactive layer additive compound (FPE) is shown in Scheme 1 below.
[반응식 1][Reaction Scheme 1]
1H NMR (300 MHz, CDCl3): δ 7.39-7.32 (m, 2 H), 7.17-7.12 (m, 1 H), 7.03-6.92 (m, 2 H). 1 H NMR (300 MHz, CDCl3 ): δ 7.39-7.32 (m, 2 H), 7.17-7.12 (m, 1 H), 7.03-6.92 (m, 2 H).
13C NMR (75 MHz, CDCl3): δ 157.2, 146.5 (qd, J1 = 243.2 Hz, J2 = 3.8 Hz, 1C), 141.6 (dd, J1 = 247.3 Hz, J2 = 14.9 Hz, 1C), 132.2 (td, J1 = 310.0 Hz, J2 = 7.0 Hz, 1C), 129.8, 123.7, 115.5, 101.8 (t, J = 22.7 Hz, 1C). 13 C NMR (75 MHz, CDCl3 ): δ 157.2, 146.5 (qd, J1 = 243.2 Hz, J2 = 3.8 Hz, 1C), 141.6 (dd, J1 = 247.3 Hz, J2 = 14.9 Hz, 1C), 132.2 (td , J1 = 310.0 Hz, J2 = 7.0 Hz, 1C), 129.8, 123.7, 115.5, 101.8 (t, J = 22.7 Hz, 1C).
HRMS: C12H5F5O calculated 260.0261, found 260.0265.HRMS: C 12 H 5 F 5 O calculated 260.0261, found 260.0265.
소자실시예Device Example 1: One: 실시예Example 1의 1 of FPEFPE 첨가제, additive, 제조예Manufacturing example 3의 3 of 전자주개Electronic drill 고분자( Polymers PTB7PTB7 -Th), -Th), 제조예Manufacturing example 2의 2 of 전자받개Electronic receiver 고분자( Polymers NDIODNDIOD -T2)를 포함한 -T2) 광활성층을The photoactive layer 포함하는 유기태양전지 Including organic solar cells
(제 1전극 및 전자수송층 형성)(Formation of first electrode and electron transport layer)
패턴닝된 11Ω/sq ITO를 증류수(Deionized Water), 아세톤, 아이소프로필 알코올 순서로 각각 10분씩 세척하여 150℃ 오븐에 건조하였다. 그리고 ZnO를 세척된 ITO 위에 6000rpm 30초 조건에서 스핀코팅을 하였다. The patterned 11 Ω / sq ITO was washed with deionized water, acetone, and isopropyl alcohol in the order of 10 minutes each, and dried in an oven at 150 ° C. ZnO was spin-coated on the cleaned ITO at 6000 rpm for 30 seconds.
(광활성층용 용액 및 광활성층 형성)(Formation of photoactive layer solution and photoactive layer)
광활성층은 PTB7-Th:NDIOD-T2을 9mg:9mg(1:1) 무게 비율로 혼합한 고분자 혼합물을 클로로벤젠 (0.97mL)과 실시예 1에 따라 제조된 FPE 첨가제(0.03mL)를 혼합한 혼합용액에 첨가하여, 70℃ 온도에서 교반하여 광활성층용 혼합용액을 제조하였다. 상기 혼합용액을 ZnO를 코팅한 표면 위에 1200rpm 40초 조건에서 스핀 코팅시켜 광활성층을 형성하였다. 이때, 광활성층 면적은 0.04cm2이다. The photoactive layer was prepared by mixing chlorobenzene (0.97 mL) and FPE additive (0.03 mL) prepared according to Example 1 in a mixture of PTB7-Th: NDIOD-T2 at a weight ratio of 9 mg: 9 mg (1: 1) And the mixture was stirred at a temperature of 70 ° C to prepare a photoactive layer mixed solution. The mixed solution was spin-coated on the ZnO-coated surface at 1200 rpm for 40 seconds to form a photoactive layer. At this time, the photoactive layer area is 0.04 cm 2 .
(정공수송층 및 제 2전극 형성)(Forming a hole transport layer and a second electrode)
이후 10-8 내지 10-7 Torr 기압의 조건에서 상기 형성된 광활성층 상에 MoO3 (20nm)와 Ag(100nm)를 진공 증착하였다. Then, MoO 3 (20 nm) and Ag (100 nm) were vacuum-deposited on the formed photoactive layer under the condition of 10 -8 to 10 -7 Torr.
소자실시예Device Example 2: 2: 실시예Example 1의 1 of FPEFPE 첨가제, additive, 제조예Manufacturing example 3의 3 of 전자주개Electronic drill 고분자( Polymers PTB7PTB7 -Th), -Th), 제조예Manufacturing example 1의 1 of 전자받개Electronic receiver 고분자( Polymers PNDISPNDIS -HD)를 포함한 -HD) 광활성층을The photoactive layer 포함하는 유기태양전지 Including organic solar cells
소자실시예 1의 PTB7-Th:NDIOD-T2을 9mg:9mg(1:1) 무게 비율로 혼합한 고분자 혼합물을 대신에 PTB7-Th:PNDIS-HD를 9mg:9mg(1:1) 무게 비율로 혼합한 고분자 혼합물을 사용한 것을 제외하고는 소자실시예 1과 동일한 방법으로 소자실시예 2의 유기태양전지를 제조하였다.PT: 7: Th: PNDIS-HD in a weight ratio of 9 mg: 9 mg (1: 1) instead of PTM7-Th: NDIOD-T2 of Embodiment Example 1 in a weight ratio of 9 mg: An organic solar cell of Example 2 was prepared in the same manner as in Example 1 except that a mixed polymer mixture was used.
소자비교예Device comparison example 1: One: 전자주개Electronic drill 고분자( Polymers PTB7PTB7 -- ThTh ), ), 전자받개Electronic receiver 고분자( Polymers NDIODNDIOD -T2)를 포함한 광활성층을 포함하는 유기태양전지Lt; RTI ID = 0.0 > -T2) < / RTI >
PTB7-Th:NDIOD-T2을 9mg:9mg(1:1) 무게 비율로 혼합한 고분자 혼합물을 클로로벤젠 (0.97mL)과 실시예 1에 따라 제조된 FPE 첨가제(0.03mL)를 혼합한 혼합용액 대신에 PTB7-Th:NDIOD-T2을 9mg:9mg(1:1) 무게 비율로 혼합한 고분자 혼합물을 사용하여 광활성층을 형성한 것을 제외하고는 소자실시예 1과 동일한 방법으로 유기태양전지를 제조하였다.Instead of a mixed solution obtained by mixing 0.97 mL of chlorobenzene and 0.03 mL of the FPE additive prepared according to Example 1 in a polymer mixture prepared by mixing PTB7-Th: NDIOD-T2 at a weight ratio of 9 mg: 9 mg (1: 1) An organic solar cell was prepared in the same manner as in Example 1 except that a photoactive layer was formed using a polymer mixture of PTB7-Th: NDIOD-T2 in a weight ratio of 9 mg: 9 mg (1: 1) .
소자비교예Device comparison example 2: 2: DIODIO (1,8-(1,8- diiodooctane디오드 오탄탄 ) 첨가제, ) additive, 전자주개Electronic drill 고분자( Polymers PTB7PTB7 -- ThTh ), 전자받개 고분자(NDIOD-T2)를 포함한 광활성층을 포함하는 유기태양전지), An organic solar cell including a photoactive layer including an electron acceptor polymer (NDIOD-T2)
PTB7-Th:NDIOD-T2을 9mg:9mg(1:1) 무게 비율로 혼합한 고분자 혼합물을 클로로벤젠(0.97mL)과 실시예 1에 따라 제조된 FPE 첨가제(0.03mL)를 혼합한 혼합용액 대신에 PTB7-Th:NDIOD-T2을 9mg:9mg(1:1) 무게 비율로 혼합한 고분자 혼합물을 클로로벤젠(0.97mL)과 화학식 6으로 표시되는 DIO(1,8-diiodooctane) 첨가제(0.03mL)를 혼합한 혼합용액 사용하여 광활성층을 형성한 것을 제외하고는 소자실시예 1과 동일한 방법으로 유기태양전지를 제조하였다.Instead of a mixed solution obtained by mixing 0.97 mL of chlorobenzene and 0.03 mL of the FPE additive prepared according to Example 1 in a polymer mixture prepared by mixing PTB7-Th: NDIOD-T2 at a weight ratio of 9 mg: 9 mg (1: 1) (0.97 mL) and a DIO (1,8-diiodooctane) additive (0.03 mL) represented by the formula (6) were mixed in a weight ratio of PTB7-Th: NDIOD-T2 of 9 mg: Was used to form a photoactive layer, an organic solar cell was manufactured in the same manner as in Example 1 of the present invention.
[화학식 6][Chemical Formula 6]
소자비교예Device comparison example 3: 3: 전자주개Electronic drill 고분자( Polymers PNDISPNDIS -HD), -HD), 전자받개Electronic receiver 고분자( Polymers NDIODNDIOD -T2)를 포함한 -T2) 광활성층을The photoactive layer 포함하는 유기태양전지 Including organic solar cells
PTB7-Th:NDIOD-T2을 9mg:9mg(1:1) 무게 비율로 혼합한 고분자 혼합물을 사용한 것 대신에 PTB7-Th:PNDIS-HD을 9mg:9mg(1:1) 무게 비율로 혼합한 고분자 혼합물을 이용하여 광활성층을 형성한 것을 제외하고는 소자비교예 1과 동일한 방법으로 유기태양전지를 제조하였다.PT: a mixture of PTM7-Th: PNDIS-HD at a weight ratio of 9mg: 9mg (1: 1) instead of using a mixture of PTM7-Th: NDIOD-T2 at a weight ratio of 9mg: 9mg An organic solar cell was prepared in the same manner as in Comparative Example 1 except that the photoactive layer was formed using the mixture.
소자비교예Device comparison example 4: 4: DIODIO (1,8-(1,8- diiodooctane디오드 오탄탄 ) 첨가제, ) additive, 전자주개Electronic drill 고분자( Polymers PTB7PTB7 -- ThTh ), 전자받개 고분자(NDIOD-T2)를 포함한 광활성층을 포함하는 유기태양전지), An organic solar cell including a photoactive layer including an electron acceptor polymer (NDIOD-T2)
PTB7-Th:NDIOD-T2을 9mg:9mg(1:1) 무게 비율로 혼합한 고분자 혼합물을 클로로벤젠(0.97mL)과 DIO(1,8-diiodooctane) 첨가제(0.03mL)를 혼합한 혼합용액을 사용한 것 대신에 PTB7-Th:PNDIS-HD을 9mg:9mg(1:1) 무게 비율로 혼합한 고분자 혼합물을 클로로벤젠(0.97mL)과 DIO(1,8-diiodooctane) 첨가제(0.03mL)를 혼합한 혼합용액을 사용하여 광활성층을 형성한 것을 제외하고는 소자비교예 2와 동일한 방법으로 유기태양전지를 제조하였다.A mixed solution of chlorobenzene (0.97 mL) and DIO (1,8-diiodooctane) additive (0.03 mL) was mixed with PTM7-Th: NDIOD-T2 in a weight ratio of 9 mg: (0.97 mL) and DIO (1,8-diiodooctane) additive (0.03 mL) were mixed in a weight ratio of 9 mg: 9 mg (1: 1) instead of PTB7-Th: PNDIS- An organic solar cell was manufactured in the same manner as in Comparative Example 2 except that a photoactive layer was formed using a mixed solution.
소자실시예 1, 소자실시예 2, 소자비교예 1 및 소자비교예 2에 따라 제조된 유기태양전지의 광활성층을 구성하는 전자주개 고분자, 전자받개 고분자 및 첨가제의 종류를 정리하여 하기 표 1에 나타내었다.The electron donor polymer, electron acceptor polymer and additive constituting the photoactive layer of the organic solar cell manufactured according to the device example 1, the device example 2, the device comparative example 1 and the device comparative example 2 were summarized in the following Table 1 Respectively.
[시험예] [Test Example]
시험예Test Example 1: One: 전자주개Electronic drill 고분자와 Polymer and 전자받개Electronic receiver 고분자 사이의 선택적 4극 전자 정역학 상호작용(quadrupolar electrostatic interaction) Selective quadrupolar electrostatic interaction between polymers.
도 1은 실시예 1에 따라 제조된 FPE를 첨가제로서 사용한 모든 PSCs(polymer solar cells)에서 도너/억셉터의 모폴리지컬 제어를 체계적으로 분석한 것을 나타낸 것이다.Figure 1 shows a systematic analysis of the parental / acceptor homopolymeric control in all PSCs (polymer solar cells) using FPE prepared according to Example 1 as an additive.
도 1을 참조하면, 펜타플루오로페닐기는 전자 풍부한 방향족 고리(electron-rich aromatic rings)로 상호작용하는 양의 4극자 부호(positive quadrupolar sign)를 가지고 있다. 또한, 페닐기는 전자 부족한 방향족 고리로 음의 4극자 부호를 갖는다. 특히, 페닐기(phenyl group)와 퍼플루오르페닐기(perfluorophenyl group) 사이의 이러한 4극자성 정전기적 상호작용은 분자 간 페이스-투-페이스(face-to-face) 스태킹의 형성을 가능하게 한다.Referring to Figure 1, the pentafluorophenyl group has a positive quadrupolar sign that interacts with electron-rich aromatic rings. Further, the phenyl group has a negative quadrupolar sign with an electron shortage aromatic ring. In particular, this quadrupole electrostatic interaction between a phenyl group and a perfluorophenyl group enables the formation of intermolecular face-to-face stacking.
따라서, 첨가제로서 FPE의 도입이 도너와 억셉터 폴리머 사이의 선택적 파이-파이 상호작용을 형성한다. 이는 최적의 도너/억셉터 모폴로지 및 대규모 상분리 없이 이원적인 상호침투 도너/억셉터 네트워크(bicontinuous interpenetrating D/A network)가 일어나게 한다.Thus, the introduction of FPE as an additive forms a selective pi-pi interconnection between the donor and the acceptor polymer. This leads to an optimal donor / acceptor morphology and a bicontinuous interpenetrating D / A network without large scale phase separation.
그러므로 FPE로부터 모폴로지 변화는 계면 도너/억셉터 영역을 증가시킴으로써, PSCs에 대한 효율적인 전하 수송을 촉진시킬 것으로 기대된다. 또한, FPE 첨가제는 도너 및 억셉터 고분자 간의 면대면(face-to-face)스태킹을 유도함으로써, 수직 전하 수송을 향상시킬 수 있을 것으로 기대된다.Therefore, morphology changes from FPE are expected to promote efficient charge transport to PSCs by increasing the interfacial donor / acceptor region. In addition, the FPE additive is expected to enhance vertical charge transport by inducing face-to-face stacking between donor and acceptor polymers.
시험예 2: 광활성층의 광학특성 분석Test Example 2: Optical characteristics of photoactive layer
도 2는 고분자-고분자 필름의 UV-vis 흡수(UV-vis absorption) 분석결과이고, 도 3은 photoluminescence (PL) 스펙트럼 분석 결과를 나타낸 것이다.FIG. 2 shows the result of UV-vis absorption of the polymer-polymer film, and FIG. 3 shows the result of photoluminescence (PL) spectral analysis.
도 2를 참조하면, 모든 고분자-고분자 필름이 거의 동일한 흡수 스펙트럼을 갖는 것으로 나타났다. 이는 종래에 사용되던 첨가제 DIO와 본 발명의 첨가제 FPE 모두 고분자-고분자 필름(PTB7-Th:NDIOD-T2)의 흡수 거동에 영향을 미치지 않은 것을 의미한다.Referring to FIG. 2, all of the polymer-polymer films have almost the same absorption spectrum. This means that both the conventionally used additive DIO and the additive FPE of the present invention did not affect the absorption behavior of the polymer-polymer film (PTB7-Th: NDIOD-T2).
도 3을 살펴보면, 고분자-고분자 필름의 PL 스펙트럼은 약 980nm의 방출 차이를 보여주며, PL 퀀칭(PL quenching)은 CB + FPE> CB + DIO> CB 순서로 감소하는 것을 알 수 있었다.Referring to FIG. 3, PL spectra of the polymer-polymer films showed a difference of about 980 nm, and PL quenching was decreased in the order of CB + FPE> CB + DIO> CB.
이러한 결과는 FPE 첨가제를 포함하는 고분자-고분자 필름이 첨가제를 처리하지 않은 고분자-고분자 필름 및 종래의 첨가제(DIO)를 포함하는 고분자-고분자 필름 보다 PTB7-Th/NDIOD-T2 고분자-고분자 계면에서 전하이동이 더 효율적인 것을 나타내며, 본 발명의 첨가제 FPE를 포함하는 고분자-고분자 필름이 질 좋은 고분자-고분자 필름 모폴로지를 갖는 것을 알 수 있다.These results indicate that polymer-polymer films containing FPE additives have higher charge-to-charge ratios at the PTB7-Th / NDIOD-T2 polymer-polymer interface than polymer-polymer films containing no additives and polymer- And the polymer-polymer film including the additive FPE of the present invention has a good polymer-polymer film morphology.
시험예 3: 광활성층의 모폴로지 분석Test Example 3: Morphology analysis of the photoactive layer
도 4는 CB(a, d), CB + DIO(b), 및 CB + FPE(c)로 처리된 PTB7-Th:NDI2OD-T2 고분자-고분자 필름의 AFM 높이 및 3D 이미지 분석 결과를 나타낸 것이다.FIG. 4 shows AFM height and 3D image analysis results of PTB7-Th: NDI2OD-T2 polymer-polymer films treated with CB (a, d), CB + DIO (b), and CB + FPE (c).
도너 및 억셉터 고분자의 상분리에 첨가제가 미치는 영향을 살펴보기 위하여 CB, CB+DIO, CB+FPE로 처리된 고분자-고분자 필름의 원자력 현미경 지형이미지 (5?m x 5?m) 분석하였다.To investigate the effect of additives on the phase separation of donor and acceptor polymers, atomic force microscope topographic images (5? M x 5? M) of polymer-polymer films treated with CB, CB + DIO and CB + FPE were analyzed.
도 4를 참조하면, CB, CB+DIO로 처리된 고분자-고분자 필름은 모두 뚜렷한 상분리 된 도메인 구조가 나타났으나, CB+FPE로 처리된 고분자-고분자 필름은 질 좋은 표면 형태가 나타났다.Referring to FIG. 4, the polymer-polymer films treated with CB and CB + DIO exhibited distinct phase-separated domain structures. However, the polymer-polymer films treated with CB + FPE showed a good surface morphology.
또한, CB, CB + DIO 및 CB + FPE로 처리된 고분자-고분자 필름의 표면 거칠기(RMS) 거칠기는 각각 6.07, 5.89 및 1.85nm 인 것으로 나타났다.In addition, the surface roughness (RMS) roughness of the polymer-polymer films treated with CB, CB + DIO and CB + FPE were 6.07, 5.89 and 1.85 nm, respectively.
이러한 질 좋은 표면 모폴로지는 PL 퀀칭(PL quenching) 결과와 일치하며, 이는 FPE 첨가제가 효율적인 엑시톤 해리 및 전하 이동에 유리한 나노미터 규모에서 도너와 억셉터 고분자를 혼합하는 역할을 할 수 있다는 것을 의미한다.This good surface morphology is consistent with PL quenching results, which means that the FPE additive can act as a blend of donor and acceptor polymers on a nanometer scale that is beneficial for efficient exciton dissociation and charge transfer.
또한, FPE 첨가제를 포함하는 고분자-고분자 필름의 매끄러운 표면은 광활성층과 상대 전극 사이의 계면에서 전하 수송을 개선함으로써, 광전지 성능을 향상시킬 수 있다.In addition, the smooth surface of the polymer-polymer film comprising the FPE additive can improve photocell performance by improving charge transport at the interface between the photoactive layer and the counter electrode.
시험예Test Example 4: 입사 광각 X-선 산란(Grazing incidence wide-angle X-ray scattering, GIWAXS) 분석 4: Analysis of grazing incidence wide-angle X-ray scattering (GIWAXS)
도 5는 입사 광각 X선 산란 분석 결과를 나타낸 것으로 고분자-고분자 필름의 패킹구조 및 결정 배향과 같은 미세 구조 변화를 확인하였다.FIG. 5 shows the results of the incident wide angle X-ray scattering analysis, which confirmed the microstructure changes such as the packing structure and crystal orientation of the polymer-polymer film.
도 5를 참조하면, 고분자-고분자 필름은 면외(out-of-plane) 방향에서 ~17 nm-1에서 π-π 스태킹(010) 피크를 가지며, 면내(in-plane) 방향에서 ~ 2.6 nm-1에서 알킬 스태킹(100) 피크를 가지는 것으로 나타났다. 이는 고분자가 우선적으로 기재에 대한 정면(face-on) 배향을 채택하는 것으로 분석된다.5, the polymer-polymer film out-of-plane (out-of-plane) has a π-π stacking (010) peak at ~ 17 nm -1 in the direction of in-plane ~ 2.6 nm in the (in-plane) direction - from 1 it appeared to have the alkyl stacking (100) peak. It is analyzed that the polymer preferentially adopts a face-on orientation to the substrate.
또한, CB+DIO로 처리된 고분자-고분자 필름은 면외 방향에서 약간 증가한 (010) 피크 강도가 나타나며, 이는 NDI2OD-T2에 대한 결정화도가 증가했다는 것을 의미한다.In addition, the polymer-polymer film treated with CB + DIO exhibits a slightly increased (010) peak intensity in the out-of-plane direction, which means that the crystallinity to NDI2OD-T2 is increased.
또한, CB+FPE로 처리된 고분자-고분자 필름은 CB, CB+DIO로 처리된 고분자-고분자 필름에 비해 π-π 스태킹에 대해 더 강한 (010) 피크 강도가 나타났다.In addition, the polymer-polymer films treated with CB + FPE exhibited stronger (010) peak intensities for the π-π stacking than the polymer-polymer films treated with CB and CB + DIO.
이러한 결과는 FPE 첨가제 처리가 고분자 사슬 사이에서 정면(face-on) 방향을 갖는 정렬된 π-π 스태킹을 효과적으로 촉진하는 것으로, FPE에 의해 유도된 정전기 인력은 도너 및 억셉터 고분자 사이의 면대면(face-to-face) 상호 작용을 향상시킬 수 있다.These results indicate that the FPE additive treatment effectively promotes aligned pi-pi stacking with face-on orientation between the polymer chains, and the electrostatic attraction induced by FPE is a surface-to-face interaction between donor and acceptor polymers face-to-face interaction.
따라서, FPE 첨가제가 정면(face-on) 배향의 결정성을 크게 향상시킨 것을 의미한다.Thus, it is meant that the FPE additive has greatly improved the crystallinity of the face-on orientation.
시험예Test Example 5: CB, CB+ 5: CB, CB + DIODIO 및 CB+ And CB + FPEFPE 각각으로 처리된 고분자-고분자( Each treated polymer-polymer ( PTB7PTB7 -Th/NDI2OD-T) 필름을 -Th / NDI2OD-T) film 광활성층에In the photoactive layer 포함하는 유기태양전지 광전지( Including Organic Photovoltaic Cells ( photovoltaicphotovoltaic ) 특성 분석) Characteristic analysis
도 6은 CB, CB+DIO 및 CB+FPE 각각으로 처리된 PTB7-Th/NDI2OD-T2 고분자-고분자 필름 기반의 유기태양전지의 J-V 특성 곡선(a), IPCE 스펙트럼(b), JSC의 통계 분석(c) 및 VOC 분석결과를 나타낸 것이다. FIG. 6 shows the JV characteristic curves (a), IPCE spectrum (b), and J SC 's of PTB7-Th / NDI2OD-T2 polymer-polymer film-based organic solar cells treated with CB, CB + DIO and CB + Analysis (c) and V OC analysis results.
도 6을 참조하면, CB+FPE로 처리된 고분자-고분자 필름 기반의 유기태양전지의 가 PCE 값이 4.0%, JSC가 9.5 mA/cm2, 및 FF가 58.8%로 CB 또는 CB+DIO로 처리된 고분자 필름을 광활성층에 포함하는 유기 태양전지보다 광전지 특성이 현저히 우수한 것을 확인할 수 있었다. 이는 FPE 첨가제가 전자주개 고분자와 전자받개 고분자 간의 효율적인 전하이동이 일어나게 하였음을 의미한다.Referring to FIG. 6, the PCE value of the polymer-polymer film-based organic solar cell treated with CB + FPE is 4.0%, J SC is 9.5 mA / cm 2 , and FF is 58.8% It was confirmed that the treated polymer film was superior in photovoltaic cell characteristics to the organic solar cell containing the photoactive layer. This means that the FPE additive caused efficient charge transfer between the electron donor polymer and the electron acceptor polymer.
이와 관련하여 CB, CB+DIO 및 CB+FPE 각각으로 처리된 PTB7-Th/NDI2OD-T2 고분자-고분자 필름 기반의 유기태양전지의 PCE, JSC, VOC 및 FF 값을 하기 표 2에 정리하여 나타내었다.The PCE, J SC , V OC and FF values of PTB7-Th / NDI2OD-T2 polymer-polymer film-based organic solar cells treated with CB, CB + DIO and CB + FPE, respectively, Respectively.
(mA/cm2)JSC
(mA / cm 2 )
(V)VOC
(V)
(%)FF
(%)
(%)PCE
(%)
a괄호 안의 데이터는 20개의 디바이스의 평균 결과를 나타낸 것입니다. a The data in parentheses is the average result of 20 devices.
시험예Test Example 6: CB, CB+ 6: CB, CB + DIODIO 및 CB+ And CB + FPEFPE 각각으로 처리된 고분자-고분자( Each treated polymer-polymer ( PTB7PTB7 -- ThTh // PNDIS-HD) 필름을 PNDIS-HD) film 광활성층에In the photoactive layer 포함하는 유기태양전지 광전지( Including Organic Photovoltaic Cells ( photovoltaicphotovoltaic ) 특성 분석) Characteristic analysis
도 7은 CB, CB+DIO 및 CB+FPE 각각으로 처리된 PTB7-Th/PNDIS-HD 고분자-고분자 필름 기반의 유기태양전지의 J-V 특성 곡선(a), PCE 스펙트럼(b), JSC의 통계 분석(c) 및 FF 분석결과를 나타낸 것이다. FIG. 7 shows the JV characteristic curves (a), PCE spectrum (b), and J SC of organic solar cells based on PTB7-Th / PNDIS-HD polymer-polymer films treated with CB, CB + DIO and CB + (C) and FF analysis results.
도 7을 참조하면, CB+FPE로 처리된 고분자-고분자 필름 기반의 유기태양전지의 가 PCE값이 5.33%, JSC가 12.2 mA/cm2, 및 FF가 56.8%로 CB 또는 CB+DIO로 처리된 고분자-고분자 필름을 광활성층에 포함하는 유기태양전지 보다 광전지 특성이 현저히 우수한 것을 확인할 수 있었으며, 전자받개 고분자가 바뀜에도 불구하고 FPE 첨가제는 클로로벤젠(CB)으로 처리된 소자에 비해 30%의 광전환 효율 상승을 보여주었다.Referring to FIG. 7, the PCE value of the polymer-polymer film-based organic solar cell treated with CB + FPE is 5.33%, J SC is 12.2 mA / cm 2 , and FF is 56.8% It was confirmed that the photopolymer - treated polymer - polymer film showed better photovoltaic characteristics than the organic solar cell containing the photoactive layer. In spite of the change of the electron acceptor polymer, the FPE additive was 30% less than the chlorobenzene (CB) Of light conversion efficiency.
이와 관련하여 CB, CB+DIO 및 CB+FPE 각각으로 처리된 PTB7-Th/PNDIS-HD 고분자-고분자 필름 기반의 유기태양전지의 PCE, JSC, 및 FF 값을 하기 표 3에 정리하여 나타내었다.The PCE, J SC , and FF values of PTB7-Th / PNDIS-HD polymer-polymer film-based organic solar cells treated with CB, CB + DIO and CB + FPE, respectively, .
(mA/cm2)JSC
(mA / cm 2 )
(V)VOC
(V)
(%)FF
(%)
(%)PCE
(%)
a괄호 안의 데이터는 20개의 디바이스의 평균 결과를 나타낸 것입니다. a The data in parentheses is the average result of 20 devices.
발명의 범위는 상기 상세한 설명보다는 후술하는 특허청구범위에 의하여 나타내어지며, 특허청구범위의 의미 및 범위 그리고 그 균등 개념으로부터 도출되는 모든 변경 또는 변형된 형태가 본 발명의 범위에 포함되는 것으로 해석되어야 한다.The scope of the invention is defined by the appended claims rather than the foregoing description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be interpreted as being included in the scope of the present invention .
Claims (18)
[화학식 1]
[Chemical Formula 1]
[구조식 2]
상기 구조식 2에서,
X1 내지 X5가 서로 같거나 다르고, X1 내지 X5가 각각 독립적으로 할로겐 원자이고,
R1 내지 R5는 서로 같거나 다르고, R1 내지 R5 는 서로 독립적으로, 수소원자, C1 내지 C20 직쇄형 또는 분쇄형 알킬기이고
Y는 산소(O), 황(S) 및 셀레늄(Se) 중에서 선택된 어느 하나이고,
[구조식 5]
상기 구조식 5에서,
X1 내지 X6이 서로 같거나 다르고, X1 내지 X6이 각각 독립적으로 할로겐 원자이고,
[구조식 6]
상기 구조식 6에서,
R1 내지 R5는 서로 같거나 다르고, R1 내지 R5는 서로 독립적으로, 수소원자, C1 내지 C20 직쇄형 또는 분쇄형 알킬기이고,
Y는 산소(O), 황(S) 및 셀레늄(Se) 중에서 선택된 어느 하나이다.Reacting a compound represented by the following structural formula (5) with a compound represented by the following structural formula (6) to produce a compound represented by the following structural formula (2).
[Structural formula 2]
In the above formula 2,
X 1 to X 5 are the same or different from each other, X 1 to X 5 are each independently a halogen atom,
R 1 to R 5 are the same or different from each other, and R 1 to R 5 are independently of each other a hydrogen atom, a C1 to C20 linear or branched alkyl group
Y is any one selected from oxygen (O), sulfur (S) and selenium (Se)
[Structural Formula 5]
In the above formula 5,
X 1 to X 6 are the same or different from each other, each of X 1 to X 6 is independently a halogen atom,
[Structural Formula 6]
In the above formula 6,
R 1 to R 5 are the same or different from one another and each of R 1 to R 5 independently represents a hydrogen atom, a C1 to C20 linear or branched alkyl group,
Y is any one selected from oxygen (O), sulfur (S) and selenium (Se).
상기 구조식 5가 하기 화학식 2로 표시되는 화합물이고, 상기 구조식 6이 하기 화학식 3으로 표시되는 화합물이고, 상기 구조식 2가 하기 화학식 1로 표시되는 화합물인 것을 특징으로 하는 광활성층 첨가제용 화합물의 제조방법.
[화학식 1]
[화학식 2]
[화학식 3]
Wherein the structural formula 5 is a compound represented by the following formula 2, the structural formula 6 is a compound represented by the following formula 3, and the structural formula 2 is a compound represented by the following formula 1 .
[Chemical Formula 1]
(2)
(3)
상기 제 1전극 상에 형성된 전자수송층;
상기 전자수송층 상에 형성되고, 제1항의 광활성층 첨가제용 화합물, 전자주개 고분자 및 전자받개 고분자를 포함하는 광활성층;
상기 광활성층 상에 형성된 정공수송층; 및
상기 정공수송층 상에 형성된 제 2전극; 을
포함하는 유기태양전지.A first electrode;
An electron transport layer formed on the first electrode;
A photoactive layer formed on the electron transporting layer and comprising the compound for a photoactive layer additive of claim 1, an electron donating polymer, and an electron acceptor polymer;
A hole transport layer formed on the photoactive layer; And
A second electrode formed on the hole transport layer; of
Including organic solar cells.
상기 전자수송층이 ZnO, LiF, TiOx, TiO2, CsCO3 및 Ca 중에서 선택된 1종 이상을 포함하는 것을 특징으로 하는 유기태양전지.11. The method of claim 10,
The electron transport layer is ZnO, LiF, TiOx, TiO 2 , CsCO 3 , and organic solar cells comprising the at least one selected from Ca.
상기 전자받개 고분자가 플러렌(fullerene), 6,6-페닐-C61-부틸릭엑시드메틸에스터(PCBM(C61)), PCBM(C60), PCBM(C70), PCBM(C71), PCBM(C76), PCBM(C80), PCBM(C82), indene-C60 bisadduct(ICBA) 및 6,6-페닐-C61-부틸릭엑시드콜레스테릴에스터(PCBCR) 중에서 선택되는 플러렌 유도체, 폴리벤지미다졸(polybenzimidazole), 페릴렌(perylene), poly[[N,N'-bis(2-octyldodecyl)-napthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)](NDI2OD-T2), naphthalene diimide(NDI)-selenophene copolymer(PNDIS-HD), poly[(E)-2,7-bis(2-decyltetradecyl)-4-methyl-9-(5-(2-(5-methylthiophen-2-yl)vinyl)thiophen-2-yl)benzo[lmn][3,8] phenanthroline-1,3,6,8(2H, 7H)-tetraone] (PNDI-TVT) 및 poly[[N,N′-bis(2-hexyldecyl)naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5′-thiophene] (PNDI2HD-T) 중에서 선택된 1종 이상을 포함하는 것을 특징으로 하는 유기태양전지.11. The method of claim 10,
Wherein the electron acceptor polymer is selected from the group consisting of fullerene, 6,6-phenyl-C61-butylic acid methyl ester (PCBM (C61)), PCBM (C60), PCBM (C70), PCBM (C71) A fullerene derivative selected from PCBM (C80), PCBM (C82), indene-C60 bisadduct (ICBA) and 6,6-phenyl-C61-butylic acid cholesteryl ester (PCBCR), polybenzimidazole, Perylene, poly [[N, N'-bis (2-octyldodecyl) -napthalene-1,4,5,8-bis (dicarboximide) (2,2'-bithiophene)] (NDI2OD -T2), naphthalene diimide (NDI) -selenophene copolymer (PNDIS-HD), poly [(E) -2,7-bis (2-decyltetradecyl) -4-methyl- 9- (5- (2- (5- methylthiophen-2-yl) vinyl) thiophen-2-yl) benzo [lmn] [3,8] phenanthroline-1,3,6,8 (2 H, 7 H) -tetraone] (PNDI-TVT) and poly [[N, N'-bis (2-hexyldecyl) naphthalene-1,4,5,8-bis (dicarboximide) -Thiophene (PNDI2HD-T). ≪ / RTI >
상기 전자주개 고분자가 Poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl]](PTB73), Poly[3,6-bis(5-thiophen-2-yl)-2,5-bis(2-octyldodecyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione- 2,2'-diyl-alt- thieno[3,2-b]thiophen-2,5-diyl]( PDPP2T-TT), Poly(3-octylthiophene-2,5-diyl) (P3OT), Poly(p-phenylene vinylene)(PPV), Poly(dioctyl fluorene), Poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene](MEHPPV), Poly[2-methoxy-5-(3',7′'-dimethyloctyloxy)-1,4-phenylenevinylene](MDMO-PPV), Poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta [2,1-b;3,4-b']dithiophene)-alt-4,7(2,1,3-benzothiadiazole)](PCPDTBT), poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)-benzo[1,2-b:4,5-b′]dithiophene-alt-5-octyl-4H-thieno[3,4-c] pyrrole-4,6(5H)-dione] (PBDTTTPD), poly[(2,5-bis(2-hexyldecyloxy)phenylene)-alt-(5,6-difluoro-4,7-di(thiophen-2-yl)benzo-[c][1,2,5]thiadiazole)] (PPDT2FBT), poly(3-hexylthiophene) (P3HT), poly{1-(5-(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)-6-methylbenzo[1,2-b:4, 5-b']-dithiophen-2-yl)thiophen-2-yl)-5,7-bis(2-ethylhexyl)-3-(5-methylthiophen-2-yl)benzo-[1,2-c:4,5-c′']dithiophene-4,8-dione} (PBDTBDD-T) 및 이들의 유도체 중에서 선택된 1종 이상을 포함하는 것을 특징으로 하는 유기태양전지.11. The method of claim 10,
Wherein the electron donor polymer is selected from the group consisting of Poly [[4,8-bis [(2-ethylhexyl) oxy] benzo [1,2-b: 4,5- b '] dithiophene-2,6-diyl] - [(2-ethylhexyl) carbonyl] thieno [3,4-b] thiophenediyl]] (PTB73), Poly [3,6-bis (5-thiophen- pyrrolo [3,4-c] pyrrole-1,4 (2H, 5H) -dione-2,2'-diyl-thieno [3,2-b] thiophen-2,5-diyl] (PDPP2T- TT), Poly (3-octylthiophene-2,5-diyl) (P3OT), Poly (p-phenylene vinylene) (PPV), Poly (dioctyl fluorene) 1,4-phenylenevinylene] (MEHPPV), Poly [2-methoxy-5- (3 ', 7'-dimethyloctyloxy) -1,4- 4-bis (2-ethylhexyl) -4H-cyclopenta [2,1-b; 3,4-b '] dithiophene) [4,8-bis (5- (2-ethylhexyl) thiophen-2-yl) -benzo [1,2- b: 4,5- b '] dithiophene-5-octyl- 4-c] pyrrole-4,6 (5H) -dione (PBDTTTPD), poly [(2,5-bis (2-hexyldecyloxy) phenylene) poly (3-hexylthiophene) (P3HT), poly {1- (5- (4,8- bis (5- (2-ethylhexyl) thiophen-2-yl) -6-methylbenzo [1,2- b: 4,5-bistihophen-2-yl) thiophen- -bis (2-ethylhexyl) -3- (5-methylthiophen-2-yl) benzo [1,2- c: 4,5-c "dithiophene-4,8-dione} (PBDTBDD- And derivatives thereof. ≪ Desc / Clms Page number 24 >
상기 전자받개 고분자와 전자주개 고분자가 혼합된 벌크 헤테로 접합(bulk hetero junction) 구조인 것을 특징으로 하는 유기태양전지.11. The method of claim 10,
And a bulk heterojunction structure in which the electron acceptor polymer and the electron donor polymer are mixed.
상기 광활성층 첨가제용 화합물이 상기 광활성층에 포함된 고분자의 배향 및 결정성을 제어하는 것을 특징으로 하는 유기태양전지.11. The method of claim 10,
Wherein the compound for the photoactive layer additive controls the orientation and crystallinity of the polymer contained in the photoactive layer.
상기 정공수송층이 몰리브데늄옥사이드(Molybdenum oxide, MoO2, MoO3), 피닷피에스에스(PEDOT:PSS, poly(3,4-ethylenedioxythiophene) polystyrene sulfonate), 텅스텐옥사이드(WO3), 니켈옥사이드(Nickel oxide) 및 세륨 도핑된 텅스텐옥사이드(CeWO3) 중에서 선택된 1종 이상을 포함하는 것을 특징으로 하는 유기태양전지.11. The method of claim 10,
The hole transport layer may include at least one of molybdenum oxide, MoO 2 , MoO 3 , PEDOT, poly (3,4-ethylenedioxythiophene) polystyrene sulfonate, tungsten oxide (WO 3 ), nickel oxide oxide and cerium-doped tungsten oxide (CeWO 3 ).
상기 제1 전극이 인듐 틴 옥사이드(ITO), 플루오린 틴 옥사이드(FTO), 은 나노와이어(Ag nanowires) 및 은 나노메쉬(nanomesh) 중에서 선택된 1종 이상을 포함하는 것을 특징으로 하는 유기태양전지.11. The method of claim 10,
Wherein the first electrode comprises at least one selected from the group consisting of indium tin oxide (ITO), fluorine tin oxide (FTO), silver nanowires, and silver nanomesh.
상기 제2 전극이 Au, Fe, Ag, Cu, Cr, W, Al, Mo, Zn, Ni, Pt, Pd, Co, In, Mn, Si, Ta, Ti, Sn, Pb, V, Ru, Ir, Zr, Rh 및 Mg 중에서 선택된 1종 이상을 포함하는 것을 특징으로 하는 유기태양전지.
11. The method of claim 10,
Wherein the second electrode is made of Au, Fe, Ag, Cu, Cr, W, Al, Mo, Zn, Ni, Pt, Pd, Co, In, Mn, Si, Ta, Ti, Sn, Pb, , Zr, Rh, and Mg.
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