KR101439998B1 - Novel cyclopentadithiophene derivatives, preparation method thereof and organic solar cell having the same - Google Patents
Novel cyclopentadithiophene derivatives, preparation method thereof and organic solar cell having the same Download PDFInfo
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- KR101439998B1 KR101439998B1 KR1020120144321A KR20120144321A KR101439998B1 KR 101439998 B1 KR101439998 B1 KR 101439998B1 KR 1020120144321 A KR1020120144321 A KR 1020120144321A KR 20120144321 A KR20120144321 A KR 20120144321A KR 101439998 B1 KR101439998 B1 KR 101439998B1
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- South Korea
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- dye
- formula
- solar cell
- cyclopentadithiophene
- compound
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- 238000002360 preparation method Methods 0.000 title description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 21
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims description 53
- 239000000758 substrate Substances 0.000 claims description 28
- 239000003792 electrolyte Substances 0.000 claims description 23
- -1 2- ethylhexyl Chemical group 0.000 claims description 19
- 239000004065 semiconductor Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims description 9
- 150000004706 metal oxides Chemical class 0.000 claims description 9
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical compound C1=CC(OC)=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 XDXWNHPWWKGTKO-UHFFFAOYSA-N 0.000 claims description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 239000000975 dye Substances 0.000 description 67
- 239000011521 glass Substances 0.000 description 41
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- 238000002451 electron ionisation mass spectrometry Methods 0.000 description 18
- 229910010413 TiO 2 Inorganic materials 0.000 description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 15
- 239000012153 distilled water Substances 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
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- 230000000052 comparative effect Effects 0.000 description 14
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- HCURECRAYBRAJM-UHFFFAOYSA-N 10-bromo-7,7-dihexyl-3,11-dithiatricyclo[6.3.0.02,6]undeca-1(8),2(6),4,9-tetraene-4-carbaldehyde Chemical compound S1C(C=O)=CC2=C1C(SC(Br)=C1)=C1C2(CCCCCC)CCCCCC HCURECRAYBRAJM-UHFFFAOYSA-N 0.000 description 7
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
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- 238000000149 argon plasma sintering Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 5
- IJVRPNIWWODHHA-UHFFFAOYSA-N 2-cyanoprop-2-enoic acid Chemical compound OC(=O)C(=C)C#N IJVRPNIWWODHHA-UHFFFAOYSA-N 0.000 description 4
- ZHQNDEHZACHHTA-UHFFFAOYSA-N 9,9-dimethylfluorene Chemical compound C1=CC=C2C(C)(C)C3=CC=CC=C3C2=C1 ZHQNDEHZACHHTA-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000008033 biological extinction Effects 0.000 description 4
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- HBENZIXOGRCSQN-VQWWACLZSA-N (1S,2S,6R,14R,15R,16R)-5-(cyclopropylmethyl)-16-[(2S)-2-hydroxy-3,3-dimethylpentan-2-yl]-15-methoxy-13-oxa-5-azahexacyclo[13.2.2.12,8.01,6.02,14.012,20]icosa-8(20),9,11-trien-11-ol Chemical compound N1([C@@H]2CC=3C4=C(C(=CC=3)O)O[C@H]3[C@@]5(OC)CC[C@@]2([C@@]43CC1)C[C@@H]5[C@](C)(O)C(C)(C)CC)CC1CC1 HBENZIXOGRCSQN-VQWWACLZSA-N 0.000 description 2
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- 125000002524 organometallic group Chemical group 0.000 description 2
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/04—Ortho-condensed systems
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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
- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
- Y02E10/542—Dye sensitized solar cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
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Abstract
본 발명은 신규한 사이클로펜타디티오펜 유도체에 관한 것으로, 더욱 구체적으로는 상기 유도체를 염료감응 태양전지의 염료로 사용하여 광전변환효율이 현저히 향상될 뿐만 아니라, 사이클로펜타디티오펜에 알킬기를 도입함으로써 염료 분자간의 응집이 방지되고 열적, 광적 안정성이 향상되므로, 고체상 전해질을 사용하는 염료감응 태양전지의 염료 및 고분자/단분자 혼합형 태양전지의 단분자로 유용하게 사용될 수 있다.The present invention relates to a novel cyclopentadithiophene derivative, more specifically, to a dye-sensitized solar cell using the derivative as a dye, and not only the photoelectric conversion efficiency is remarkably improved but also the dye is incorporated into the cyclopentadithiophene Molecular cohesion is prevented and thermal and photonic stability are improved. Therefore, it can be used as a single molecule of a dye and a polymer / monomolecular hybrid type solar cell of a dye-sensitized solar cell using a solid electrolyte.
Description
본 발명은 신규한 사이클로펜타디티오펜 유도체 및 이를 포함하는 유기태양전지에 관한 것이다.
The present invention relates to a novel cyclopentadithiophene derivative and an organic solar cell comprising the same.
유기태양전지(Organic Photovoltaics, Organic Solar Cells)는 광기전력효과에 의해 빛 에너지를 전기에너지로 변환시키는 장치이다. 이러한 유기태양전지에는 빛을 흡수하는 활성층에 유기반도체 혹은 유기 분자를 포함하고 있다.
Organic Photovoltaics (Organic Solar Cells) are devices that convert light energy into electrical energy by photovoltaic effects. Such an organic solar cell contains an organic semiconductor or an organic molecule in an active layer that absorbs light.
유기태양전지의 특성은 재료의 저가성, 공정의 용이성 및 유연성을 지닌 재료와의 호환성 등이 있으며 이러한 특성을 바탕으로 차세대 태양전지로서의 연구가 활발히 진행되고 있다. 유기태양전지의 가장 보편적인 기술로서는 염료감응 태양전지, 유무기 복합 태양전지, 기상증착 또는 용액공정에 기반을 둔 고분자, 유기 저분자, 고분자/플러렌 등을 이용한 유기태양전지 등이 있다.
The properties of organic solar cells are low cost, easy processability and compatibility with materials having flexibility. Based on these characteristics, researches as next generation solar cells are actively conducted. The most common technologies for organic solar cells include dye-sensitized solar cells, organic and inorganic hybrid solar cells, polymers based on vapor deposition or solution processes, organic low-molecular materials, and organic solar cells using polymers / fullerene.
고분자/단분자 혼합형 태양전지(Bulk heterojunction solar cells, BHJ)는 유기태양전지의 중요한 연구분야 중 하나이다. 고분자/단분자 혼합형 태양전지는 전자주게(Electron-donor)와 전자받게(Electron-acceptor)의 구성을 기본으로 하여 그들의 계면에서 전하가 생성되어 결과적으로 홀/전자의 이동이 각각 전자주게/전자받게 분자의 자기조립 구조를 따라 이루어지는 광전변환효과의 적용에 가장 이상적인 장치이다. Bulk heterojunction solar cells (BHJ) are one of the important research fields of organic solar cells. Polymer / monomolecular hybrid solar cells are based on the structure of electron-donor and electron-acceptor, and charge is generated at their interface, resulting in the transfer of holes / It is the most ideal device for application of the photoelectric conversion effect that follows the self-assembled structure of molecules.
대표적인 고분자/단분자 혼합형 태양전지의 구성물질은 P3HT[poly(3-hexylthiophene)]/PCBM[(6,6)-phenyl-C61-butyric acid methyl ester]로서 4 내지 5%의 효율이 보고되었다.
As a constituent material of a typical polymer / monomolecular hybrid type solar cell, efficiency of 4 to 5% was reported as P3HT [poly (3-hexylthiophene)] / PCBM [(6,6) -phenyl-C61-butyric acid methyl ester].
그러나, P3HT은 좁은 광흡수 영역을 가지는 단점 때문에 더 이상의 효율 증대를 기대할 수 없는 단점이 있다. 이러한 한계점을 극복하기 위해 새로운 로우-밴드갭(low-bandgap) 고분자 또는 유기 저분자 염료가 전자주게기로서의 역할로서 개발되고 있다. However, P3HT has a disadvantage that further increase in efficiency can not be expected due to the disadvantage of having a narrow light absorption region. To overcome these limitations, new low-bandgap polymers or organic low-molecular dyes have been developed as electron donors.
원초적으로 유기 저분자는 분자구조의 다양성과 합성 및 정제의 용이성, 아울러 광전자적인 성질에 근거한 분자구조의 변환이 용이한 장점들을 지니고 있다. Originally, organic low molecular weight molecules have various advantages of molecular structure, easiness of synthesis and purification, and easy conversion of molecular structure based on photoelectron properties.
아울러 실제 소자 제작시에 분자들 간의 정렬된 형태의 자기조립성질을 지니고 있으므로 높은 전하 이동도를 나타내는 장점도 있다. 이러한 여러 가지 장점들로 인해 고분자/단분자 혼합형 태양전지의 전자주게로서의 유기 저분자 염료의 개발이 활발히 진행되고 있다.
In addition, there is also an advantage of high charge mobility since it has self-assembling properties of molecules aligned in the actual device. Due to these various advantages, development of an organic low molecular weight dye as an electron donor of a polymer / monomolecular hybrid type solar cell is progressing actively.
염료감응 태양전지는 실리콘 태양전지와는 달리 감광성 염료분자와 전이금속 산화물을 구성 재료로 하는 광전기 화학적 태양전지이다. 상세하게 상기 감광성 염료분자는 가시광선을 흡수하여 전자-홀 쌍(electron-hole pair)을 생성하고, 상기 생성된 전자가 상기 전이금속 산화물에 의해 기판으로 전달되어 광전기 화학적 특성을 갖는다.
Unlike silicon solar cells, dye-sensitized solar cells are photo-electrochemical solar cells that contain photosensitive dye molecules and transition metal oxides. In detail, the photosensitive dye molecule absorbs visible light to generate an electron-hole pair, and the generated electrons are transferred to the substrate by the transition metal oxide to have photoelectrochemical properties.
지금까지 알려진 염료감응 태양전지 중 대표적인 예가 스위스의 그라첼(Gratzel) 등에 의하여 발표된 염료감응 태양전지가 있다(특허문헌 1 및 특허문헌 2). 일반적으로 그라첼 등에 의한 염료감응 태양전지들은 염료분자가 입혀진 나노입자 이산화티탄(TiO2)으로 이루어지는 반도체 전극, 백금 전극, 그리고 이들 사이에 채워진 전해질 용액으로 구성되어 있다.
A representative example of dye-sensitized solar cells known so far is a dye-sensitized solar cell disclosed by Gratzel et al., Switzerland (Patent Document 1 and Patent Document 2). Generally, dye-sensitized solar cells by Gratel et al. Consist of a semiconductor electrode made of nanoparticle titanium dioxide (TiO 2 ) coated with a dye molecule, a platinum electrode, and an electrolyte solution filled therebetween.
상기와 같은 염료감응 태양전지는 실리콘 태양전지에 비해 전력당 제조 원가가 저렴하기 때문에 태양전지로 유용성이 있다는 점에서 주목받아 왔다. 염료감응 태양전지에 이용되는 염료는 크게 두 가지로 나누어진다. 하나는 유기금속 염료(organometallic dye)이고, 다른 하나는 유기염료(organic dye)이다.The above-described dye-sensitized solar cell has attracted attention because it is more useful as a solar cell because its manufacturing cost is lower than that of a silicon solar cell. Dyes used in dye-sensitized solar cells are divided into two types. One is an organometallic dye and the other is an organic dye.
<유기금속 염료의 예>≪ Example of organic metal dye &
특허문헌 2에는 유기금속 염료로서 Ru(II)-폴리피리딜 화합물을 연결시킨 Ru(dcb)(bpy)2 2+가 주요 염료로 개시되어 있다.
In Patent Document 2, Ru (dcb) (bpy) 2 2+ in which Ru (II) -polypyridyl compound is connected as an organic metal dye is disclosed as a main dye.
또한, 이외에 종래에는 Ru, Os, Cu, Zn 등의 전이 금속에 질소를 포함하는 다양한 리간드를 포함하는 염료 등이 개시되어 있다(특허문헌 3 내지 특허문헌 6).
In addition, conventionally, dyes including various ligands including nitrogen in transition metals such as Ru, Os, Cu, and Zn have been disclosed (Patent Documents 3 to 6).
상기 염료들 중에서 나노입자 염료감응 태양전지의 Ru계 염료로 붉은 주홍색과 진한 청색을 나타내는 상기 화학식의 화합물들이(상표명: 'N719', 'N3' 등) 유기금속 염료로 가장 널리 사용되고 있다.
Of the above dyes, compounds of the above formula, which are reddish-purple and dark blue, are most widely used as organometallic dyes (trade names: 'N719', 'N3', etc.) as Ru-based dyes of nanoparticle dye-sensitized solar cells.
유기염료는 가시광선 영역에서 높은 흡광 효율을 나타내고, 유기금속 염료에 비해 저가 합성이 가능하다는 이유로 점차 주목받고 있는 실정이다. 그러나 유기염료는 여기 상태에서의 지속시간이 짧고, 염료의 응집(aggregation) 현상이 발생하여, 효율이 우수하지 않다는 문제점이 있다. 따라서 응집이 방지되며, 효율이 우수한 신규한 유기염료의 필요성이 증가하고 있다.
Organic dyes exhibit high absorption efficiency in the visible light region and are attracting attention because they can be synthesized at a low cost compared with organic metal dyes. However, organic dyes have a short duration in the excited state and aggregation phenomenon of dyes, resulting in poor efficiency. Therefore, there is an increasing need for novel organic dyes that are less agglomerated and have better efficiency.
또한, 현재 기본적으로 제작되어 지고 있는 염료감응형 태양전지 셀은 액체 전해질을 기본으로 사용하고 있다. 그러나, 이러한 액체 전해질은 모듈 제작시 밀봉의 한계성과 장기간 안정성에 대한 문제점을 내포하고 있다. 그러므로 문제점을 내포한 액체 전해질을 대체하기 위한 준고상 및 고체상 전해질의 개발이 필연적으로 요구되어 왔다.
In addition, a dye-sensitized solar cell, which is basically manufactured at present, uses a liquid electrolyte as a basis. However, these liquid electrolytes have problems in the limit of sealing and long-term stability in the manufacture of the module. Therefore, it has been inevitably required to develop quasi-solid and solid electrolytes for replacing liquid electrolytes containing problems.
이에, 본 발명자들은 염료의 응집이 발생하지 않고 광전변환효율이 우수한 염료를 연구하던 중, 신규한 사이클로펜타디티오펜 유도체가 준고상 및 고체상 전해질을 사용하는 염료감응 태양전지에서 광전변환효율이 우수한 염료로 사용될 수 있는 것을 발견하고 본 발명을 완성하였다.
Accordingly, the inventors of the present invention have been studying dyes having excellent photoelectric conversion efficiency without causing aggregation of dyes, and have found that the novel cyclopentadithiophene derivatives are superior in dye-sensitized solar cells using quasi-solid and solid-state electrolytes, And the present invention has been completed.
본 발명의 목적은 신규한 사이클로펜타디티오펜 유도체를 제공하는 것이다.It is an object of the present invention to provide novel cyclopentadithiophene derivatives.
본 발명의 다른 목적은 상기 사이클로펜타디티오펜 유도체의 제조방법을 제공하는 것이다.It is another object of the present invention to provide a process for preparing the cyclopentadithiophene derivative.
본 발명의 또 다른 목적은 상기 사이클로펜타디티오펜 유도체를 염료로 사용하는 염료감응 태양전지를 제공하는 것이다.Another object of the present invention is to provide a dye-sensitized solar cell using the cyclopentadithiophene derivative as a dye.
본 발명의 다른 목적은 상기 사이클로펜타디티오펜 유도체를 단분자로 사용하는 고분자/단분자 혼합형 태양전지를 제공하는 것이다.
Another object of the present invention is to provide a polymer / monomolecular hybrid type solar cell using the cyclopentadithiophene derivative as a single molecule.
상기 목적을 달성하기 위하여, 본 발명은 하기 화학식 1로 표시되는 사이클로펜타디티오펜 유도체를 제공한다.In order to achieve the above object, the present invention provides a cyclopentadithiophene derivative represented by the following general formula (1).
[화학식 1][Chemical Formula 1]
(상기 화학식 1에서, R 및 R1은 본 명세서에서 정의한 바와 같다).
(Wherein R and R < 1 > are as defined herein).
또한, 본 발명은 하기 반응식 1에 나타낸 바와 같이,Also, as shown in the following Reaction Scheme 1,
화학식 2로 표시되는 화합물과 화학식 3으로 표시되는 화합물을 반응시켜 화학식 4의 화합물을 제조하는 단계(단계 1); 및Reacting a compound represented by formula (2) with a compound represented by formula (3) to prepare a compound represented by formula (4) (step 1); And
상기 단계 1에서 제조된 화학식 4의 화합물을 시아노아세트산과 반응시켜 화학식 1로 표시되는 사이클로펜타디티오펜 유도체를 제조하는 단계(단계 2)를 포함하는 사이클로펜타디티오펜 유도체의 제조방법을 제공한다.A step of reacting the compound of Formula 4 prepared in Step 1 with cyanoacetic acid to prepare a cyclopentadithiophene derivative represented by Formula 1 (Step 2).
[반응식 1][Reaction Scheme 1]
(상기 반응식 1에서, R 및 R1은 본 명세서에서 정의한 바와 같다).
(In the above Reaction Scheme 1, R and R 1 are as defined herein).
나아가, 본 발명은 전도성 기판;Further, the present invention relates to a semiconductor device comprising: a conductive substrate;
상기 전도성 기판 상에 형성되고, 상기 화학식 1의 화합물을 포함하는 염료가 흡착된 금속 산화물층을 포함하는 반도체 전극;A semiconductor electrode formed on the conductive substrate and including a dye-adsorbed metal oxide layer containing the compound of Formula 1;
대향 전극; 및An opposing electrode; And
상기 반도체 전극과 상기 대향 전극 사이를 채우는 전해질을 포함하는 것을 특징으로 하는 염료감응 태양전지를 제공한다.
And an electrolyte filling the space between the semiconductor electrode and the counter electrode.
또한, 본 발명은 화학식 1의 사이클로펜타디티오펜 유도체를 단분자로 사용하는 고분자/단분자 혼합형 태양전지를 제공한다.
The present invention also provides a polymer / monomolecular hybrid type solar cell using a cyclopentadithiophene derivative represented by the formula (1) as a single molecule.
본 발명에 따른 신규한 사이클로펜타디티오펜 유도체는 염료로서, 특히 준고상 및 고체상 전해질을 사용하는 염료감응 태양전지에서 광전변환효율이 현저히 향상될 뿐만 아니라, 사이클로펜타디티오펜기에 알킬기를 도입함으로써 염료 분자간의 응집이 방지되고 열적, 광적 안정성이 향상되므로, 준고상 및 고체상 전해질을 사용하는 염료감응 태양전지의 염료 및 고분자/단분자 혼합형 태양전지의 단분자로 유용하게 사용될 수 있다.
The novel cyclopentadithiophene derivative according to the present invention not only remarkably improves the photoelectric conversion efficiency in the dye-sensitized solar cell using the quasi-solid and solid electrolyte as the dye but also improves the dye-sensitized solar cell by introducing the alkyl group into the cyclopentadithiophene group, Aggregation of the dye-sensitized solar cell is prevented and the thermal and optical stability is improved. Therefore, it can be used as a single molecule of a dye and a polymer / monomolecular hybrid type solar cell using a dye-sensitized solar cell using a quasi-solid and a solid electrolyte.
도 1은 본 발명에 따른 염료감응 태양전지를 개략적으로 나타낸 도면이다.
도 2는 본 발명에 따른 고분자/단분자 혼합형 태양전지를 개략적으로 나타낸 도면이다. 1 is a schematic view of a dye-sensitized solar cell according to the present invention.
2 is a schematic view of a polymer / monomolecular hybrid type solar cell according to the present invention.
이하, 본 발명을 상세히 설명한다.
Hereinafter, the present invention will be described in detail.
본 발명은 하기 화학식 1로 표시되는 사이클로펜타디티오펜 유도체를 제공한다.The present invention provides a cyclopentadithiophene derivative represented by the following formula (1).
상기 화학식 1에서, In Formula 1,
R 및 R1은 서로 독립적으로, 수소, C1 내지 C20 직쇄 또는 측쇄 알킬이다.
R and R < 1 > are independently from each other hydrogen, C1 to C20 straight chain or branched chain alkyl.
바람직하게는, 상기 화학식 1에서,Preferably, in the above formula (1)
상기 R 및 R1은 서로 독립적으로, 수소, 메틸, 에틸, 프로필, 이소프로필, 부틸, 이소부틸, tert-부틸, 펜틸, 헥실, 2-에틸헥실, 헵틸, 2-에틸펜틸, 옥틸, 3-프로필펜틸, 노닐, 데카닐, 운데카닐, 도데카닐 또는 2-옥틸도데카닐이다.
Wherein R and R 1 are each independently of the other hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, 2-ethylhexyl, Propyl, pentyl, nonyl, decanyl, undecanyl, dodecanyl or 2-octyldodecanyl.
더욱 바람직하게는, 상기 화학식 1에서,More preferably, in Formula 1,
상기 R 및 R1은 서로 독립적으로, 메틸, 에틸, 프로필, 부틸, 펜틸, 헥실, 헵틸, 옥틸, 노닐, 데카닐, 운데카닐 또는 도데카닐이다.
R and R 1 are, independently of each other, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decanyl, undecanyl or dodecanyl.
가장 바람직하게는, 상기 화학식 1의 사이클로펜타디테오펜 유도체는 하기 화합물들로 이루어지는 군으로부터 선택되는 어느 하나이다.Most preferably, the cyclopentadithiophene derivative of the above formula (1) is any one selected from the group consisting of the following compounds.
1) (E)-3-(6-(4-(비스(9,9-디메틸-9H-플루오렌-2-일)아미노)페닐)-4,4-디헥실-4H-사이클로펜타[1,2-b:5,4-b']디티오펜-2-일)-2-시아노아크릴산; 및1) Synthesis of (E) -3- (6- (4- (Bis (9,9-dimethyl-9H- fluoren-2-yl) amino) phenyl) -4,4-dihexyl-4H-cyclopenta [ , 2-b: 5,4-b '] dithiophen-2-yl) -2-cyanoacrylic acid; And
2) (E)-3-(6-(4-(비스(9,9-디메틸-9H-플루오렌-2-일)아미노)페닐)-4,4-디도데실-4H-사이클로펜타[1,2-b:5,4-b']디티오펜-2-일)-2-시아노아크릴산.
2) Synthesis of (E) -3- (6- (4- (Bis (9,9-dimethyl-9H- fluoren- , 2-b: 5,4-b '] dithiophen-2-yl) -2-cyanoacrylic acid.
본 발명에 따른 화학식 1로 표시되는 사이클로펜타디티오펜 유도체는 염료감응 태양전지용 염료로써 몰흡광계수가 높아 얇은 TiO2층을 사용할 수 있을 뿐만 아니라, 광전변화효율 등의 물리적 특성이 상당히 증가하게 된다. 또한, 사이클로펜타디티오펜에 알킬기를 도입함에 따라 분자 간의 응집이 방지되고, 열적, 광적 안정성이 증대된다.The cyclopentadithiophene derivative represented by the formula (1) according to the present invention is a dye for a dye-sensitized solar cell and has a high molar extinction coefficient, so that not only a thin TiO 2 layer can be used but also physical properties such as photoelectric conversion efficiency are significantly increased. Further, by introducing an alkyl group into the cyclopentadithiophene, cohesion between molecules is prevented, and the thermal and optical stability is increased.
특히, 본 발명에 따른 화학식 1로 표시되는 사이클로펜타디티오펜 유도체는 준고상 및 고체상 전해질을 사용하는 염료감응 태양전지용 염료로써 매우 우수한 물리적 특성을 나타낸다.
In particular, the cyclopentadithiophene derivative represented by Formula 1 according to the present invention exhibits excellent physical properties as a dye for a dye-sensitized solar cell using a quasi-solid and a solid electrolyte.
또한, 본 발명은 하기 반응식 1에 나타낸 바와 같이,Also, as shown in the following Reaction Scheme 1,
화학식 2로 표시되는 화합물과 화학식 3으로 표시되는 화합물을 반응시켜 화학식 4의 화합물을 제조하는 단계(단계 1); 및Reacting a compound represented by formula (2) with a compound represented by formula (3) to prepare a compound represented by formula (4) (step 1); And
상기 단계 1에서 제조된 화학식 4의 화합물을 시아노아세트산과 반응시켜 화학식 1로 표시되는 사이클로펜타디티오펜 유도체를 제조하는 단계(단계 2)를 포함하는 상기 화학식 1의 사이클로펜타디티오펜 유도체의 제조방법을 제공한다.A process for producing a cyclopentadithiophene derivative represented by the above formula (1), comprising the step of reacting a compound of the formula (4) prepared in the above step 1 with cyanoacetic acid to prepare a cyclopentadithiophene derivative represented by the formula (1) .
[반응식 1][Reaction Scheme 1]
상기 반응식 1에서, R 및 R1은 상기 화학식 1에서 정의한 바와 같다.
In the above Reaction Scheme 1, R and R 1 are the same as defined in Formula 1 above.
이하, 상기 제조방법을 단계별로 상세히 설명한다.
Hereinafter, the manufacturing method will be described step by step.
본 발명에 따른 반응식 1에 있어서, 단계 1은 화학식 2로 표시되는 화합물과 화학식 3으로 표시되는 화합물을 반응시켜 화학식 4의 화합물을 제조하는 단계로서, 보다 상세하게는 화학식 2로 표시되는 화합물과 화학식 3으로 표시되는 화합물을 팔라듐(Pd) 촉매를 이용하여 결합시키는 단계이다.In Scheme 1 of the present invention, Step 1 is a step of reacting a compound represented by Formula 2 with a compound represented by Formula 3 to prepare a compound represented by Formula 4, more specifically, 3 with a palladium (Pd) catalyst.
이때, 사용가능한 팔라듐 촉매로는 테트라키스트리페닐포스핀팔라듐(Pd(PPh3)4), 팔라듐아세테이트(Pd(OAc)2), 비스벤질리덴아세톤팔라듐(Pd(dba)2), 또는 트리스디벤질리덴아세톤디팔라듐(Pd2(dba)3) 등을 사용할 수 있다.At this time, the available palladium catalyst include tetrakistriphenylphosphine palladium (Pd (PPh 3) 4) , palladium acetate (Pd (OAc) 2), bis- dibenzylidene acetone palladium (Pd (dba) 2), or tris-di Benzylidene acetone dipalladium (Pd 2 (dba) 3 ) and the like can be used.
또한, 사용가능한 용매로는 반응에 악영향을 미치지 않는 용매인 테트라하이드로퓨란(THF), 디옥산, 디메틸포름아미드(DMF) 또는 톨루엔 등을 사용할 수 있다.As the usable solvent, tetrahydrofuran (THF), dioxane, dimethylformamide (DMF) or toluene which is a solvent which does not adversely affect the reaction can be used.
나아가, 반응 온도는 특별히 제한되지는 않으나, 상온 내지 용매의 환류 온도 범위 내에서 수행될 수 있다.Further, the reaction temperature is not particularly limited, but can be performed within a range of room temperature to reflux temperature of the solvent.
또한, 극초단파(microwave)를 이용하여 반응을 수행할 수 있으며, 이 경우, 반응온도는 상온 내지 용매의 환류 온도 범위 내에서 수행될 수 있다.
In addition, the reaction can be carried out using microwaves, and in this case, the reaction temperature can be performed within a range of room temperature to reflux temperature of the solvent.
또한 본 발명에 따른 반응식 1에 있어서, 단계 2는 상기 단계 1에서 제조된 화학식 4의 화합물을 시아노아세트산과 반응시켜 화학식 1로 표시되는 사이클로펜타디티오펜 유도체를 제조하는 단계로서, 보다 상세하게는 화학식 4로 표시되는 화합물과 시아노아세트산 사이의 축합반응을 통해서 화학식 1로 표시되는 사이클로펜타디티오펜 유도체를 제조하는 단계이다.Further, in Scheme 1 of the present invention, Step 2 is a step of preparing a cyclopentadithiophene derivative represented by Formula 1 by reacting the compound of Formula 4 prepared in Step 1 with cyanoacetic acid, A cyclopentadithiophene derivative represented by the formula (1) is produced through a condensation reaction between a compound represented by the formula (4) and cyanoacetic acid.
이때, 사용가능한 용매로는 반응에 악영향을 미치지 않는 용매인 디클로로메탄, 디메틸포르아미드(DMF) 또는 클로로포름 등을 사용할 수 있다.At this time, as the usable solvent, dichloromethane, dimethylformamide (DMF), chloroform or the like which is a solvent which does not adversely affect the reaction can be used.
또한, 참가제로 피리딘 또는 피페리딘 등을 사용할 수 있다.In addition, pyridines or piperidines which are participating in the reaction may be used.
나아가, 반응 온도는 특별히 제한되지는 않으나, 상온 내지 용매의 환류 온도 범위 내에서 수행될 수 있다.
Further, the reaction temperature is not particularly limited, but can be performed within a range of room temperature to reflux temperature of the solvent.
나아가, 본 발명은 도 1에 나타낸 바와 같이, Further, as shown in Fig. 1,
전도성 기판;Conductive substrate;
상기 전도성 기판 상에 형성되고, 하기 화학식 1의 화합물을 포함하는 염료가 흡착된 금속 산화물층을 포함하는 반도체 전극;A semiconductor electrode formed on the conductive substrate, the semiconductor electrode comprising a dye-adsorbed metal oxide layer comprising a compound of Formula 1;
대향 전극; 및An opposing electrode; And
상기 반도체 전극과 상기 대향 전극 사이를 채우는 전해질을 포함하는 것을 특징으로 하는 염료감응 태양전지를 제공한다.
And an electrolyte filling the space between the semiconductor electrode and the counter electrode.
이하, 도 1을 참조하여 본 발명에 따른 염료감응 태양전지를 설명한다.
Hereinafter, a dye-sensitized solar cell according to the present invention will be described with reference to FIG.
본 발명에 따른 염료감응 태양전지(100)는 제1기판(110), 반도체 전극(120), 대향 전극(130), 제2기판(140), 전해질(150) 및 고분자층(160)을 구비한다.The dye-sensitized
상기 제1기판(110)은 전도성 유리로 이루어질 수 있다. 바람직하게는 유리 기판 위에 ITO(indium tinoxide), FTO(fluorine-doped tin oxide)가 코팅되어 있다. The
그리고, 제1기판(110)과 반도체 전극(120) 사이에는 TiCl4층(미도시)이 형성될 수 있다.A TiCl 4 layer (not shown) may be formed between the
상기 반도체 전극(120)은 제1기판(110) 상에 형성되며, 염료가 흡착되어 있는 나노입자 금속 산화물층으로 이루어진다. 반도체 전극(120)은 5 내지 15 μm 정도의 두께로 형성될 수 있다.The
상기 나노입자 금속 산화물층을 이루는 금속 산화물은 이산화티탄(TiO2), 이산화주석(SnO2) 또는 산화아연(ZnO)일 수 있으며, 약 5 내지 30 nm 정도의 크기를 가질 수 있다.The metal oxide constituting the nanoparticle metal oxide layer may be titanium dioxide (TiO 2 ), tin dioxide (SnO 2 ) or zinc oxide (ZnO), and may have a size of about 5 to 30 nm.
나노입자 금속 산화물에 흡착되어 있는 염료는 화학식 1로 표시되는 사이클로펜타디티오펜 유도체를 함유하는 화합물이다. 화학식 1의 화합물은 상술한 바와 같다. The dye adsorbed on the nanoparticle metal oxide is a compound containing the cyclopentadithiophene derivative represented by the formula (1). The compound of the formula (1) is as described above.
그리고, 화학식 1의 디플루오렌페닐아민기는 전자주게(electron donor) 역할을 하고, 시아노아크릴산기는 전자받게(electron acceptor) 역할을 한다.The difluorophenylamine group of formula (1) serves as an electron donor and the cyanoacrylate group serves as an electron acceptor.
상기 제2기판(140)은 제1기판(110)과 마찬가지로 전도성 유리, 즉 ITO 또는 FTO가 코팅되어 있는 유리 기판일 수 있다.The
상기 대향 전극(130)은 제2기판(140) 상에 형성되며, 백금(Pt)으로 이루어질 수 있다. 또한, 대향 전극(130)은 반도체 전극(120)과 대향 되도록 배치된다.The
상기 전해질(150)은 반도체 전극(120)과 대향 전극(130) 사이의 공간을 채우는 물질이다. 전해질(150)은 전해질 용액, 용매가 제거된(solvent-free) 이온성 액체(ionic-liquid) 전해질, 고상(solid-state) 전해질 또는 준고상(quasi solid state) 전해질이 사용될 수 있다. 바람직하게는, DMPII 액상 전해질, 준고상 전해질로 PVH70, PVH80, PVDF-HFP, 고체상 전해질로 spiro-MeOTAD 등이 사용될 수 있다.
The
이하, 본 발명에 따른 염료감응 태양전지의 작동원리에 대하여 설명한다.
Hereinafter, the principle of operation of the dye-sensitized solar cell according to the present invention will be described.
제1기판(110)을 투과한 태양 빛이 반도체 전극(120)의 나노입자 금속 산화물에 흡착된 화학식 1의 화합물의 염료 분자에 의하여 흡수되면, 여기 상태로 들뜨게 된 염료 분자는 전자를 나노입자 금속 산화물의 전도대로 주입하게 된다. 나노입자 금속 산화물로 주입된 전자는 입자간 계면을 통하여 제1기판(110)에 전달되고 외부 전선을 통하여 대향 전극(120)으로 이동된다.
When the sunlight transmitted through the
전자 전이의 결과로 산화된 염료 분자는 전해질(150) 내의 요오드 이온의 산화 환원 작용(3I- →I3 - + 2e-)에 의하여 제공되는 전자를 받아 다시 환원되며, 산화된 요오드 이온(I3 -)은 대향 전극(130)에 도달한 전자에 의해 다시 환원되어 염료감응 태양전지의 작동과정이 완성된다.
The dye molecules oxidized as a result of electron transfer is an iodine ion redox action of in the electrolyte (150) (3I - → I 3 - + 2e -) accept electrons provided by the will be reduced again, the oxidized iodine ions (I 3 - ) is reduced again by the electrons reaching the
또한, 본 발명은 상기 화학식 1의 사이클로펜타디테오펜 유도체를 단분자로 사용하는 고분자/단분자 혼합형 태양전지를 제공한다.
The present invention also provides a polymer / monomolecular hybrid type solar cell using the cyclopentadithiophene derivative of Formula 1 as a single molecule.
도 2에 나타낸 상기 고분자/단분자 혼합형 태양전지(Bulk heterojunction solar cells, BHJ)는 다음과 같이 제조될 수 있다.
The polymer / monomolecular mixed solar cell (BHJ) shown in FIG. 2 can be prepared as follows.
하부에서부터 기판(110), 제1전극(120), 버퍼층(130), 광전변환층(140) 및 제2전극(150)이 적층된 구조를 갖는다. 광전변환층(140)과 제2전극(150) 사이에 전자 전달층, 정공 저지층 혹은 옵티컬 스페이스(optical space)층을 도입할 수 있다.The
상기 기판(110)은 유리 또는 폴리에틸렌테레프탈레이트(PET), 폴리에틸렌나프탈레이트(PEN), 폴리프로필렌(PP), 폴리아미드(PI), 트리아세틸셀루로오즈(TAC) 등을 포함하는 플라스틱과 같은 투명 물질로 제조될 수 있으며, 바람직하게는 유리로 제조된다.The
상기 제1전극(120)은 스퍼터링, 스핀코팅 등의 방법을 사용하여 투명 물질을 상기 기판(110)의 일면에 도포되거나 필름 형태로 코팅됨으로써 형성되는 전극이다. 제1전극(120)은 애노드로 기능하는 부분으로서 후술하는 제2전극(150)에 비하여 일함수가 작은 물질로서 투명성 및 도전성을 갖는 임의의 물질이 사용될 수 있는데, 예컨대 ITO(indium-tin oxide), FTO(Fluorine doped tin oxide), ZnO-(Ga2O3 또는 Al2O3), SnO2-Sb2O3 등이 사용될 수 있으나, ITO를 사용하는 것이 바람직하다.The
상기 제1전극(120)의 상부로 버퍼층(130)이 예를 들어 스핀코팅 등의 방법을 통하여 도입되는데, 본 발명과 관련하여서는 예컨대 폴리(스티렌 설포네이트)로 도핑된 폴리(3,4-에틸렌디옥시티펜)을 사용하여 정공 이동도를 향상시킬 수 있다.The
한편, 상기 버퍼층(130)의 상부에는 스핀 코팅 등의 방법으로 도입된 광전변환층(140)이 적층되는데, 전도성 고분자와 화학식 1로 표시되는 사이클로펜타디티오펜 유도체가 1:0.5 내지 1:4의 중량비로 배합되어 있는 광전 물질을 사용할 수 있다. 이와 같이 배합된 광전변환 물질을 한 가지 유기용매 혹은 2가지 이상의 비점이 상이한 유기용매에 용해시킨 용액을 스핀코팅 등의 방법으로 약 80 nm 이상 두께의 광전변환층(140)으로 도입한다. 광전변환층을 형성하는 단계에서는 스핀 코팅 방법 이외에 스프레이 코팅, 스크린 인쇄, 닥터 블레이드법을 응용할 수 있다. On top of the
또한, 상기 제2전극(150)은 광전변환층(140)이 도입된 상태에서 약 10-7 torr 이하의 진공도에서 알루미늄 등의 금속 물질을 100 - 200 nm 두께로 진공 열 증착한 후에 아르곤 분위기에서 약 150 ℃에서 약 10분 이상 후처리를 함으로써, 광전변환층(140)의 상부에 적층될 수 있다. 상기 제2전극(150)으로 사용될 수 있는 물질로는 금, 알루미늄, 구리, 은 또는 그들의 합금, 칼슘/알루미늄 합금, 마그네슘/은 합금, 알루미늄/리튬 합금 등을 포함하며, 바람직하게는 알루미늄, 또는 알루미늄/칼슘 합금이다.
In addition, the
본 발명에 따른 신규한 사이클로펜타디티오펜 유도체는 염료로서, 특히 준고상 및 고체상 전해질을 사용하는 염료감응 태양전지에서 광전변환효율이 현저히 향상될 뿐만 아니라, 사이클로펜타디티오펜기에 알킬기를 도입함으로써 염료 분자 간의 응집이 방지되고 열적, 광적 안정성이 향상되므로, 준고상 및 고체상 전해질을 사용하는 염료감응 태양전지의 염료 및 고분자/단분자 혼합형 태양전지의 단분자로 유용하게 사용될 수 있다.
The novel cyclopentadithiophene derivative according to the present invention not only remarkably improves the photoelectric conversion efficiency in the dye-sensitized solar cell using as a dye, particularly a quasi-solid and a solid electrolyte, And the thermal and photonic stability can be improved. Therefore, it can be useful as a single molecule of a dye and a polymer / monomolecular hybrid type solar cell of a dye-sensitized solar cell using a quasi-solid and a solid electrolyte.
이하, 본 발명을 하기의 실시예에 의하여 더욱 상세히 설명한다. Hereinafter, the present invention will be described in more detail with reference to the following examples.
단, 하기의 실시예는 본 발명을 예시하는 것일 뿐, 본 발명의 내용이 하기의 실시예에 의해 한정되는 것은 아니다.
However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.
<< 제조예Manufacturing example 1> N-(9,9-디메틸-9H- 1 > N- (9,9-Dimethyl-9H- 플루오렌Fluorene -2-일)-9,9-디메틸-N-(4-(4,4,5,5-Yl) -9,9-dimethyl-N- (4- (4,4,5,5- 테rim 트라메틸-1,3,2-Trimethyl-l, 3,2- 디옥사포로란Dioxapolane -2-일)-2 days) 페닐Phenyl )-9H-) -9H- 플로렌Floren -2--2- 아민의Amine 제조(화합물 2) Preparation (Compound 2)
[반응식 2][Reaction Scheme 2]
단계 1: 2-Step 1: 2- 아이오도Iodo -9H--9H- 플루오렌의Fluorene 제조(화합물 6) Preparation (Compound 6)
플루오렌 (5)(5 g, 30.1 mmol)을 아세트산:증류수:황산=100:20:3 의 비율로 섞인 용액으로 용해시킨 다음, 과요오드산(HIO4, 1.1 g, 4.81 mmol), 아이오딘(2.5 g, 9.84 mmol)을 첨가하고 60 내지 65 ℃로 등온하여, 24시간 동안 교반하였다. 그 후, 상온으로 냉각시키고 여과하여 2N 소듐카보네이트 수용액(15 mL) 및 증류수(15 mL)로 세척하였다. 다음으로 혼합물의 유기층을 감압농축시키고, 관크로마토그래피(실리카겔; 에틸아세테이트/헥산=1/99 (v:v))로 정제한 다음, 헥산으로 재결정하여 흰색의 목적화합물 (6)(5 g, 57 %)을 얻었다.Fluorene (5) (5 g, 30.1 mmol) acetic acid: distilled water: sulfuric acid = 100: 20: was dissolved in a solution mixed at a ratio of 3, and then periodic acid (HIO 4, 1.1 g, 4.81 mmol) and iodine (2.5 g, 9.84 mmol) were added, the mixture was stirred at 60-65 캜 and stirred for 24 hours. It was then cooled to room temperature, filtered and washed with 2N aqueous sodium carbonate solution (15 mL) and distilled water (15 mL). The organic layer of the mixture was concentrated under reduced pressure and purified by column chromatography (silica gel; ethyl acetate / hexane = 1/99 (v: v)) and then recrystallized with hexane to obtain the target compound (6) 57%).
1H NMR (300MHz, CDCl3), δ(ppm): 7.89(s, 1H), 7.77(d, 1H), 7.71(d, 1H), 7.54(d, J=6.7, 2H), 7.38-7.32(m, 2H), 3.87(s, 2H); 1 H NMR (300MHz, CDCl 3 ), δ (ppm): 7.89 (s, 1H), 7.77 (d, 1H), 7.71 (d, 1H), 7.54 (d, J = 6.7, 2H), 7.38-7.32 (m, 2 H), 3.87 (s, 2 H);
EI-MS. clad. for C13H9I : 291.97 (found : 292).
EI-MS. clad. for C 13 H 9 I: 291.97 (found: 292).
단계 2: 2-Step 2: 2- 아이오도Iodo -9,9-디메틸-9H--9,9-dimethyl-9H- 플루오렌의Fluorene 제조(화합물 7) Preparation (Compound 7)
상기 단계 1에서 제조한 2-아이오도-9H-플루오렌 (6)(2 g, 6.85 mmol)와 트리에틸벤질암모니움 클로라이드(0.16 g, 0.68 mmol)을 디메틸술폭사이드(DMSO, 136 mL)에 용해시킨 다음, 50% 소듐히드록사이드 수용액(1.41 mL)을 첨가하고 교반하였다. 아이오도메탄(1.56 mL, 25.4 mmol)을 첨가하고, 상온에서 6시간 동안 교반한 뒤, 1M 염산 용액(5 mL)으로 반응을 종결시켰다. 상기 혼합물에 메틸렌클로라이드(MC, 20 mL)로 추출하고, 추출한 유기층을 감압농축시킨 다음, 관크로마토그래피(실리카겔; 에틸아세테이트/헥산=1/99 (v:v))로 정제하여, 목적화합물 (7)(1.6 g, 77 %)을 얻었다.(2 g, 6.85 mmol) and triethylbenzylammonium chloride (0.16 g, 0.68 mmol) prepared in Step 1 above were dissolved in dimethylsulfoxide (DMSO, 136 mL) After dissolution, 50% aqueous sodium hydroxide solution (1.41 mL) was added and stirred. Iodomethane (1.56 mL, 25.4 mmol) was added, stirred at room temperature for 6 hours, and the reaction was terminated with 1M hydrochloric acid solution (5 mL). The mixture was extracted with methylene chloride (MC, 20 mL), and the extracted organic layer was concentrated under reduced pressure. The residue was purified by column chromatography (silica gel; ethyl acetate / hexane = 1/99 (v: v) 7) (1.6 g, 77%).
1H NMR (300MHz, CDCl3), δ(ppm): 7.75(s, 1H), 7.69-7.63(m, 2H), 7.47(d, J=8.0, 1H), 7.41-7.39(m, 1H), 7.34-7.31(m, 2H), 1.46(s, 6H); 1 H NMR (300 MHz, CDCl 3 ),? (Ppm): 7.75 (s, 1H), 7.69-7.63 (m, 2H), 7.47 (d, J = 8.0, 1H), 7.41-7.39 , 7.34-7. 31 (m, 2H), 1.46 (s, 6H);
EI-MS. clad. for C15H13I : 320.01 (found : 320).
EI-MS. clad. for C 15 H 13 I: 320.01 (found: 320).
단계 3: N-(4-Step 3: N- (4- 브로모페닐Bromophenyl )-N-(9,9-디메틸-9H-) -N- (9,9-dimethyl-9H- 플루오렌Fluorene -2-일)-9,9-디메틸-9H-플루오렌-2-Yl) -9,9-dimethyl-9H-fluoren-2- 아민의Amine 제조(화합물 8) Preparation (Compound 8)
상기 단계 2에서 제조된 2-아이오도-9,9-디메틸-9H-플루오렌 (7)(1.6 g, 5.0 mmol), 4-브로모아닐린(0.34 g, 2.0 mmol), 염화구리(40 mg, 0.4 mmol), 포타슘히드록사이드(0.89 g, 15.8 mmol) 및 1,10-페난트롤린(79 mg, 0.4 mmol)을 1시간 동안 진공건조를 시킨 다음, 톨루엔(10 mL)에 용해시켰다. 상기 혼합물을 115 ℃로 가열하여 24시간 동안 교반한 후, 증류수(5 mL)로 반응을 종결시키고 메틸렌클로라이드(20 mL)로 추출하였다. 추출된 혼합물의 유기층을 감압농축하고, 관크로마토그래피(실리카겔; 에틸아세테이트/헥산=1/9 (v:v))로 정제하여, 목적화합물 (8)(0.46 g, 42 %)을 얻었다.(1.6 g, 5.0 mmol), 4-bromoaniline (0.34 g, 2.0 mmol), copper chloride (40 mg , 0.4 mmol), potassium hydroxide (0.89 g, 15.8 mmol) and 1,10-phenanthroline (79 mg, 0.4 mmol) were vacuum dried for 1 hour and then dissolved in toluene (10 mL). The mixture was heated to 115 [deg.] C and stirred for 24 hours, then the reaction was terminated with distilled water (5 mL) and extracted with methylene chloride (20 mL). The organic layer of the extracted mixture was concentrated under reduced pressure and purified by column chromatography (silica gel; ethyl acetate / hexane = 1/9 (v: v)) to obtain the desired compound (8) (0.46 g, 42%).
1H NMR (300MHz, CDCl3), δ(ppm): 7.67(d, J=7.7, 2H), 7.62(d, J=8.1, 2H), 7.41-7.36(m, 4H), 7.33-7.27(m, 4H), 7.22(d, J=1.9, 2H), 7.10(d, J=8.7, 4H), 1.44 (s, 12H); 1 H NMR (300MHz, CDCl 3 ), δ (ppm): 7.67 (d, J = 7.7, 2H), 7.62 (d, J = 8.1, 2H), 7.41-7.36 (m, 4H), 7.33-7.27 ( m, 4H), 7.22 (d, J = 1.9, 2H), 7.10 (d, J = 8.7,4H), 1.44 (s, 12H);
EI-MS. clad. for C36H30BrN : 555.16, (found : 555).
EI-MS. clad. for C 36 H 30 BrN: 555.16, (found: 555).
단계 4: N-(9,9-디메틸-9H-Step 4: N- (9,9-Dimethyl-9H- 플루오렌Fluorene -2-일)-9,9-디메틸-N-(4-(4,4,5,5-Yl) -9,9-dimethyl-N- (4- (4,4,5,5- 테트라메틸Tetramethyl -1,3,2--1,3,2- 디옥사보로란Dioxaborolane -2-일)-2 days) 페닐Phenyl )-9H-) -9H- 플루오렌Fluorene -2--2- 아민의Amine 제조(화합물 2) Preparation (Compound 2)
상기 단계 3에서 제조된 N-(4-브로모페닐)-N-(9,9-디메틸-9H-플루오렌-2-일)-9,9-디메틸-9H-플루오렌-2-아민 (8)(1.1 g, 1.98 mmol), 비스(피나콜라토)디보론(1 g, 3.96 mmol), [1,1'-비스(디페닐포스피노)페로센]디클로로팔라듐(Ⅱ)(0.14g,0.20mmol) 및 포타슘아세테이트(0.58g,5.94mmol)를 디메틸술폭사이드(DMSO, 10 mL)로 용해시키고, 상기 혼합물을 90 ℃로 가열한 다음, 24시간 동안 교반하였다. 그 후, 상온으로 냉각시킨 다음, 증류수(5 mL)를 첨가하고 에틸아세테이트(15 mL)로 추출하여, 추출된 혼합물의 유기층을 감압농축시켰다. 농축된 상기 혼합물을 관크로마토그래피(실리카겔; 에틸아세테이트/헥산=1/9 (v:v))로 정제하여, 목적화합물 (2)(0.4 g, 33.5 %)를 얻었다.To a solution of N- (4-bromophenyl) -N- (9,9-dimethyl-9H-fluoren-2-yl) -9,9-dimethyl- 8) (1.1 g, 1.98 mmol), bis (pinacolato) diboron (1 g, 3.96 mmol) and [1,1'-bis (diphenylphosphino) ferrocene] dichloropalladium 0.20 mmol) and potassium acetate (0.58 g, 5.94 mmol) were dissolved in dimethylsulfoxide (DMSO, 10 mL) and the mixture was heated to 90 < 0 > C and then stirred for 24 hours. After cooling to room temperature, distilled water (5 mL) was added and extracted with ethyl acetate (15 mL), and the organic layer of the extracted mixture was concentrated under reduced pressure. The concentrated mixture was purified by column chromatography (silica gel; ethyl acetate / hexane = 1/9 (v: v)) to obtain the desired compound (2) (0.4 g, 33.5%).
1H NMR (300MHz, CDCl3), δ(ppm): 7.71-7.63(m, 4H), 7.60(d, J=8.1, 2H), 7.39-7.28(m, 5H), 7.25-7.13(m, 4H), 7.10-7.07(m, 3H), 1.40(s, 12H); 1 H NMR (300MHz, CDCl 3 ), δ (ppm): 7.71-7.63 (m, 4H), 7.60 (d, J = 8.1, 2H), 7.39-7.28 (m, 5H), 7.25-7.13 (m, 4H), 7.10-7.07 (m, 3H), 1.40 (s, 12H);
EI-MS. clad. for C42H42BNO2 : 603.33 (found : 603).
EI-MS. clad. for C 42 H 42 BNO 2 : 603.33 (found: 603).
<< 제조예Manufacturing example 2> 6- 2> 6- 브로모Bromo -4,4--4,4- 디알킬Dialkyl -4H--4H- 사이클로펜타[1,2-b:5,4-b']디티오펜Cyclopenta [1,2-b: 5,4-b '] dithiophene -2--2- 카르발데히드의Carbaldehyde 제조(화합물 3a, 3b) Preparation (compounds 3a, 3b)
[반응식 3][Reaction Scheme 3]
단계 1: Step 1: 비스(2-아이오도티오펜-3-일)메탄올의Bis (2-iodothiophen-3-yl) methanol 제조(화합물 9) Preparation (Compound 9)
-78 ℃상에서, 무수 디에틸에테르(50 ml)에 2.5 M의 n-부틸리튬(61.3 mL, 153.3 mmol)을 용해시키고, 무수 디에틸에테르(25 ml)에 용해시킨 3-브로모티오펜(25 g, 153.3 mmol)을 천천히 적가한 다음, 3시간 동안 교반하였다. -78 ℃상에서 티오펜-3-카르발데히드(17.2 g, 153.3 mmol)를 천천히 첨가하고 30분간 교반한 뒤, 상온으로 등온하고 30분간 교반하였다. 다시 -23 ℃로 냉각시키고 2.5 M의 n-부틸리튬(122.6 mL, 306.6 mmol)을 적가한 뒤, 2시간 동안 다시 교반하고, 상온으로 등온하여 30분 동안 교반하였다. 아이오딘(116.7 g,459.9 mmol)을 에테르에 용해시켜 천천히 적가하여 24시간 동안 교반하였다. 1N 염산 수용액과 소듐 설피트 수용액을 이용하여 pH 6으로 조절하고, 에테르(100 mL)로 추출한 다음, 추출한 유기층을 감압농축시켰다. 농축된 상기 혼합물을 관크로마토그래피(실리카겔; 에틸아세테이트/헥산=1/9 (v:v))로 정제하여 목적화합물 (9)(25 g, 36.4 %)를 얻었다.2.5 M n-butyllithium (61.3 mL, 153.3 mmol) was dissolved in anhydrous diethyl ether (50 mL) at -78 ° C and 3-bromothiophene (25 mL) dissolved in anhydrous diethyl ether g, 153.3 mmol) was slowly added dropwise, followed by stirring for 3 hours. Thiophene-3-carbaldehyde (17.2 g, 153.3 mmol) was added slowly at -78 deg. C, and the mixture was stirred for 30 minutes and then was stirred at room temperature for 30 minutes. The mixture was cooled to -23 DEG C again, and 2.5 M n-butyl lithium (122.6 mL, 306.6 mmol) was added dropwise. The mixture was stirred again for 2 hours, isothermalized at room temperature and stirred for 30 minutes. Iodine (116.7 g, 459.9 mmol) was dissolved in ether, slowly added dropwise, and stirred for 24 hours. The mixture was adjusted to pH 6 with a 1N hydrochloric acid aqueous solution and a sodium sulfite aqueous solution, extracted with ether (100 mL), and the extracted organic layer was concentrated under reduced pressure. The concentrated mixture was purified by column chromatography (silica gel; ethyl acetate / hexane = 1/9 (v: v)) to obtain the desired compound (9) (25 g, 36.4%).
1H NMR (300MHz, CDCl3), δ(ppm): 7.45(d, J=5.4, 2H), 7.05(d, J=4.9, 2H), 5.77(d, J=3.0, 1H), 2.03(s, OH); 1 H NMR (300MHz, CDCl 3 ), δ (ppm): 7.45 (d, J = 5.4, 2H), 7.05 (d, J = 4.9, 2H), 5.77 (d, J = 3.0, 1H), 2.03 ( s, OH);
EI-MS. clad. for C9H6I2OS2 : 447.79 (found : 448).
EI-MS. clad. for C 9 H 6 I 2 OS 2 : 447.79 (found: 448).
단계 2: Step 2: 비스(2-아이오도티오펜-3-일)메타논의Bis (2-iodothiophen-3-yl) methanone 제조(화합물 10) Preparation (Compound 10)
상기 단계 1에서 제조된 비스(2-아이오도티오펜-3-일)메탄올 (9)(25 g, 55.8 mmol)을 클로로포름(50 mL)에 용해시키고 피리디늄 클로로크로메이트(PCC, 18 g, 83.7 mmol)를 첨가한 다음, 상온에서 12시간 동안 교반하였다. 그 후, 상기 혼합물을 감압농축하고, 농축된 상기 혼합물을 관크로마토그래피(실리카겔; 에틸아세테이트/헥산=1/8 (v:v))로 정제하여 목적화합물 (10)(19.9 g, 80 %)을 얻었다.(25 g, 55.8 mmol) was dissolved in chloroform (50 mL) and pyridinium chlorochromate (PCC, 18 g, 83.7 mmol) was added dropwise to the solution of bis (2-iodothiophen- ) Was added, followed by stirring at room temperature for 12 hours. The mixture was then concentrated under reduced pressure and the concentrated mixture was purified by column chromatography (silica gel; ethyl acetate / hexane = 1/8 (v: v)) to obtain the desired compound (10) (19.9 g, 80% ≪ / RTI >
1H NMR (300MHz, CDCl3), δ(ppm): 7.48(d, J=5.4, 2H), 7.06(d, J=5.4, 2H); 1 H NMR (300 MHz, CDCl 3 ),? (Ppm): 7.48 (d, J = 5.4, 2H), 7.06 (d, J = 5.4, 2H);
EI-MS. clad. for C9H4I2OS2 : 445.78 (found : 446).
EI-MS. clad. for C 9 H 4 I 2 OS 2 : 445.78 (found: 446).
단계 3: 4H-Step 3: 4H- 사이클로펜타[1,2-b:5,4-b']디티오펜Cyclopenta [1,2-b: 5,4-b '] dithiophene -4-온의 제조(화합물 11)One (Compound 11)
상기 단계 2에서 제조된 비스(2-아이오도티오펜-3-일)메타논 (10)(9.2 g, 20.6 mmol)을 무수 디메틸포름이미드(DMF, 50 mL)에 용해하여 교반한 다음, 구리 분말(Cu powder, 3.92 g, 61.8 mmol)을 한번에 첨가하고, 24시간 동안 환류시켰다. 환류시킨 상기 혼합물을 상온으로 냉각시키고 여과하여, 증류수(10 ml)를 첨가한 후, 에테르(20 ml)로 추출하였다. 추출한 유기층을 감압농축시키고, 농축된 상기 혼합물을 관크로마토그래피(실리카겔; 에틸아세테이트/헥산=1/9 (v:v))로 정제하여 목적화합물 (11)(3 g, 76.6 %)을 얻었다.(9.2 g, 20.6 mmol) was dissolved in anhydrous dimethylformamide (DMF, 50 mL) and stirred. Then, a solution of copper (II) Powder (Cu powder, 3.92 g, 61.8 mmol) was added in one portion and refluxed for 24 hours. The refluxed mixture was cooled to room temperature, filtered, added with distilled water (10 ml), and then extracted with ether (20 ml). The extracted organic layer was concentrated under reduced pressure, and the concentrated mixture was purified by column chromatography (silica gel; ethyl acetate / hexane = 1/9 (v: v)) to obtain the target compound (11) (3 g, 76.6%).
1H NMR (300MHz, CDCl3), δ(ppm): 7.04(d, J=4.7, 2H), 6.99(d, J=4.7, 2H); 1 H NMR (300 MHz, CDCl 3 ),? (Ppm): 7.04 (d, J = 4.7, 2H), 6.99 (d, J = 4.7, 2H);
EI-MS. clad. for C9H4OS2 : 191.97 (found : 192).
EI-MS. clad. for C 9 H 4 OS 2 : 191.97 (found: 192).
단계 4: 4H-Step 4: 4H- 사이클로펜타[1,2-b:5,4-b']디티오펜의Cyclopenta [1,2-b: 5,4-b '] dithiophene 제조(화합물 12) Preparation (Compound 12)
상기 단계 3에서 제조된 4H-사이클로펜타-1,2-b:5,4-b']디티오펜-4-온 (11)(3.04 g, 15.8 mmol)과 포타슘히드록사이드(3.02 g, 53.8 mmol)를 트리에틸렌클리콜(200 mL)에 용해시킨 뒤, 80 % 하이드라진 하이드레이트(18.2 mL)를 첨가하고, 180 ℃로 가열하여 24시간 동안 교반하였다. 그 후, 상온으로 냉각시키고 여과한 다음, 증류수(30 mL)를 첨가하였다. 상기 혼합물을 에테르(100 mL)로 추출하고,추출한 유기층을 감압농축시켰다. 농축된 상기 혼합물을 관크로마토그래피(실리카겔; 에틸아세테이트/헥산=1/20 (v:v))으로 정제하여 목적화합물 (12)(1.6 g, 56.7 %)을 얻었다.Cyclopenta-1,2-b: 5,4-b '] dithiophen-4-one (11) (3.04 g, 15.8 mmol) and potassium hydroxide (3.02 g, 53.8 mmol) were dissolved in triethylene glycol (200 mL), 80% hydrazine hydrate (18.2 mL) was added, and the mixture was heated to 180 ° C and stirred for 24 hours. After that, it was cooled to room temperature, filtered, and distilled water (30 mL) was added. The mixture was extracted with ether (100 mL), and the extracted organic layer was concentrated under reduced pressure. The concentrated mixture was purified by column chromatography (silica gel; ethyl acetate / hexane = 1/20 (v: v)) to obtain the desired compound (12) (1.6 g, 56.7%).
1H NMR (300MHz, CDCl3), δ(ppm): 7.37(d, J=4.7, 2H), 7.08(d, J=4.7, 2H), 3.52(s, 2H); 1 H NMR (300 MHz, CDCl 3 ),? (Ppm): 7.37 (d, J = 4.7, 2H), 7.08 (d, J = 4.7, 2H), 3.52
EI-MS. clad. for C9H6S2 : 177.99 (found : 178).
EI-MS. clad. for C 9 H 6 S 2 : 177.99 (found: 178).
단계 5: 4,4-Step 5: 4,4- 디알킬Dialkyl -4H--4H- 사이클로펜타[1,2-b:5,4-b']디티오펜의Cyclopenta [1,2-b: 5,4-b '] dithiophene 제조(화합물 13a, 13b) Preparation (compounds 13a, 13b)
상기 단계 4에서 제조된 4H-사이클로펜타[1,2-b:5,4-b']디티오펜 (12)(1.6 g, 8.98 mmol), 포타슘아이오다이드(3.72 mg, 0.02 mmol) 및 포타슘히드록사이드(1 g, 17.9 mmol)을 디메틸술폭사이드(DMSO, 10 mL)에 용해하고 1-브로모헥산(2.96 g, 17.9 mmol) 또는 1-브로모도데칸(4.46 g, 17.9 mmol)을 첨가하여 상온에서 24시간 동안 교반하였다. 상기 혼합물을 증류수(10 mL)를 첨가한 다음, 메틸렌클로라이드(MC, 30 mL)로 추출하고, 추출한 유기층을 감압농축시켰다. 농축된 상기 혼합물을 관크로마토그래피(실리카겔; 에틸아세테이트/헥산=1/20 (v:v))으로 정제하여 목적화합물 (13a) 또는 (13b)(13a: 2.26 g, 72.6 %; 13b: 3.48 g, 75.3 %)를 얻었다.Cyclopenta [1,2-b: 5,4-b '] dithiophene (12) (1.6 g, 8.98 mmol), potassium iodide (3.72 mg, 0.02 mmol) (2.96 g, 17.9 mmol) or 1-bromododecane (4.46 g, 17.9 mmol) was added to a solution of 1 g (17.9 mmol) of the hydroxide in dimethylsulfoxide (DMSO, And stirred at room temperature for 24 hours. The mixture was added with distilled water (10 mL) and extracted with methylene chloride (MC, 30 mL), and the extracted organic layer was concentrated under reduced pressure. The concentrated mixture was purified by column chromatography (silica gel; ethyl acetate / hexane = 1/20 (v: v)) to give the desired compound (13a) or (13b) (13a: 2.26 g, 72.6% , 75.3%).
화합물 (13a): 1H NMR (300MHz, CDCl3), δ(ppm): 7.25-7.13(m, 2H), 6.93-6.91(m, 2H), 1.85-1.81(m, 4H), 1.31-1.12(m, 16H), 0.96-0.92(m, 6H);Compound (13a): 1 H NMR (300 MHz, CDCl 3 ),? (Ppm): 7.25-7.13 (m, 2H), 6.93-6.91 (m, 2H), 1.85-1.81 (m, 16H), 0.96 - 0.92 (m, 6H);
EI-MS. clad. for C9H6S2 : 346.18 (found : 346).
EI-MS. clad. for C 9 H 6 S 2 : 346.18 (found: 346).
화합물 (13b): 1H NMR (300MHz, CDCl3), δ(ppm): 7.12(d, J=4.8, 2H), 6.91(d, J=4.8, 2H), 1.83-1.78(m, 4H), 1.26-0.95(m, 40H), 0.89-0.84(m, 6H);Compound (13b): 1 H NMR ( 300MHz, CDCl 3), δ (ppm): 7.12 (d, J = 4.8, 2H), 6.91 (d, J = 4.8, 2H), 1.83-1.78 (m, 4H) , 1.26-0.95 (m, 40H), 0.89-0.84 (m, 6H);
EI-MS. clad. for C33H54S2 : 514.37 (found : 514).
EI-MS. clad. for C 33 H 54 S 2 : 514.37 (found: 514).
단계 6: 4,4-디알킬-4H-Step 6: 4,4-Dialkyl-4H- 사이클로펜타[1,2-b:5,4-b']디티오펜Cyclopenta [1,2-b: 5,4-b '] dithiophene -2--2- 카르발데히드Carbaldehyde 의 제조(화합물 14a, 14b)(Compounds 14a and 14b)
상기 단계 5에서 제조된 4,4-디헥실-4H-사이클로펜타[1,2-b:5,4-b']디티오펜 (13a)(0.865 g, 2.50 mmol) 또는 4,4-디도데실-4H-사이클로펜타[1,2-b:5,4-b']디티오펜 (13b)(1.29 g, 2.50 mmol)을 1,2-디클로로에탄(10mL)에 용해시킨다. 0 ℃ 상에서, 디메틸포름이미드(DMF, 2.4 mL, 30.5 mmol) 및 포스포릭클로라이드(POCl3, 0.46 mL, 5 mmol)를 순서대로 첨가한 뒤, 90 ℃로 가열하여 24시간 동안 교반하였다. 반응이 종결되면 상온으로 냉각하고 포화 소듐히드록사이드 수용액으로 pH 6으로 조절하였다. 메틸렌클로라이드(MC, 20 mL)로 추출하고, 추출된 유기층을 감압농축시켰다. 농축된 상기 혼합물을 관크로마토그래피(실리카겔; 에틸아세테이트/헥산=1/8 (v:v))로 정제하여 목적화합물 (14a) 또는 (14b)(14a: 0.45 g, 48 %; 14b: 0.68 g, 50.3 %)을 얻었다.4-dihexyl-4H-cyclopenta [1,2-b: 5,4-b '] dithiophene 13a (0.865 g, 2.50 mmol) or 4,4- (1.29 g, 2.50 mmol) is dissolved in 1,2-dichloroethane (10 mL). Dimethylformimide (DMF, 2.4 mL, 30.5 mmol) and phosphoric chloride (POCl 3 , 0.46 mL, 5 mmol) were added sequentially at 0 ° C, and the mixture was heated to 90 ° C and stirred for 24 hours. When the reaction was completed, the reaction mixture was cooled to room temperature and adjusted to pH 6 with a saturated aqueous solution of sodium hydroxide. The mixture was extracted with methylene chloride (MC, 20 mL), and the extracted organic layer was concentrated under reduced pressure. The concentrated mixture was purified by column chromatography (silica gel; ethyl acetate / hexane = 1/8 (v: v)) to obtain the desired compound (14a) or (14b) (14a: 0.45 g, 48% , 50.3%).
화합물 (14a): 1H NMR (300MHz, CDCl3), δ(ppm): 9.83(s, 1H), 7.57(s, 1H), 7.40(d, J=4.9, 1H), 6.99(d, J=4.9, 1H), 1.89-1.85(m, 4H), 1.30-1.12(m, 16H), 0.91-0.81(m, 6H);Compound (14a): 1 H NMR ( 300MHz, CDCl 3), δ (ppm): 9.83 (s, 1H), 7.57 (s, 1H), 7.40 (d, J = 4.9, 1H), 6.99 (d, J = 4.9, 1H), 1.89-1.85 (m, 4H), 1.30-1.12 (m, 16H), 0.91-0.81 (m, 6H);
EI-MS. clad. for C22H30OS2 : 374.17 (found : 374).
EI-MS. clad. for C 22 H 30 OS 2 : 374.17 (found: 374).
화합물 (14b): 1H NMR (300MHz, CDCl3), δ(ppm): 9.83(s, 1H), 7.56(s, 1H), 7.40(d, J=4.8, 1H), 6.99(d, J=4.8, 1H), 1.88-1.83(m, 4H), 1.28-1.13(m, 40H), 0.93-0.84(m, 6H);Compound (14b): 1 H NMR ( 300MHz, CDCl 3), δ (ppm): 9.83 (s, 1H), 7.56 (s, 1H), 7.40 (d, J = 4.8, 1H), 6.99 (d, J = 4.8, 1H), 1.88-1.83 (m, 4H), 1.28-1.13 (m, 40H), 0.93-0.84 (m, 6H);
EI-MS. clad. for C34H54OS2 : 542.36 (found : 542).
EI-MS. clad. for C 34 H 54 OS 2 : 542.36 (found: 542).
단계 7: 6-Step 7: 6- 브로모Bromo -4,4--4,4- 디알킬Dialkyl -4H--4H- 사이클로펜타[1,2-b:5,4-b']디티오펜Cyclopenta [1,2-b: 5,4-b '] dithiophene -2--2- 카르발데히드의Carbaldehyde 제조(화합물 3a, 3b) Preparation (compounds 3a, 3b)
상기 단계 6에서 제조된 4,4-디헥실-4H-사이클로펜타[1,2-b:5,4-b']디티오펜-2-카르발데히드 (14a)(0.45 g, 1.20 mmol) 또는 4,4-디도데실-4H-사이클로펜타[1,2-b:5,4-b']디티오펜-2-카르발데히드 (14b)(0.65 g, 1.20 mmol)를 테트라하이드로퓨란(THF, 10 mL)에 용해시키고 0 ℃ 상태에서 N-브로소숙신이미드(NBS, 0.24 g, 1.35 mmol)를 첨가하였다. 그 후, 상온까지 서서히 가열하여 24시간 동안 교반한 다음, 상기 혼합물에 증류수(5 mL)로 반응을 종결하였다. 다음으로 상기 혼합물을 메틸렌클로라이드(MC, 15 mL)로 추출하고, 추출한 유기층을 감압농축시켰다. 농축된 상기 혼합물을 관크로마토그래피(실리카겔; 에틸아세테이트/헥산=1/8 (v:v))로 정제하여 목적화합물 (3a) 또는 (3b)(3a:0.28 g, 51 %; 3b: 0.41 g, 55.6 %)을 얻었다.4,4-dihexyl-4H-cyclopenta [1,2-b: 5,4-b '] dithiophene-2-carbaldehyde 14a (0.45 g, 1.20 mmol) prepared in step 6 or (14b) (0.65 g, 1.20 mmol) was dissolved in tetrahydrofuran (THF, 20 mL) and tetrahydrofuran 10 mL) and N-bromosuccinimide (NBS, 0.24 g, 1.35 mmol) was added at 0 ° C. Thereafter, the mixture was slowly heated to room temperature and stirred for 24 hours, and then the reaction was terminated with distilled water (5 mL). Next, the mixture was extracted with methylene chloride (MC, 15 mL), and the extracted organic layer was concentrated under reduced pressure. The concentrated mixture was purified by column chromatography (silica gel; ethyl acetate / hexane = 1/8 (v: v)) to obtain the desired compound (3a) or (3b) (3a: 0.28 g, 51% , 55.6%).
화합물 (3a): 1H NMR (300MHz, CDCl3), δ(ppm): 9.84(s, 1H), 7.56(s, 1H), 7.01(s, 1H), 1.87-1.85(m, 4H), 1.26-1.12(m, 16H), 0.91-0.81(m, 6H);Compound (3a): 1 H NMR ( 300MHz, CDCl 3), δ (ppm): 9.84 (s, 1H), 7.56 (s, 1H), 7.01 (s, 1H), 1.87-1.85 (m, 4H), 1.26-1.12 (m, 16H), 0.91-0.81 (m, 6H);
EI-MS. clad. for C22H29BrOS2 : 454.08 (found : 454).
EI-MS. clad. for C 22 H 29 BrOS 2 : 454.08 (found: 454).
화합물 (3b): 1H NMR (300MHz, CDCl3), δ(ppm): 9.83(s, 1H), 7.55(s, 1H), 7.00(s, 1H), 1.83-1.79(m, 4H), 1.26-1.13(m, 40H), 0.91-0.81(m, 6H);Compound (3b): 1 H NMR ( 300MHz, CDCl 3), δ (ppm): 9.83 (s, 1H), 7.55 (s, 1H), 7.00 (s, 1H), 1.83-1.79 (m, 4H), 1.26-1.13 (m, 40H), 0.91-0.81 (m, 6H);
EI-MS. clad. for C34H53BrOS2 : 622.27 (found : 622).
EI-MS. clad. for C 34 H 53 BrOS 2 : 622.27 (found: 622).
<< 실시예Example 1> (E)-3-(6-(4-(비스(9,9-디메틸-9H-플루오렌-2-일)아미노)페닐)-4,4-디헥실-4H- (E) -3- (6- (4- (Bis (9,9-dimethyl-9H-fluoren-2-yl) amino) phenyl) -4,4-dihexyl- 사이클로펜타[1,2-b:5,4-b']디티오펜Cyclopenta [1,2-b: 5,4-b '] dithiophene -2-일)-2-Yl) -2- 시아노아크릴산의Of cyanoacrylic acid 제조(화합물 1a) Preparation (Compound 1a)
단계 1: 6-(4-(Step 1: 6- (4- ( 비스(9,9-디메틸-9H-플루오렌-2-일)아미노Bis (9,9-dimethyl-9H-fluoren-2-yl) amino )) 페닐Phenyl )-4,4-) -4,4- 디헥실Dihexyl -4H-사-4H-4 이클로펜타[1,2-b:5,4-b']디티오Cyclopenta [1,2-b: 5,4-b '] dithio 펜-2-Pen-2- 카르발데히드의Carbaldehyde 제조(화합물 4a) Preparation (Compound 4a)
상기 제조예 1에서 제조된 N-(9,9-디메틸-9H-플루오렌-2-일)-9,9-디메틸-N-(4-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-일)페닐)-9H-플루오렌-2-아민 (2)(0.35 g, 0.58 mmol), 상기 제조예 2에서 제조된 6-브로모-4,4-디헥실-4H-사이클로펜타[1,2-b:5,4-b']디티오펜-2-카르발데히드 (3a)(0.26 g, 0.58 mmol) 및 테트라키스트리페닐포스핀팔라듐(Pd(PPh3)4, 67.4 mg, 0.058 mmol)을 무수 테트라히드로퓨란(THF, 6 mL)에 용해시키고, 2M의 포타슘카보네이트 수용액(1 mL)을 첨가하였다. 20분 동안 충분히 가스를 제거해주고 환류 상태에서 24시간 동안 교반하였다. 반응이 종결되면 상온으로 냉각시키고 메틸렌클로라이드(MC, 15 mL)로 추출하여 추출된유기층을 감압농축시켰다. 농축된 상기 혼합물을 관크로마토그래피(실리카겔; 에틸아세테이트/헥산=1/8 (v:v))로 정제하여 목적화합물 (4a)(0.25 g, 53.8 %)을 얻었다.(9,9-dimethyl-9H-fluoren-2-yl) -9,9-dimethyl-N- (4- (4,4,5,5-tetramethyl- Yl) phenyl) -9H-fluorene-2-amine (2) (0.35 g, 0.58 mmol) and 6-bromo- , 4-dihexyl-4H-cyclopenta [1,2-b: 5,4-b '] dithiophene-2-carbaldehyde 3a (0.26 g, 0.58 mmol) and tetrakistriphenylphosphine palladium a (Pd (PPh 3) 4, 67.4 mg, 0.058 mmol) in anhydrous tetrahydrofuran (THF, 6 mL), potassium carbonate solution (1 mL) was dissolved in a 2M was added. The gas was sufficiently removed for 20 minutes and stirred at reflux for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, extracted with methylene chloride (MC, 15 mL), and the extracted organic layer was concentrated under reduced pressure. The concentrated mixture was purified by column chromatography (silica gel; ethyl acetate / hexane = 1/8 (v: v)) to give the desired compound (4a) (0.25 g, 53.8%).
1H NMR (300MHz, CDCl3), δ(ppm): 9.82(s, 1H), 7.67(d, J=7.5, 4H), 7.60-7.55(m, 3H), 7.52-7.29(m, 6H), 7.25-7.10(m, 7H), 1.89-1.85(m, 4H), 1.42(s, 12H), 1.26-1.12(m, 16H), 0.95-0.81(m, 6H); 1 H NMR (300MHz, CDCl 3 ), δ (ppm): 9.82 (s, 1H), 7.67 (d, J = 7.5, 4H), 7.60-7.55 (m, 3H), 7.52-7.29 (m, 6H) , 7.25-7.10 (m, 7H), 1.89-1.85 (m, 4H), 1.42 (s, 12H), 1.26-1.12 (m, 16H), 0.95-0.81 (m, 6H);
EI-MS. clad. for C58H59NOS2 : 849.40 (found : 849).
EI-MS. clad. for C 58 H 59 NOS 2 : 849.40 (found: 849).
단계 2: (E)-3-(6-(4-(Step 2: (E) -3- (6- (4- ( 비스(9,9-디메틸-9H-플루오렌-2-일)아미노Bis (9,9-dimethyl-9H-fluoren-2-yl) amino )) 페닐Phenyl )-4,4-디헥실-4H-) -4,4-dihexyl-4H- 사이클로펜타[1,2-b:5,4-b']디티오펜Cyclopenta [1,2-b: 5,4-b '] dithiophene -2-일)-2-Yl) -2- 시아노아크릴산의Of cyanoacrylic acid 제조(화합물 1a) Preparation (Compound 1a)
상기 단계 1에서 제조된 6-(4-(비스(9,9-디메틸-9H-플루오렌-2-일)아미노)페닐)-4,4-디헥실-4H-사이클로펜타[1,2-b:5,4-b']디티오펜-2-카르발데히드 (4a)(70 mg, 0.08 mmol)를 클로로포름(5 mL)에 용해시킨 다음, 시아노아세트산(21 mg, 0.24 mmol) 및 피페리딘(55.3uL, 0.56 mmol)을 첨가하고, 환류 상태에서 24시간 동안 교반시켰다. 반응이 종결되면 상온으로 냉각시키고 용매를 감압농축시켰다. 농축된 상기 혼합물을 관크로마토그래피(실리카겔; 메틸렌클로라이드/메탄올=1/15 (v:v))로 정제하여, 목적화합물 (1a)(30 mg, 40 %)을 얻었다.(9,9-dimethyl-9H-fluoren-2-yl) amino) phenyl) -4,4-dihexyl-4H-cyclopenta [ b) 5,4-b '] dithiophene-2-carbaldehyde 4a (70 mg, 0.08 mmol) was dissolved in chloroform (5 mL) and then cyanoacetic acid (21 mg, 0.24 mmol) (55.3 uL, 0.56 mmol) were added and stirred at reflux for 24 hours. When the reaction was completed, the reaction mixture was cooled to room temperature and the solvent was concentrated under reduced pressure. The concentrated mixture was purified by column chromatography (silica gel; methylene chloride / methanol = 1/15 (v: v)) to obtain the desired compound (1a) (30 mg, 40%).
1H NMR (300MHz, CDCl3), δ(ppm): 8.24(s, 1H), 7.77-7.72(m, 5H), 7.64(d, J=8.5, 2H), 7.56(s, 1H), 7.51(d, J=6.9, 2H), 7.31-7.26(m, 6H), 7.11(d, J=8.5, 2H), 7.05(d, J=8.1, 2H), 1.89-1.85(m, 4H), 1.42(s, 12H), 1.26-1.12(m, 16H), 0.95-0.81(m, 6H); 1 H NMR (300MHz, CDCl 3 ), δ (ppm): 8.24 (s, 1H), 7.77-7.72 (m, 5H), 7.64 (d, J = 8.5, 2H), 7.56 (s, 1H), 7.51 (d, J = 6.9, 2H ), 7.31-7.26 (m, 6H), 7.11 (d, J = 8.5, 2H), 7.05 (d, J = 8.1, 2H), 1.89-1.85 (m, 4H), 1.42 (s, 12H), 1.26-1.12 (m, 16H), 0.95-0.81 (m, 6H);
EI-MS. clad. for C61H60N2O2S2 : 916.41 (found : 917).
EI-MS. clad. for C61H 60 N 2 O 2 S 2 : 916.41 (found: 917).
<< 실시예Example 2> (E)-3-(6-(4-(비스(9,9-디메틸-9H-플루오렌-2-일)아미노)페닐)-4,4-디 2) (E) -3- (6- (4- (Bis (9,9-dimethyl-9H- fluoren- 도Degree 데실-4H-Decyl-4H- 사이클로펜타[1,2-b:5,4-b']디티오펜Cyclopenta [1,2-b: 5,4-b '] dithiophene -2-일)-2-Yl) -2- 시아노아크릴산의Of cyanoacrylic acid 제조(화합물 1b) Preparation (Compound 1b)
단계 1: 6-(4-(Step 1: 6- (4- ( 비스(9,9-디메틸-9H-플루오렌-2-일)아미노Bis (9,9-dimethyl-9H-fluoren-2-yl) amino )) 페닐Phenyl )-4,4-) -4,4- 디도데Didod 실-4H-Sil-4H- 사이클로펜타[1,2-b:5,4-b']디티오펜Cyclopenta [1,2-b: 5,4-b '] dithiophene -2--2- 카르발데히드의Carbaldehyde 제조(화합물 4b) Preparation (Compound 4b)
상기 실시예 1의 단계 1에서 6-브로모-4,4-디헥실-4H-사이클로펜타[1,2-b:5,4-b']디티오펜-2-카르발데히드 (3a) 대신에 6-브로모-4,4-디헥실-4H-사이클로펜타[1,2-b:5,4-b']디티오펜-2-카르발데히드 (3b)를 사용한 것을 제외하고, 상기 실시예 1과 동일한 방법으로 수행하여 목적화합물 (4b)(0.55 g, 53 %)를 얻었다.
Instead of 6-bromo-4,4-dihexyl-4H-cyclopenta [1,2-b: 5,4-b '] dithiophene-2-carbaldehyde (3a) Except that 6-bromo-4,4-dihexyl-4H-cyclopenta [1,2-b: 5,4-b '] dithiophene-2-carbaldehyde (3b) The objective compound (4b) (0.55 g, 53%) was obtained by carrying out the same processes as in Example 1.
1H NMR (300MHz, CDCl3), δ(ppm): 9.81(s, 1H), 7.67(d, J=7.2, 2H), 7.62(d, J=8.1, 2H) 7.55-7.52(m, 3H), 7.41-7.24(m, 8H), 7.21(d, J=8.3, 2H), 7.16(s, 1H), 7.13(d, J=8.1, 2H)(m, 4H), 1.89-1.87(m, 4H), 1.42(s, 12H), 1.25-1.14(m, 40H), 0.95-0.86(m, 6H); 1 H NMR (300MHz, CDCl 3 ), δ (ppm): 9.81 (s, 1H), 7.67 (d, J = 7.2, 2H), 7.62 (d, J = 8.1, 2H) 7.55-7.52 (m, 3H ), 7.41-7.24 (m, 8H) , 7.21 (d, J = 8.3, 2H), 7.16 (s, 1H), 7.13 (d, J = 8.1, 2H) (m, 4H), 1.89-1.87 (m , 4H), 1.42 (s, 12H), 1.25-1.14 (m, 40H), 0.95-0.86 (m, 6H);
EI-MS. clad. for C70H83NOS2 : 1017.59 (found : 1017.5).
EI-MS. clad. for C 70 H 83 NOS 2 : 1017.59 (found: 1017.5).
단계 2: (E)-3-(6-(4-(Step 2: (E) -3- (6- (4- ( 비스(9,9-디메틸-9H-플루오렌-2-일)아미노Bis (9,9-dimethyl-9H-fluoren-2-yl) amino )) 페닐Phenyl )-4,4-디) -4,4-di 도Degree 데실-4H-Decyl-4H- 사이클로펜타[1,2-b:5,4-b']디티오펜Cyclopenta [1,2-b: 5,4-b '] dithiophene -2-일)-2-Yl) -2- 시아노아크릴산의Of cyanoacrylic acid 제조(화합물 1b) Preparation (Compound 1b)
상기 실시예 1의 단계 2에서 6-(4-(비스(9,9-디메틸-9H-플루오렌-2-일)아미노)페닐)-4,4-디헥실-4H-사이클로펜타[1,2-b:5,4-b']디티오펜-2-카르발데히드 (4a) 대신에 6-(4-(비스(9,9-디메틸-9H-플루오렌-2-일)아미노)페닐)-4,4-디도데실-4H-사이클로펜타[1,2-b:5,4-b']디티오펜-2-카르발데히드 (4b)를 사용한 것을 제외하고, 상기 실시예 1의 단계 2와 동일한 방법으로 수행하여 목적화합물 (1b)(0.33 g, 56.3 %)를 얻었다.Phenyl) -4,4-dihexyl-4H-cyclopenta [1, < / RTI > 2-b: 5,4-b '] dithiophene-2-carbaldehyde (4a) ) -4,4-butadecyl-4H-cyclopenta [1,2-b: 5,4-b '] dithiophene-2-carbaldehyde (4b) 2, the title compound (1b) (0.33 g, 56.3%) was obtained.
1H NMR (300MHz, CDCl3), δ(ppm): 8.30(s, 1H), 7.65(d, J=7.2, 2H), 7.61(d, J=8.1, 2H), 7.56(s, 1H), 7.51(d, J=8.4, 2H), 7.41-7.38(m, 2H), 7.31(s, 1H), 7.27-7.24(m, 5H), 7.18(s, 1H), 7.15-7.14(m, 2H), 7.11(d, J=8.1, 2H), 1.89-1.87(m, 4H), 1.42(s, 12H), 1.25-1.14(m, 40H), 0.95-0.86(m, 6H) 1 H NMR (300MHz, CDCl 3 ), δ (ppm): 8.30 (s, 1H), 7.65 (d, J = 7.2, 2H), 7.61 (d, J = 8.1, 2H), 7.56 (s, 1H) , 7.51 (d, J = 8.4, 2H), 7.41-7.38 (m, 2H), 7.31 (s, 1H), 7.27-7.24 2H), 7.11 (d, J = 8.1, 2H), 1.89-1.87 (m, 4H), 1.42 (s, 12H), 1.25-1.14 (m, 40H), 0.95-0.86 (m, 6H)
EI-MS. clad. for C73H84N2O2S2 : 1084.60, found : 1084.6
EI-MS. clad. for C 73 H 84 N 2 O 2 S 2 : 1084.60, found: 1084.6
<< 실시예Example 3> 3> 사이클로펜타디티오펜Cyclopentadithiophene 유도체를 유기염료로 사용한 염료감응 태양전지의 제조 - 1 Preparation of Dye-Sensitized Solar Cells Using Derivatives as Organic Dyes - 1
단계 1: 작업 전극의 제조Step 1: Manufacture of working electrode
FTO 글라스(Florine-doped tin oxide coated conduction glass)를 2 ㎝×1.5 ㎝ 크기로 잘라 글라스 세정 세제로 10분간 초음파 분해 세척을 한 후 증류수를 사용하여 비눗물을 완전히 제거하였다. 그 후에 에탄올로 초음파 분해 세척을 20분간 2회 반복하고, 무수 에탄올로 완전히 헹군 후에 100 ℃ 오븐에서 건조시켜, FTO 글라스를 준비하였다.FTO glass (fluorine-doped tin oxide coated conduction glass) was cut into a size of 2 cm x 1.5 cm, and was washed with a glass washing detergent for 10 minutes, and then washed with distilled water to completely remove the soapy water. Thereafter, ultrasonic washing with ethanol was repeated twice for 20 minutes, completely rinsed with anhydrous ethanol, and then dried in an oven at 100 ° C to prepare an FTO glass.
상기에서 준비한 FTO 글라스 위에 TiO2 분말과의 접촉력을 향상시키기 위하여 70 ℃의 0.04 M TiCl4 용액에 30분간 담근 후 증류수로 세정한 후, 100 ℃ 오븐에서 수분을 완전히 건조시켜, TiCl4 처리된 FTO 글라스를 준비하였다.After soaking 0.04 M TiCl of 70 ℃ 30 minutes at 4 solution in order to improve the contact force of the TiO 2 powder on the FTO glass prepared in the above was washed with distilled water and completely dry the water at 100 ℃ oven, TiCl 4 processed FTO Glass was prepared.
상기에서 준비한 TiCl4 처리된 FTO 글라스 상에 자체 제작한 TiO2 페이스트를 스크린 프린팅하여, 11 ㎛ 두께의 TiO2 투명층이 코팅된 FTO 글라스를 준비하였다.A self-made TiO 2 paste on the TiCl 4 -treated FTO glass prepared above was screen printed to prepare an FTO glass coated with a TiO 2 transparent layer having a thickness of 11 μm.
상기 TiO2 투명층이 코팅된 FTO 글라스를 125 ℃ 오븐에서 30분 동안 건조시키는 과정을 3회 반복하였다.The process of drying the FTO glass coated with the TiO 2 transparent layer in an oven at 125 ° C for 30 minutes was repeated three times.
이어서, 상기 TiO2 투명층 상에 광산란을 위해 다른 페이스트(400 nm, PST-400C, 일본 CCIC사)를 스크린 프린팅하여 5 ㎛ 두께의 광산란층을 코팅하였다.Next, another paste (400 nm, PST-400C, manufactured by CCIC, Japan) was screen-printed on the TiO 2 transparent layer for light scattering to coat a light scattering layer having a thickness of 5 μm.
상기 광산란층이 코팅된 FTO 글라스를 125 ℃에서 10분, 350 ℃에서 5분, 375 ℃에서 5분, 450 ℃에서 20분, 500 ℃에서 10분간 소결하고 상온으로 서서히 식혔다.The FTO glass coated with the light scattering layer was sintered at 125 캜 for 10 minutes, at 350 캜 for 5 minutes, at 375 캜 for 5 minutes, at 450 캜 for 20 minutes, and at 500 캜 for 10 minutes, and gradually cooled to room temperature.
상기 소결을 거친 FTO 글라스를 70 ℃의 0.1 M TiCl4 용액에 30분간 담근 후 증류수로 세정하고, 450 ℃에서 20분, 500 ℃에서 10분간 소결하고 80 ℃까지 서서히 식혔다.The sintered FTO glass was immersed in a 0.1 M TiCl 4 solution at 70 ° C for 30 minutes, washed with distilled water, sintered at 450 ° C for 20 minutes, at 500 ° C for 10 minutes, and gradually cooled to 80 ° C.
상기의 과정들을 거친 FTO 글라스를, TBA·ACN(1:1) 혼합용매 또는 MC 용매에 실시예 1에서 제조한 염료를 첨가하여 0.3 mM 농도로 준비한 용액에 24시간 동안 함침시켜 염료가 흡착된 작업 전극을 제조하였다.
The above FTO glass was impregnated in a solution prepared in the concentration of 0.3 mM for 24 hours by adding the dye prepared in Example 1 to a TBA · ACN (1: 1) mixed solvent or MC solvent, Electrode.
단계 2: 상대 전극의 제조Step 2: Preparation of counter electrode
2 ㎝×1.5 ㎝ 크기의 FTO 글라스에 Φ0.7 mm 다이아몬드 드릴을 이용해서 전해질이 들어갈 구멍을 두 개 뚫었다. 그 후에 작업 전극에서 제시했던 세척 방법과 동일한 방법으로 세척한 후 건조시켰다. 다음으로, 하이드로겐 헥사클로로플라티네이트(H2PtCl6)2-프로판올 용액을 FTO 글라스에 입힌 후 450 ℃에서 60분간 소결시켜 상대 전극을 제조하였다.
Two holes were drilled into a 2 cm x 1.5 cm sized FTO glass using a Φ0.7 mm diamond drill to enter the electrolyte. After that, it was washed and dried in the same manner as the cleaning method suggested in the working electrode. Next, a solution of hydrogen hexachloroplatinate (H 2 PtCl 6 ) 2-propanol was coated on an FTO glass and sintered at 450 ° C. for 60 minutes to prepare a counter electrode.
단계 3: 고체형 염료감응 태양전지의 제조Step 3: Preparation of solid-state dye-sensitized solar cell
FTO 글라스(Florine-doped tin oxide coated conduction glass)를 2.5 cm × 2.5 cm 크기로 잘라 HCl:D.I. water(1:2)의 혼합액과 아연 분말(zinc powder)를 사용한 식각법을 통해 전극 모양을 제조하였다. 그 후 아세톤과 에탄올로 초음파 세척을 20분간 반복하고 건조시켰다. 세척된 FTO 글라스를 자외선 오존장치에 15분간 넣어 남아있는 잔여 유기물들을 제거하여 표면 상태를 깨끗하게 처리하였다. The FTO glass was cut into 2.5 cm × 2.5 cm HCl: D.I. water (1: 2) mixture and zinc powder were used to fabricate electrodes. Then, ultrasonic cleaning with acetone and ethanol was repeated for 20 minutes and dried. The cleaned FTO glass was placed in an ultraviolet ozone apparatus for 15 minutes to remove the remaining organic matters to clean the surface state.
상기에서 준비한 FTO 글라스 기판 위에 0.15M의 농도로 티타늄디이소프로폭사이드비스(아세틸아세토네이트)(titanium diisopropoxide bis(acetylacetonate))를 부탄올 용매에 첨가하여 만든 용액을 스핀 코팅법을 이용하여 조밀한 TiO2층을 코팅하였다.A solution prepared by adding titanium diisopropoxide bis (acetylacetonate) (titanium acetic acid) (bis (acetylacetonate)) to the above prepared FTO glass substrate at a concentration of 0.15 M to the butanol solvent was spin- Two layers were coated.
상기 조밀한 TiO2층이 코팅된 FTO 글라스 기판 위에 자체 제작한 TiO2 페이스트와 α-terpineol을 섞어 희석시킨 TiO2 paste(20 nm)를 스핀 코팅법을 이용하여 약 2 ㎛ 두께의 TiO2 층을 코팅하였다.On the FTO glass substrate coated with the dense TiO 2 layer, a TiO 2 paste (20 nm) diluted by mixing a self-made TiO 2 paste and α-terpineol was applied by spin coating to a 2 μm thick TiO 2 Lt; / RTI >
상기 TiO2층이 코팅된 FTO 글라스 기판을 125 ℃에서 10분, 350 ℃에서 5분, 375 ℃에서 5분, 450 ℃에서 20분, 500 ℃에서 10분간 소결하고 상온으로 서서히 식혔다.The FTO glass substrate coated with the TiO 2 layer was sintered at 125 ° C for 10 minutes, at 350 ° C for 5 minutes, at 375 ° C for 5 minutes, at 450 ° C for 20 minutes, at 500 ° C for 10 minutes, and slowly cooled to room temperature.
상기 소결을 거친 FTO 글라스를 0.04 M TiCl4 용액에 담근 후 70 ℃ 오븐에서 30분 처리한 후 증류수로 세정하고, 500 ℃에서 15분간 소결하고 80 ℃까지 서서히 식혔다.The sintered FTO glass was immersed in a 0.04 M TiCl 4 solution, treated in an oven at 70 ° C for 30 minutes, washed with distilled water, sintered at 500 ° C for 15 minutes, and gradually cooled to 80 ° C.
상기의 과정들을 거친 FTO 글라스 기판을 TBAACN(1:1) 혼합용매 또는 MC 용매에 실시예 1에서 제조한 염료를 첨가하여 0.3 mM 농도로 준비한 용액에 24시간 동안 함침시켜 염료를 흡착시켰다.The FTO glass substrate thus processed was impregnated with a dye prepared in Example 1 in a TBAACN (1: 1) mixed solvent or MC solvent at a concentration of 0.3 mM for 24 hours to adsorb the dye.
상기 염료가 흡착된 FTO 글라스 기판 위에 홀 전도체 물질을 코팅하기 위해 미리 홀 전도체 물질인 스파이로-OMeTAD(spiro-OMeTAD, 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenyl- amine)-9,9'-spirobifluorene)를 클로로벤젠 용매에 첨가하여 0.14M 농도의 용액을 만들고 0.11 M 농도의 4-tert-부틸피리미딘(4-tert-butylpyridine, TBP)와 21 mM 농도의 리튬비스-(트리플루오로메틸술포닐)이미드(lithium bis- (trifluoromethylsulfonyl)imide, LiTFSI)를 첨가하였다. To form a hole conductor material on the dye-adsorbed FTO glass substrate, a hole conductor material spiro-OMeTAD (2,2 ', 7,7'-tetrakis (N, N-di- methoxyphenyl-amine) -9,9'-spirobifluorene was added to a chlorobenzene solvent to prepare a 0.14 M solution, and 4-tert-butylpyridine (TBP) and a 21 mM concentration Of lithium bis- (trifluoromethylsulfonyl) imide (LiTFSI) was added to the reaction mixture.
상기 준비된 홀 전도체 용액을 염료가 흡착된 FTO 글라스 기판 위에 떨어뜨린 후 TiO2 공극 사이로 잘 들어갈 수 있게 1분 정도 두었다가 2000 rpm의 속도로 30초 동안 스핀 코팅하여 코팅시켰다.The prepared hole conductor solution was dropped on the FTO glass substrate on which the dye was adsorbed, and then allowed to stand for one minute so that it could enter the gap between the TiO 2 wells. Then, the coating was applied by spin coating at a rate of 2000 rpm for 30 seconds.
상기의 홀 전도체가 코팅된 FTO 글라스 기판을 고 진공상태(10-6 torr)의 증착기에 넣고 150 nm 두께의 은(silver)을 증착하여 고체형 염료감응 태양전지를 제조하였다.
The above-mentioned FTO glass substrate coated with the hole conductor was placed in a high vacuum (10 -6 torr) evaporator, and 150 nm thick silver was deposited thereon to prepare a solid dye-sensitized solar cell.
<< 실시예Example 4> 4> 사이클로펜타디티오펜Cyclopentadithiophene 유도체를 염료로 사용한 염료감응 태양전지의 제조 - 2 Preparation of dye-sensitized solar cell using derivative as dye - 2
실시예 1에서 제조된 사이클로펜타디티오펜 유도체를 사용하는 대신에 실시예 2에서 제조된 사이클로펜타디티오펜 유도체를 염료로 사용하는 것을 제외하고 상기 실시예 3과 동일한 방법으로 수행하여 염료감응 태양전지를 제조하였다.
A dye-sensitized solar cell was prepared in the same manner as in Example 3, except that the cyclopentadithiophene derivative prepared in Example 2 was used as a dye instead of using the cyclopentadithiophene derivative prepared in Example 1, .
<< 실시예Example 5> 5> 사이클로펜타디티오펜Cyclopentadithiophene 유도체를 유기염료로 사용한 염료감응 태양전지의 제조 - 3 Preparation of dye-sensitized solar cell using derivative as organic dye - 3
단계 1: 작업 전극의 제조Step 1: Manufacture of working electrode
FTO 글라스(Florine-doped tin oxide coated conduction glass, 모델명, 제조사)를 2 ㎝×1.5 ㎝ 크기로 잘라 글라스 세정 세제로 10분간 초음파 분해 세척을 한 후 증류수를 사용하여 비눗물을 완전히 제거하였다. 그 후에 에탄올로 초음파 분해 세척을 20분간 2회 반복하고, 무수 에탄올로 완전히 헹군 후에 100 ℃ 오븐에서 건조시켜, FTO 글라스를 준비하였다.FTO glass (model name, manufacturer) was cut into 2 cm x 1.5 cm size, and then washed with a glass washing detergent for 10 minutes, and then washed with distilled water to completely remove the soapy water. Thereafter, ultrasonic washing with ethanol was repeated twice for 20 minutes, completely rinsed with anhydrous ethanol, and then dried in an oven at 100 ° C to prepare an FTO glass.
상기에서 준비한 FTO 글라스 위에 TiO2 분말과의 접촉력을 향상시키기 위하여 70 ℃의 0.04 M TiCl4 용액에 30분간 담근 후 증류수로 세정한 후, 100 ℃ 오븐에서 수분을 완전히 건조시켜, TiCl4 처리된 FTO 글라스를 준비하였다.After soaking 0.04 M TiCl of 70 ℃ 30 minutes at 4 solution in order to improve the contact force of the TiO 2 powder on the FTO glass prepared in the above was washed with distilled water and completely dry the water at 100 ℃ oven, TiCl 4 processed FTO Glass was prepared.
상기에서 준비한 TiCl4 처리된 FTO 글라스 상에 자체 제작한 TiO2 페이스트를 스크린 프린팅하여, 11 ㎛ 두께의 TiO2 투명층이 코팅된 FTO 글라스를 준비하였다.A self-made TiO 2 paste on the TiCl 4 -treated FTO glass prepared above was screen printed to prepare an FTO glass coated with a TiO 2 transparent layer having a thickness of 11 μm.
상기 TiO2 투명층이 코팅된 FTO 글라스를 125 ℃오븐에서 30분 동안 건조시키는 과정을 3회 반복하였다.The process of drying the FTO glass coated with the TiO 2 transparent layer in an oven at 125 ° C for 30 minutes was repeated three times.
이어서, 상기 TiO2 투명층 상에 광산란을 위해 다른 페이스트(400 nm, PST-400C, 일본 CCIC사)를 스크린 프린팅하여 5 ㎛ 두께의 광산란층을 코팅하였다.Next, another paste (400 nm, PST-400C, manufactured by CCIC, Japan) was screen-printed on the TiO 2 transparent layer for light scattering to coat a light scattering layer having a thickness of 5 μm.
상기 광산란층이 코팅된 FTO 글라스를 125 ℃에서 10분, 350 ℃에서 5분, 375 ℃에서 5분, 450 ℃에서 20분, 500 ℃에서 10분간 소결하고 상온으로 서서히 식혔다.The FTO glass coated with the light scattering layer was sintered at 125 캜 for 10 minutes, at 350 캜 for 5 minutes, at 375 캜 for 5 minutes, at 450 캜 for 20 minutes, and at 500 캜 for 10 minutes, and gradually cooled to room temperature.
상기 소결을 거친 FTO 글라스를 70 ℃의 0.1 M TiCl4 용액에 30분간 담근 후 증류수로 세정하고, 450 ℃에서 20분, 500 ℃에서 10분간 소결하고 80 ℃까지 서서히 식혔다.The sintered FTO glass was immersed in a 0.1 M TiCl 4 solution at 70 ° C for 30 minutes, washed with distilled water, sintered at 450 ° C for 20 minutes, at 500 ° C for 10 minutes, and gradually cooled to 80 ° C.
상기의 과정들을 거친 FTO 글라스를, TBA·ACN(1:1) 혼합용매 또는 MC 용매에 실시예 1에서 제조한 염료를 첨가하여 0.3 mM 농도로 준비한 용액에 24시간 동안 함침시켜 염료가 흡착된 작업 전극을 제조하였다.
The above FTO glass was impregnated in a solution prepared in the concentration of 0.3 mM for 24 hours by adding the dye prepared in Example 1 to a TBA · ACN (1: 1) mixed solvent or MC solvent, Electrode.
단계 2: 상대 전극의 제조Step 2: Preparation of counter electrode
2 ㎝×1.5 ㎝ 크기의 FTO 글라스에 Φ0.7 mm 다이아몬드 드릴을 이용해서 전해질이 들어갈 구멍을 두 개 뚫었다. 그 후에 작업 전극에서 제시했던 세척 방법과 동일한 방법으로 세척한 후 건조시켰다. 다음으로, 하이드로겐 헥사클로로플라티네이트(H2PtCl6)2-프로판올 용액을 FTO 글라스에 입힌 후 450 ℃에서 60분간 소결시켜 상대 전극을 제조하였다.
Two holes were drilled into a 2 cm x 1.5 cm sized FTO glass using a Φ0.7 mm diamond drill to enter the electrolyte. After that, it was washed and dried in the same manner as the cleaning method suggested in the working electrode. Next, a solution of hydrogen hexachloroplatinate (H 2 PtCl 6 ) 2-propanol was coated on an FTO glass and sintered at 450 ° C. for 60 minutes to prepare a counter electrode.
단계 3: 전해질의 제조Step 3: Preparation of electrolyte
MPN 용매 1.0 ml에 5 중량% PVH70 (Poly(vinylidenefluoride-co-hexafluoropropylene))을 첨가하고, 상온에서 교반한 다음, 0.1M I2, 0.5 M NMBI 및 0.6 M IL-DMPII를 첨가하고 하룻밤 동안 교반하여 PVH70 전해질을 제조하였다.
Was added to 5 wt% PVH70 (Poly (vinylidenefluoride- co -hexafluoropropylene )) in 1.0 ml solvent, MPN, and the addition of stirring at room temperature, 0.1MI 2, 0.5 M NMBI and 0.6 M IL-DMPII and stirred overnight to PVH70 Electrolyte was prepared.
단계 4: 염료감응 태양전지의 제조Step 4: Preparation of dye-sensitized solar cell
상기 단계 1에서 제조한 작업 전극과 단계 2에서 제조한 상대 전극 사이에 사각형 띠 모양으로 자른 슈린(Surlyn, SX1170-25 Hot Melt)을 놓고, 상기 두 전극을 클립으로 고정시킨 다음, 100 ℃ 오븐을 이용하여 두 전극을 서로 붙였다. 다음으로, 상대 전극에 있는 2개의 작은 구멍을 통해 상기 단계 3에서 제조한 전해질을 주입한 후 슈린 스티립과 커버 글라스로 실링하여 염료감응 태양전지를 제작하였다.
A Surlyn (SX1170-25 Hot Melt) cut in a rectangular band shape was placed between the working electrode prepared in Step 1 and the counter electrode prepared in Step 2, the two electrodes were fixed with a clip, The two electrodes were stuck together. Next, the electrolyte prepared in step 3 was injected through two small holes in the counter electrode, and then sealed with a shurin stiff and a cover glass to prepare a dye-sensitized solar cell.
<< 실시예Example 6> 6> 사이클로펜타디티오펜Cyclopentadithiophene 유도체를 유기염료로 사용한 염료감응 태양전지의 제조 - 4 Preparation of Dye-Sensitized Solar Cells Using Derivatives as Organic Dyes - 4
실시예 1에서 제조된 사이클로펜타디티오펜 유도체를 사용하는 대신에 실시예 2에서 제조된 사이클로펜타디티오펜 유도체를 염료로 사용하는 것을 제외하고 상기 실시예 5과 동일한 방법으로 수행하여 염료감응 태양전지를 제조하였다.
A dye sensitized solar cell was prepared in the same manner as in Example 5 except that the cyclopentadithiophene derivative prepared in Example 2 was used as a dye instead of the cyclopentadithiophene derivative prepared in Example 1, .
<< 비교예Comparative Example 1> 1> Z907Z907 을 염료로 사용한 염료감응 태양전지의 제조-1Preparation of dye-sensitized solar cell using dye as a dye-1
실시예 1에서 제조된 사이클로펜타디티오펜 유도체 대신에 상기 Z907(Solaronix사의 Ruthenizer 520-DN)을 염료로 사용하는 것을 제외하고 상기 실시예 3과 동일한 방법으로 수행하여 염료감응 태양전지를 제조하였다.
A dye-sensitized solar cell was prepared in the same manner as in Example 3 except that Z907 (Ruthenizer 520-DN from Solaronix) was used as a dye in place of the cyclopentadithiophene derivative prepared in Example 1.
<< 비교예Comparative Example 2> 2> Z907Z907 을 염료로 사용한 염료감응 태양전지의 제조-2Preparation of dye-sensitized solar cell using dye as a dye-2
실시예 1에서 제조된 사이클로펜타디티오펜 유도체 대신에 상기 Z907(Solaronix사의 Ruthenizer 520-DN)을 염료로 사용하는 것을 제외하고 상기 실시예 5와 동일한 방법으로 수행하여 염료감응 태양전지를 제조하였다.
A dye-sensitized solar cell was prepared in the same manner as in Example 5 except that the Z907 (Ruthenizer 520-DN from Solaronix) was used as a dye in place of the cyclopentadithiophene derivative prepared in Example 1.
<< 실험예Experimental Example 1> 고체상 전해질에서의 태양전지의 물리적 특성 평가 1> Evaluation of Physical Properties of Solar Cell in Solid State Electrolyte
전해질로서, 고체상 전해질을 사용하고, 본 발명에 따른 사이클로펜타디티오펜 유도체를 염료로 사용하여 제조된 태양 전지의 물리적 특성을 평가하기 위해 다음과 같이 실험을 수행하였다.
The following experiment was conducted to evaluate the physical properties of a solar cell produced using a solid electrolyte as an electrolyte and a cyclopentadithiophene derivative according to the present invention as a dye.
전해질로서, 고체상 전해질을 이용한 본 발명에 따른 실시예 3, 실시예 4 및 비교예 1에서 제조된 태양전지의 개방전압, 단회로 광전류 밀도, 충전인자 및 광전변환효율의 물리적 특성을 측정하여 하기 표 1에 나타내었다.
The physical properties of the open-circuit voltage, single-photocurrent density, charge factor and photoelectric conversion efficiency of the solar cell prepared in Example 3, Example 4 and Comparative Example 1 using the solid electrolyte as the electrolyte were measured, Respectively.
상기 표 1에서,In Table 1,
Voc는 개방전압(open circuit voltage)을 나타내고,V oc represents the open circuit voltage,
Jsc는 단회로 광전류 밀도(short circuit current)를 나타내고,J sc represents a short circuit current,
FF는 충전인자(Fill factor)를 나타내고,FF represents a fill factor,
PCE는 광전변환효율(photon-to-current conversion efficiency)을 나타낸다.
PCE represents the photon-to-current conversion efficiency.
표 1에 나타난 바와 같이, 고체상 전해질을 유기태양전지에 사용할 경우, 본 발명에 따른 사이클로펜타디티오펜 유도체를 유기염료로 사용한 실시예 3 및 실시예 4의 태양전지가 Z907을 유기염료로 사용한 비교예 1의 태양전지에 비해, 뛰어난 효율을 나타내고 있는 것을 알 수 있다. 구체적으로, 본 발명에 따른 사이클로펜타디티오펜 유도체를 유기염료로 사용한 실시예 3 및 실시예 4에서 제조한 태양전지는 각각 개로전압(Voc)이 0.72 V, 0.77 V, 단회로 광전류 밀도(Jsc)가 10.63 mA/mm2, 8.98 mA/mm, 충전인자(FF)가 0.55, 0.51, 광전변환효율(PCE)이 4.19 %, 3.09 %로 나타났으며, Z907을 유기염료로 사용한 비교예 1에서 제조한 태양전지는 개로전압(Voc)이 0.72 V, 단회로 광전류 밀도(Jsc)가 9.26 mA/mm2, 충전인자(FF)가 0.35, 광전변환효율(PCE)이 2.33 %로 나타났다. 본 발명에 따른 실시예 모두 비교예 보다 광전변환효율이 훨씬 우수함을 알 수 있으며, 특히, 실시예 3의 경우에는 약 2배 정도 우수한 광전변환효율을 나타냄을 알 수 있다. 또한, 실시예 3 및 실시예 4에서 제조된 태양전지의 몰 흡광계수는 각각, 6.0 × 104 M-1cm-1(487 nm), 7.2 × 104 M-1cm-1(483 nm)으로 비교예 1에서 제조된 태양전지의 몰 흡광계수 1.2 × 104 M-1cm-1(521 nm)에 비해 5 내지 6배 높은 값을 가지는 것을 알 수 있다. 이로부터, 고체상 전해질을 사용하는 태양전지에 있어서, 본 발명에 따른 사이클로펜타디티오펜 유도체를 유기염료로 사용한 태양전지는 Z907을 유기염료로 사용한 태양전지에 비해, 충전인자, 광전변환효율 및 몰 흡광계수가 상당히 뛰어난 것을 알 수 있다.
As shown in Table 1, when the solid electrolyte was used for an organic solar cell, the solar cells of Examples 3 and 4, in which the cyclopentadithiophene derivative according to the present invention was used as an organic dye, showed a comparative example using Z907 as an organic dye 1 < / RTI > solar cell. Specifically, the solar cells produced in Examples 3 and 4, in which the cyclopentadithiophene derivative according to the present invention was used as an organic dye, exhibited an open-circuit voltage (V oc ) of 0.72 V, 0.77 V, a single-photocurrent density J sc) is 10.63 mA / mm 2, 8.98 mA / mm, fill factor (FF) of 0.55, 0.51, had a photoelectric conversion efficiency (PCE) is appeared to 4.19%, 3.09%, in Comparative example 1 with Z907 as the organic dye a solar cell open-circuit voltage (V oc) is 0.72 V, a single photoelectric current density (J sc) is 9.26 mA / mm 2, fill factor (FF) is 0.35, and photoelectric conversion efficiency (PCE) is found to be 2.33% produced in . It can be seen that the photoelectric conversion efficiency of the embodiment according to the present invention is much better than that of the comparative example. In particular, the photoelectric conversion efficiency of the embodiment 3 is about twice as high as that of the comparative example. The molar extinction coefficients of the solar cells prepared in Example 3 and Example 4 were 6.0 × 10 4 M -1 cm -1 (487 nm), 7.2 × 10 4 M -1 cm -1 (483 nm) , Which is 5 to 6 times higher than the molar extinction coefficient of 1.2 x 10 4 M -1 cm -1 (521 nm) of the solar cell prepared in Comparative Example 1. From these results, it can be seen that the solar cell using the cyclopentadithiophene derivative according to the present invention as the organic dye in the solar cell using the solid electrolyte has higher charge factor, photoelectric conversion efficiency and molar absorbance than the solar cell using Z907 as the organic dye It can be seen that the coefficient is remarkably excellent.
따라서, 본 발명에 따른 사이클로펜타디티오펜 유도체는 고체상 전해질을 사용하여 제조된 태양전지에서 우수한 물리적 특성을 나타내므로, 유기태양전지용 염료로 유용하게 사용될 수 있다.
Accordingly, the cyclopentadithiophene derivative according to the present invention exhibits excellent physical properties in a solar cell manufactured using a solid electrolyte, and thus can be usefully used as a dye for an organic solar battery.
<< 실험예Experimental Example 2> 2> 준고상Quasi-solid 전해질에서의 태양전지의 물리적 특성 평가 Evaluation of Physical Properties of Solar Cells in Electrolytes
전해질로서, 준고상 전해질을 사용하고, 본 발명에 따른 사이클로펜타디티오펜 유도체를 염료로 사용하여 제조된 태양 전지의 물리적 특성을 평가하기 위해 다음과 같이 실험을 수행하였다.
An experiment was conducted as follows to evaluate the physical properties of a solar cell produced by using a quasi-solid electrolyte as an electrolyte and a cyclopentadithiophene derivative according to the present invention as a dye.
전해질로서, 준고상 전해질을 이용하여 본 발명에 따른 실시예 5, 실시예 6 및 비교예 2에서 제조된 태양전지의 개방전압, 단회로 광전류 밀도, 충전인자 및 광전변환효율의 물리적 특성을 측정하여 하기 표 2에 나타내었다.
The open-circuit voltage, single-photocurrent density, charge factor, and photoelectric conversion efficiency of the solar cell prepared in Example 5, Example 6 and Comparative Example 2 according to the present invention were measured using a quasi-solid electrolyte as the electrolyte, The results are shown in Table 2 below.
상기 표 1에서,In Table 1,
Voc는 개방전압(open circuit voltage)을 나타내고,V oc represents the open circuit voltage,
Jsc는 단회로 광전류 밀도(short circuit current)를 나타내고,J sc represents a short circuit current,
FF는 충전인자(Fill factor)를 나타내고,FF represents a fill factor,
PCE는 광전변환효율(photon-to-current conversion efficiency)을 나타낸다.
PCE represents the photon-to-current conversion efficiency.
표 2에 나타난 바와 같이, 준고상 전해질을 유기태양전지에 사용할 경우, 본 발명에 따른 사이클로펜타디티오펜 유도체를 유기염료로 사용한 실시예 5 및 실시예 6의 태양전지가 Z907을 유기염료로 사용한 비교예 2의 태양전지에 비해, 뛰어난 효율을 나타내고 있는 것을 알 수 있다. 구체적으로, 본 발명에 따른 사이클로펜타디티오펜 유도체를 유기염료로 사용한 실시예 5 및 실시예 6에서 제조한 태양전지는 각각 개로전압(Voc)이 0.70 V, 0.72 V, 단회로 광전류 밀도(Jsc)가 12.95 mA/mm2, 11.59 mA/mm, 충전인자(FF)가 0.70, 0.70, 광전변환효율(PCE)이 6.35 %, 5.84 %로 나타났으며, Z907을 유기염료로 사용한 비교예 2에서 제조한 태양전지는 개로전압(Voc)이 0.70 V, 단회로 광전류 밀도(Jsc)가 10.08 mA/mm2, 충전인자(FF)가 0.69, 광전변환효율(PCE)이 4.87 %로 나타났다. 본 발명에 따른 실시예 모두 비교예 보다 광전변환효율이 훨씬 우수함을 알 수 있으며, 특히, 실시예 5의 경우에는 약 1.8배 정도 우수한 광전변환효율을 나타냄을 알 수 있다. 이로부터, 준고상 전해질을 사용하는 태양전지에 있어서, 본 발명에 따른 사이클로펜타디티오펜 유도체를 유기염료로 사용한 태양전지는 Z907을 유기염료로 사용한 태양전지에 비해, 충전인자, 광전변환효율 및 몰 흡광계수가 상당히 뛰어난 것을 알 수 있다.
As shown in Table 2, when the quasi-solid electrolyte was used for an organic solar cell, the solar cells of Example 5 and Example 6 in which the cyclopentadithiophene derivative according to the present invention was used as an organic dye were compared with each other using Z907 as an organic dye It can be seen that the solar cell of Example 2 exhibits excellent efficiency. Specifically, the embodiment using the cyclopenta dithiophene derivatives according to the invention as the organic dye in Example 5 and Example A solar cell 6, where the respective open-circuit voltage (V oc) 0.70 V, 0.72 V, a single photoelectric current density (J sc) is 12.95 mA / mm 2, 11.59 mA / mm, fill factor (Comparative examples 2 FF) that was shown to 0.70, 0.70, and 6.35% photoelectric conversion efficiency (PCE), 5.84%, with Z907 as the organic dye a solar cell open-circuit voltage (V oc) is 0.70 V, that is a single photoelectric current density (J sc) 10.08 mA / mm 2, fill factor (FF) 0.69, photoelectric conversion efficiency (PCE) is found to be 4.87% produced in . It can be seen that the photoelectric conversion efficiency of the embodiment according to the present invention is much better than that of the comparative example. In particular, the photoelectric conversion efficiency of the embodiment 5 is about 1.8 times higher than that of the comparative example. Thus, in a solar cell using a quasi-solid electrolyte, the solar cell using the cyclopentadithiophene derivative according to the present invention as an organic dye has a higher charge factor, photoelectric conversion efficiency, and molar efficiency than a solar cell using Z907 as an organic dye. It can be seen that the extinction coefficient is remarkably excellent.
따라서, 본 발명에 따른 사이클로펜타디티오펜 유도체는 고체상 및 준고상 전해질을 사용하여 제조된 태양전지에서 우수한 물리적 특성을 나타내므로, 유기태양전지용 염료로 유용하게 사용될 수 있다.Therefore, the cyclopentadithiophene derivative according to the present invention exhibits excellent physical properties in a solar cell manufactured using a solid phase and a quasi-solid electrolyte, and thus can be effectively used as a dye for an organic solar battery.
Claims (10)
[화학식 1]
(상기 화학식 1에서,
R 및 R1은 서로 독립적으로, C1 내지 C20 직쇄 또는 측쇄 알킬이다).
A cyclopentadithiophene derivative represented by the following formula (1):
[Chemical Formula 1]
(In the formula 1,
R and R < 1 > are, independently of each other, C1 to C20 straight chain or branched alkyl.
상기 R 및 R1은 서로 독립적으로, 메틸, 에틸, 프로필, 이소프로필, 부틸, 이소부틸, tert-부틸, 펜틸, 헥실, 2-에틸헥실, 헵틸, 2-에틸펜틸, 옥틸, 3-프로필펜틸, 노닐, 데카닐, 운데카닐, 도데카닐 및 2-옥틸도데카닐로 이루어지는 군으로부터 선택되는 1종인 것을 특징으로 하는 사이클로펜타디티오펜 유도체.
The method according to claim 1,
Wherein R and R 1 are independently of each other methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, 2- ethylhexyl, heptyl, , Nonyl, decanyl, undecanyl, dodecanyl, and 2-octyldodecanyl. The cyclopentadithiophene derivative according to claim 1,
상기 R 및 R1은 서로 독립적으로, 메틸, 에틸, 프로필, 부틸, 펜틸, 헥실, 헵틸, 옥틸, 노닐, 데카닐, 운데카닐 및 도데카닐로 이루어지는 군으로부터 선택되는 1종인 것을 특징으로 하는 사이클로펜타디티오펜 유도체.
The method according to claim 1,
Wherein R and R 1 are independently from each other selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decanyl, undecanyl and dodecanyl Dithiophene derivatives.
(1) (E)-3-(6-(4-(비스(9,9-디메틸-9H-플루오렌-2-일)아미노)페닐)-4,4-디헥실-4H-사이클로펜타[1,2-b:5,4-b']디티오펜-2-일)-2-시아노아크릴산; 및
(2) (E)-3-(6-(4-(비스(9,9-디메틸-9H-플루오렌-2-일)아미노)페닐)-4,4-디도데실-4H-사이클로펜타[1,2-b:5,4-b']디티오펜-2-일)-2-시아노아크릴산으로 이루어지는 군으로부터 선택되는 것을 특징으로 하는 사이클로펜타디티오펜 유도체.
The cyclopentadithiophene derivative according to claim 1, wherein the cyclopentadithiophene derivative represented by the formula (1)
(1) Synthesis of (E) -3- (6- (4- (Bis (9,9-dimethyl-9H- fluoren-2-yl) amino) phenyl) -4,4-dihexyl- 1,2-b: 5,4-b '] dithiophen-2-yl) -2-cyanoacrylic acid; And
(2) Synthesis of (E) -3- (6- (4- (Bis (9,9-dimethyl-9H- fluoren-2-yl) amino) phenyl) -4,4-idodecyl- 1,2-b: 5,4-b '] dithiophen-2-yl) -2-cyanoacrylic acid.
화학식 2로 표시되는 화합물과 화학식 3으로 표시되는 화합물을 반응시켜 화학식 4의 화합물을 제조하는 단계(단계 1); 및
상기 단계 1에서 제조된 화학식 4의 화합물을 시아노아세트산과 반응시켜 화학식 1로 표시되는 사이클로펜타디티오펜 유도체를 제조하는 단계(단계 2)를 포함하여 제조하는 것을 특징으로 하는 사이클로펜타디티오펜 유도체의 제조방법:
[반응식 1]
(상기 반응식 1에서, R 및 R1은 상기 제1항에서 정의한 바와 같다).
As shown in Scheme 1 below,
Reacting a compound represented by formula (2) with a compound represented by formula (3) to prepare a compound represented by formula (4) (step 1); And
Reacting the compound of Formula 4 prepared in Step 1 with cyanoacetic acid to prepare a cyclopentadithiophene derivative represented by Formula 1 (Step 2). The cyclopentadithiophene derivative Manufacturing method:
[Reaction Scheme 1]
(In the above Reaction Scheme 1, R and R 1 are the same as defined in the above 1).
상기 전도성 기판 상에 형성되고, 하기 화학식 1의 화합물을 포함하는 염료가 흡착된 금속 산화물층을 포함하는 반도체 전극;
대향 전극; 및
상기 반도체 전극과 상기 대향 전극 사이를 채우는 전해질을 포함하는 것을 특징으로 하는 염료감응 태양전지:
[화학식 1]
(상기 화학식 1에서, R 및 R1은 제1항의 화학식 1에서 정의한 바와 같다).
Conductive substrate;
A semiconductor electrode formed on the conductive substrate, the semiconductor electrode comprising a dye-adsorbed metal oxide layer comprising a compound of Formula 1;
An opposing electrode; And
And an electrolyte filling the gap between the semiconductor electrode and the counter electrode.
[Chemical Formula 1]
(Wherein R and R 1 are the same as defined in the above formula (1)).
The dye-sensitized solar cell of claim 6, wherein the electrolyte is a semi-solid or solid state electrolyte.
The method of claim 7, wherein the quasi-solid electrolyte is selected from the group consisting of PVH (poly (vinylidene-fluoride-co-hexafluoropropylene)) 70, PVH (poly (vinylidene-fluoride-co-hexafluoropropylene) And PVDF-HFP (poly (vinylidene-fluoride-hexafluoropropylene)). The dye-sensitized solar cell according to claim 1,
The method of claim 7, wherein the solid electrolyte is selected from the group consisting of Spiro-MeOTAD (2,2 ', 7,7'-tetrakis (N, N-di-p- methoxyphenyl- Fluorene). ≪ / RTI >
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