KR20210106154A - Organic Blue Dyes featuring a Diketopyrrolopyrrole, Preparation Method Thereof, and Dye-sensitized Solar Cells Comprising the Same - Google Patents
Organic Blue Dyes featuring a Diketopyrrolopyrrole, Preparation Method Thereof, and Dye-sensitized Solar Cells Comprising the Same Download PDFInfo
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- KR20210106154A KR20210106154A KR1020200020946A KR20200020946A KR20210106154A KR 20210106154 A KR20210106154 A KR 20210106154A KR 1020200020946 A KR1020200020946 A KR 1020200020946A KR 20200020946 A KR20200020946 A KR 20200020946A KR 20210106154 A KR20210106154 A KR 20210106154A
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- organic blue
- blue dye
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- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title 1
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
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- 125000006850 spacer group Chemical group 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
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- 238000000034 method Methods 0.000 claims description 8
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/004—Diketopyrrolopyrrole dyes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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Abstract
Description
본 발명은, 다이케토피롤로피(DPP) 기반의 유기 청색염료, 이의 제조방법 및 이를 포함하는 염료감응형 태양전지에 관한 것으로, 상세하게는 근적외선 영역까지 흡수가 가능한 다이케토피롤로피(DPP) 기반의 유기 청색염료, 이의 제조방법 및 이를 포함하여 우수한 광전변환 효율을 가지는 염료감응형 태양전지에 관한 것이다. The present invention relates to a diketopyrrolopy (DPP)-based organic blue dye, a method for producing the same, and a dye-sensitized solar cell including the same, and more particularly, to a diketopyrrolopy (DPP) capable of absorbing up to the near-infrared region. )-based organic blue dye, a manufacturing method thereof, and a dye-sensitized solar cell having excellent photoelectric conversion efficiency including the same.
최근 에너지의 수요가 증가함에 따라, 환경친화적인 태양전지에 대한 다양한 연구가 진행되고 있다. Recently, as the demand for energy increases, various studies on environmentally friendly solar cells are being conducted.
그러나, 실리콘 태양전지는 Si의 제작 단가가 높아 원재료 수급 문제가 있으며, 전지 효율이 상당히 부족한바, 이를 해결하기 위한 노력으로 1991년 스위스 국립 로잔 고등기술원(EPEL)의 마이클 그라첼 박사 연구팀에 의해 개발된 염료감응형 태양전지에 대한 관심이 증가하고 있다.However, silicon solar cells have a problem of supply and demand of raw materials due to the high production cost of Si, and the battery efficiency is quite insufficient. Interest in dye-sensitized solar cells is increasing.
염료감응형 태양전지는 가시광선의 빛에너지를 흡수하여 전자-홀 쌍(electron-hole pair)을 생성하는 메커니즘으로, 감광성 염료 분자 및 생성된 전자를 전달하는 전이금속 산화물을 주된 구성 재료로 하며, 기존의 실리콘 태양전지에 비해 제조 단가가 저렴하고, 투명한 특성으로 인해 건물 외벽 유리창이나 유리 온실 등에 응용이 가능하다는 이점이 있다. The dye-sensitized solar cell is a mechanism that generates electron-hole pairs by absorbing the light energy of visible light. Compared to silicon solar cells, the manufacturing cost is lower, and due to its transparent characteristics, it has the advantage that it can be applied to glass windows or glass greenhouses on the exterior walls of buildings.
이러한 염료감응형 태양전지는 광감응체 염료(dye senstizer)가 안정성과 광전환효율을 결정하는 중요 요인이다. 그러나, 종래 사용한 금속 착화합물계 염료는 금속을 포함하여 친환경적이지 못하고 제조 단가가 상대적으로 높은 문제점이 있었다.In such a dye-sensitized solar cell, a photosensitizer dye is an important factor in determining stability and light conversion efficiency. However, the conventionally used metal complex-based dye has a problem in that it is not environmentally friendly, including metal, and has a relatively high manufacturing cost.
이에 높은 몰흡광계수(molar extinction coefficient)를 가지며 간단하게 합성 및 분리가 가능하여 경제성이 높고 환경친화적인 비금속 유기 청색염료가 이의 대안으로 제시되고 있다. Accordingly, a non-metallic organic blue dye that has a high molar extinction coefficient and can be easily synthesized and separated, which is highly economical and environmentally friendly, has been proposed as an alternative.
예를 들어, 한국 공개특허 10-2010-0136931호는 염료감응형 태양전지에 염료 증감 광전변환 소자로서 사용되어 종래의 염료보다 향상된 몰흡광계수, Jsc(단회로 광전류 밀도) 및 광전기 변환효율을 나타내어 태양전지의 효율을 크게 향상시킬 수 있는 유기 청색염료가 개시되어 있다. For example, Korean Patent Publication No. 10-2010-0136931 is used as a dye-sensitized photoelectric conversion element in a dye-sensitized solar cell and exhibits improved molar extinction coefficient, Jsc (single-circuit photocurrent density) and photoelectric conversion efficiency than conventional dyes. An organic blue dye capable of greatly improving the efficiency of a solar cell is disclosed.
그러나, 상기와 같은 기존 유기 청색염료들은 장기안정성이 좋지 않고 이를 광센서로 사용하는 경우에, 태양전지가 충분한 전력 변환 효율을 나타내지 못한다는 문제점이 있다.However, the conventional organic blue dyes as described above have a problem in that long-term stability is not good and the solar cell does not exhibit sufficient power conversion efficiency when it is used as an optical sensor.
한국 공개특허 10-2010-0136931호Korean Patent Publication No. 10-2010-0136931
본 발명은 상기와 같은 종래기술의 문제점과 과거로부터 요청되어온 기술적 과제를 해결하는 것을 목적으로 한다.An object of the present invention is to solve the problems of the prior art as described above and the technical problems that have been requested from the past.
본 발명의 목적은 근적외선 영역까지 흡수가 가능한 다이케토피롤로피(DPP) 기반의 유기 청색염료를 제공하는 것이다.It is an object of the present invention to provide a diketopyrrolopy (DPP)-based organic blue dye capable of absorbing up to the near-infrared region.
본 발명의 또 다른 목적은 간단하고 효율적으로 다이케토피롤로피(DPP) 기반의 유기 청색염료의 제조방법을 제공하는 것이다.Another object of the present invention is to provide a method for manufacturing a diketopyrrolopy (DPP)-based organic blue dye simply and efficiently.
본 발명의 또 다른 목적은 상기 유기 청색염료를 포함하는 우수한 광전 변환 효율을 가지는 염료감응형 태양전지를 제공하는 것이다. Another object of the present invention is to provide a dye-sensitized solar cell having excellent photoelectric conversion efficiency including the organic blue dye.
본 발명은, The present invention is
하기 화학식 (1)로 표시되는 다이케토피롤로피(diketopyrrolopyrrole, DPP) 기반의 유기 청색염료를 제공한다.It provides an organic blue dye based on diketopyrrolopyrrole (DPP) represented by the following formula (1).
D-π-A-π'-A'화학식 (1)D-π-A-π'-A' Formula (1)
상기 화학식 (1)에서, In the above formula (1),
D(donor)는 (R1)(R2)NC6H5-이고, 여기서 상기 R1 및 R2는 각각 독립적으로 수소, 할로겐 원소, 치환 또는 비치환의 C1-C20 알킬, 치환 또는 비치환의 C1-C20 알콕시, 치환 또는 비치환의 C4-C10 아릴, 또는 치환 또는 비치환의 C3-C10 헤테로아릴이며;D(donor) is (R 1 )(R 2 )NC 6 H 5 -, wherein R 1 and R 2 are each independently hydrogen, a halogen atom, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1 -C20 alkoxy, substituted or unsubstituted C4-C10 aryl, or substituted or unsubstituted C3-C10 heteroaryl;
π(π spacer)는 -π1-π2-이고, 여기서 상기 π1 및 π2는 각각 독립적으로 치환 또는 비치환의 C2-C6 알켄, C2 알킨, 치환 또는 비치환의 C4-C10 아릴, 또는 치환 또는 비치환의 C3-C10 헤테로아릴이며; π (π spacer) is -π 1 -π 2 -, wherein π 1 and π 2 are each independently a substituted or unsubstituted C2-C6 alkene, C2 alkyne, substituted or unsubstituted C4-C10 aryl, or substituted or unsubstituted C3-C10 heteroaryl;
A는이고, 여기서 상기 R3 및 R4는 각각 독립적으로, 수소, 할로겐 원소, 치환 또는 비치환의 C1-C20 알킬, 또는 치환 또는 비치환의 C1-C20 알콕시이며;A is wherein R 3 and R 4 are each independently hydrogen, a halogen atom, substituted or unsubstituted C1-C20 alkyl, or substituted or unsubstituted C1-C20 alkoxy;
π'(π' spacer)는 -π'1-π'2-이고, 여기서 상기 π'1 및 π'2는 각각 독립적으로 치환 또는 비치환의 C2-C6 알켄, C2 알킨, 치환 또는 비치환의 C4-C10 아릴, 또는 치환 또는 비치환의 C3-C10 헤테로아릴이며; π'(π' spacer) is -π' 1 -π' 2 -, wherein π' 1 and π' 2 are each independently a substituted or unsubstituted C2-C6 alkene, C2 alkyne, substituted or unsubstituted C4- C10 aryl, or substituted or unsubstituted C3-C10 heteroaryl;
A'는 앵커링 그룹(Anchoring group)이고; A' is an anchoring group;
치환기는 할로겐 원소, 히드록시, C1-C10 알킬, 및 C1-C10 알콕시로 이루어진 군에서 선택되는 하나 이상이며; 및the substituent is at least one selected from the group consisting of a halogen atom, hydroxy, C1-C10 alkyl, and C1-C10 alkoxy; and
헤테로 원자는 N, O 및 S로 이루어진 군에서 선택된 하나 이상일 수 있다. The hetero atom may be one or more selected from the group consisting of N, O and S.
상기 R1 및 R2는 각각 독립적으로 치환 또는 비치환의 C1-C5 알킬, 치환 또는 비치환의 C6 아릴, 또는 치환 또는 비치환의 C4-C5 헤테로아릴이며; 여기서 치환기는 C1-C5 알킬, 및 C1-C5 알콕시로 이루어진 군에서 선택되는 하나 이상일 수 있다. wherein R 1 and R 2 are each independently substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted C6 aryl, or substituted or unsubstituted C4-C5 heteroaryl; Here, the substituent may be at least one selected from the group consisting of C1-C5 alkyl, and C1-C5 alkoxy.
상기 π1, π2, π'1, 및 π'2는 각각 독립적으로 C2 알킨, 치환 또는 비치환의 C6 아릴, 또는 치환 또는 비치환의 C4-C5 헤테로아릴이며; 여기서 치환기는 C1-C2 알킬 및 C1-C2 알콕시로 이루어진 군에서 선택되는 하나 이상이고; 및 헤테로 원자는 N, O 및 S로 이루어진 군에서 선택된 하나 이상일 수 있다. π 1 , π 2 , π′ 1 , and π′ 2 are each independently C2 alkyne, substituted or unsubstituted C6 aryl, or substituted or unsubstituted C4-C5 heteroaryl; wherein the substituent is at least one selected from the group consisting of C1-C2 alkyl and C1-C2 alkoxy; And the hetero atom may be at least one selected from the group consisting of N, O and S.
상기 R3 및 R4는 각각 독립적으로, 수소, 또는 치환 또는 비치환의 C1-C10 알킬이며; 여기서 치환기는 C1-C5 알킬로 이루어진 군에서 선택되는 하나 이상일 수 있다. wherein R 3 and R 4 are each independently hydrogen or substituted or unsubstituted C1-C10 alkyl; Here, the substituent may be at least one selected from the group consisting of C1-C5 alkyl.
상기 앵커링 그룹(anchoring group)은 cyanoacrylic acid 앵커(anchors), Catechol 앵커, Pyridyl 앵커, Phosphonate 앵커, 2-Hydroxylbenzonitrile 앵커, Pyridine-N-oxide 앵커, Hydroxamate 앵커 및 Sulfonate 앵커로 이루어진 군에서 선택되는 하나 이상일 수 있다.The anchoring group may be one or more selected from the group consisting of cyanoacrylic acid anchors, Catechol anchors, Pyridyl anchors, Phosphonate anchors, 2-Hydroxylbenzonitrile anchors, Pyridine-N-oxide anchors, Hydroxamate anchors and Sulfonate anchors. have.
상기 유기 청색염료는 화학식 (1-1) 및 화학식 (1-2) 중 적어도 하나 또는 둘일 수 있다.The organic blue dye may be at least one or two of Formulas (1-1) and (1-2).
화학식 (1-1) Formula (1-1)
화학식 (2-1) Formula (2-1)
한편, 본 발명은 화학식 (1)의 유기 청색염료의 제조방법으로,On the other hand, the present invention is a method for producing an organic blue dye of formula (1),
(가) D-π1과 X-π2-A-π'1-π'2-CHO의 소노가시라(Sonogashira) 커플링 반응을 통해 D-π-A-π'-CHO를 제조하는 단계; 및(A) preparing D-π-A-π'-CHO through Sonogashira coupling reaction of D-π 1 and X-π 2 -A-π' 1 -π' 2 -CHO; and
(나) 단계(가)에서 제조된 D-π-A-π'-CHO의 노베나겔(Knoevenagel) 축합반응을 통해 말단에 앵커링 그룹(anchoring group)를 결합하는 단계(상기에서, π, π1, π2, A, π', π'1, 및 π'은 제1항에서 정의한 바와 같고, X는 할로겐 원소이다);를 포함하는 제조방법을 제공한다:(B) coupling an anchoring group to the end through Knoevenagel condensation reaction of D-π-A-π'-CHO prepared in step (a) (in the above, π, π 1 , π 2 , A, π', π' 1 , and π' are as defined in claim 1, and X is a halogen element); provides a manufacturing method comprising:
D-π-A-π'-A' 화학식 (1)D-π-A-π'-A' Formula (1)
한편, 본 발명은 상기 유기 청색염료를 포함하는 것을 특징으로 하는 염료감형 태양전지를 제공한다.On the other hand, the present invention is a dye feeling comprising the organic blue dye type solar cell.
본 발명에 따른 D-π-A-π'-A' 구조의 다이케토피롤로피(DPP) 기반의 유기 청색염료는 우수한 광전변환 효율(power-conversion efficiency)을 가지며 근적외선 영역까지 흡수가 가능하다. 또한, 친환경적이고 제조 단가가 저렴하며 장기안정성이 뛰어나다. The organic blue dye based on diketopyrrolopy (DPP) of the D-π-A-π'-A' structure according to the present invention has excellent power-conversion efficiency and can be absorbed up to the near-infrared region. . In addition, it is eco-friendly, has a low manufacturing cost, and has excellent long-term stability.
이러한 다이케토피롤로피(DPP) 기반의 유기 청색염료는 간단하고 효율적인 방법으로 합성할 수 있으며, 이를 이용하여 고효율의 염료감응형 태양전지를 제조할 수 있다.Such a diketopyrrolopy (DPP)-based organic blue dye can be synthesized in a simple and efficient way, and a high-efficiency dye-sensitized solar cell can be manufactured using it.
도 1은 본 발명에 따른 유기 청색염료를 포함하는 염료감응형 태양전지의 단면 모식도이다;
도2는 실험예 1에서 실시예 1의 CSD-08, 실시예 2의 CSD-09의 UV-vis 흡광스펙트럼을 측정한 결과이다;
도 3은 실험예 2에서 실시예 1의 CSD-08, 실시예 2의 CSD-09를 이용한 태양전지의 전류밀도-전압(J-V) 특성을 측정한 결과이다; 및
도 4는 실험예 3에서 실시예 1의 CSD-08, 실시예 2의 CSD-09를 이용한 태양전지의 외부양자효율(External Quantum Efficiency, EQE)을 측정하여 하기 도4에 나타내었다.1 is a schematic cross-sectional view of a dye-sensitized solar cell including an organic blue dye according to the present invention;
2 is a result of measuring UV-vis absorption spectra of CSD-08 of Example 1 and CSD-09 of Example 2 in Experimental Example 1;
3 is a current density-voltage (JV) characteristic of a solar cell using CSD-08 of Example 1 and CSD-09 of Example 2 in Experimental Example 2; and
FIG. 4 shows the measurement of External Quantum Efficiency (EQE) of the solar cell using CSD-08 of Example 1 and CSD-09 of Example 2 in Experimental Example 3, and is shown in FIG. 4 below.
다이케토피롤로피(diketopyrrolopyrrole, DPP) 기반의 유기 청색염료Organic blue dye based on diketopyrrolopyrrole (DPP)
앞서 설명한 바와 같이, 광감응체 염료는 염료감응형 태양전지의 안정성과 광전환효율을 결정하는 주요 요인으로, 종래 쿠마린계, 플루오린계, 폴리피리딜계, 포르피린계 염료 등과 같이 수많은 비금속 유기 청색염료가 개발되어 왔다. 비금속 유기 청색염료는 제조 단가가 낮고 환경 친화적이나, 전형적인 공여체-파이 결합 스페이서-수용체(donor-π conjugation spacer-acceptor, D-π-A) 구조로 한정적인 흡수영역을 보이므로 낮은 에너지 변환 효율을 나타내었다.As described above, photosensitizer dyes are a major factor in determining the stability and light conversion efficiency of dye-sensitized solar cells, and numerous non-metal organic blue dyes such as coumarin-based, fluorine-based, polypyridyl-based, and porphyrin-based dyes have been used in the past. has been developed The non-metallic organic blue dye has a low manufacturing cost and is environmentally friendly, but exhibits a limited absorption region with a typical donor-π conjugation spacer-acceptor (D-π-A) structure, resulting in low energy conversion efficiency. indicated.
이에, 본 발명의 발명자들은 심도있는 연구와 다양한 실험을 계속한 끝에 이후 설명하는 바와 같이, 다이케토피롤로피 기반의 공여체-파이 결합 스페이서-수용체-파이 결합 스페이서'-수용체'(donor-π conjugation spacer-acceptor-π conjugation spacer'-acceptor', D-π-A-π'-A') 구조의 비금속 유기 청색염료가 높은 광전환효율 및 장기 안정성을 나타내며 이를 이용하여 고효율의 염료감응형 태양전지를 제조할 수 있음을 확인하였는 바, 본 발명은 이러한 발견에 기초하여 완성되었다.Accordingly, the inventors of the present invention, as described later after continuing in-depth research and various experiments, a diketopyrrolopy-based donor-pi binding spacer-acceptor-pi binding spacer'-acceptor' (donor-π conjugation) The non-metallic organic blue dye with the spacer-acceptor-π conjugation spacer'-acceptor', D-π-A-π'-A') structure shows high light conversion efficiency and long-term stability. It was confirmed that it can be prepared, the present invention has been completed based on these findings.
구체적으로, 본 발명은,Specifically, the present invention
하기 화학식 (1)로 표시되는 다이케토피롤로피(diketopyrrolopyrrole, DPP) 기반의 유기 청색염료를 제공한다.It provides an organic blue dye based on diketopyrrolopyrrole (DPP) represented by the following formula (1).
D-π-A-π'-A'화학식 (1)D-π-A-π'-A' Formula (1)
상기 화학식 (1)에서, In the above formula (1),
D(donor)는 (R1)(R2)NC6H5-이고, 여기서 상기 R1 및 R2는 각각 독립적으로 수소, 할로겐 원소, 치환 또는 비치환의 C1-C20 알킬, 치환 또는 비치환의 C1-C20 알콕시, 치환 또는 비치환의 C4-C10 아릴, 또는 치환 또는 비치환의 C3-C10 헤테로아릴이며;D(donor) is (R 1 )(R 2 )NC 6 H 5 -, wherein R 1 and R 2 are each independently hydrogen, a halogen atom, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1 -C20 alkoxy, substituted or unsubstituted C4-C10 aryl, or substituted or unsubstituted C3-C10 heteroaryl;
π(π spacer)는 -π1-π2-이고, 여기서 상기 π1 및 π2는 각각 독립적으로 치환 또는 비치환의 C2-C6 알켄, C2 알킨, 치환 또는 비치환의 C4-C10 아릴, 또는 치환 또는 비치환의 C3-C10 헤테로아릴이며; π (π spacer) is -π 1 -π 2 -, wherein π 1 and π 2 are each independently a substituted or unsubstituted C2-C6 alkene, C2 alkyne, substituted or unsubstituted C4-C10 aryl, or substituted or unsubstituted C3-C10 heteroaryl;
A는이고, 여기서 상기 R3 및 R4는 각각 독립적으로, 수소, 할로겐 원소, 치환 또는 비치환의 C1-C20 알킬, 또는 치환 또는 비치환의 C1-C20 알콕시이며;A is wherein R 3 and R 4 are each independently hydrogen, a halogen atom, substituted or unsubstituted C1-C20 alkyl, or substituted or unsubstituted C1-C20 alkoxy;
π'(π' spacer)는 -π'1-π'2-이고, 여기서 상기 π'1 및 π'2는 각각 독립적으로 치환 또는 비치환의 C2-C6 알켄, C2 알킨, 치환 또는 비치환의 C4-C10 아릴, 또는 치환 또는 비치환의 C3-C10 헤테로아릴이며; π'(π' spacer) is -π' 1 -π' 2 -, wherein π' 1 and π' 2 are each independently a substituted or unsubstituted C2-C6 alkene, C2 alkyne, substituted or unsubstituted C4- C10 aryl, or substituted or unsubstituted C3-C10 heteroaryl;
A'는 앵커링 그룹(Anchoring group)이고; A' is an anchoring group;
치환기는 할로겐 원소, 히드록시, C1-C10 알킬, 및 C1-C10 알콕시로 이루어진 군에서 선택되는 하나 이상이며; 및the substituent is at least one selected from the group consisting of a halogen atom, hydroxy, C1-C10 alkyl, and C1-C10 alkoxy; and
헤테로 원자는 N, O 및 S로 이루어진 군에서 선택된 하나 이상이다.The hetero atom is at least one selected from the group consisting of N, O and S.
한편, 본 명세서의 용어를 이하 설명하기로 한다.On the other hand, the terminology of the present specification will be described below.
용어 "알킬"은 지방족 탄화수소 그룹을 의미한다. 본 발명에서 알킬은 어떠한 알켄이나 알킨 부위를 포함하고 있지 않음을 의미하는 "포화 알킬(saturated alkyl)"과, 적어도 하나의 알켄 또는 알킨 부위를 포함하고 있음을 의미하는 "불포화 알킬(unsaturated alkyl)"을 모두 포함하는 개념으로 사용되고 있으며, 상세하게는 "포화 알킬"일 수 있다. 상기 알킬은 분지형, 직쇄형 또는 환형을 포함할 수 있고, 또한 구조 이성질체를 포함하므로, 예를 들어, C3 알킬의 경우, 프로필, 이소 프로필을 의미할 수 있다The term “alkyl” refers to an aliphatic hydrocarbon group. In the present invention, alkyl is "saturated alkyl" meaning that it does not contain any alkene or alkyne moiety, and "unsaturated alkyl" meaning that it contains at least one alkene or alkyne moiety. It is used as a concept that includes all of them, and in detail, may be "saturated alkyl". The alkyl may include branched, straight-chain or cyclic, and also includes structural isomers, so, for example, in the case of C3 alkyl, it may mean propyl or isopropyl.
용어 "알콕시"는 산소 연결(-O-)을 통해 결합된 상기 기재된 바와 같은 알킬기를 의미한다.The term “alkoxy” refers to an alkyl group as described above attached through an oxygen linkage (—O—).
용어 "아릴"은 공유 파이 전자계를 가지고 있는 적어도 하나의 링을 가지고 있는 방향족치환체를 의미한다. 상기 용어는 모노시클릭 또는 폴리시클릭(즉, 탄소원자들의 인접한 쌍들을 나눠 가지는 링들) 그룹들을 포함한다. 치환될 경우, 치환기는 오쏘(o), 메타(m), 파라(p) 위치에 적절하게 결합될 수 있다.The term "aryl" refers to an aromatic substituent having at least one ring with a shared pi electron system. The term includes monocyclic or polycyclic (ie, rings that share adjacent pairs of carbon atoms) groups. When substituted, the substituent may be appropriately bonded at ortho (o), meta (m), or para (p) positions.
용어 "헤테로아릴"은 상기 기재된 바와 같은 아릴 고리의 일부가 산소, 질소, 황 등으로 치환되어 있는 치환체이다.The term “heteroaryl” is a substituent in which part of the aryl ring as described above is substituted with oxygen, nitrogen, sulfur, or the like.
용어 "할로겐 원소"는 주기율표의 17족에 속하는 원소들로, 상세하게는 플루오르, 염소, 브롬, 요오드일 수 있다. The term “halogen element” is an element belonging to group 17 of the periodic table, and specifically, may be fluorine, chlorine, bromine, or iodine.
본 발명에 따른 다이케토피롤로피 기반의 유기 청색염료는 공여체-파이 결합 스페이서-수용체-파이 결합 스페이서'-수용체'(donor-π conjugation spacer-acceptor-π conjugation spacer'-acceptor', D-π-A- π'-A') 구조로, 두 종료의 파이 결합 스페이서를 포함하며, 각각 수용체(A) 및 수용체'(A')가 연결되어 있는 형태이다. The organic blue dye based on diketopyrrolophy according to the present invention is a donor-pi bonding spacer-acceptor-pi bonding spacer'-acceptor' (donor-π conjugation spacer-acceptor-π conjugation spacer'-acceptor', D-π -A- π'-A') structure, including two-terminated pi-bonded spacers, in which the receptor (A) and the receptor '(A') are connected, respectively.
상기 다이케토피롤로피 기반의 유기 청색염료에서 공여체(D)는 분자내 전하 이동(intramolecular charge translation, ICT)에 기여하며, 수용체(A)는 두 개의 락탐(lactam)기로 인한 강한 전자 당김으로 전자 부족 현상을 나타내고 수용체'(A')는 전자 트랩(electron trap)으로 작용한다. 이러한 구조는 유기 청색염료 구조 내에서 전하의 분리 및 전자의 이동을 촉진하므로 높은 광전환효율 및 장기 안정성을 나타낼 수 있다. In the diketopyrrolopy-based organic blue dye, the donor (D) contributes to intramolecular charge translation (ICT), and the acceptor (A) is an electron with strong electron pulling due to two lactam groups. It shows a shortage phenomenon and the acceptor '(A') acts as an electron trap. This structure promotes the separation of charges and the movement of electrons in the organic blue dye structure, so it can exhibit high light conversion efficiency and long-term stability.
또한, 본 발명에 따른 다이케토피롤로피 기반의 유기 청색염료는 이하 살펴보는 바와 같이, 적색광 및 근적외선 영역의 흡수율이 우수하므로, 청색 염료로 바람직하게 이용될 수 있다. In addition, the diketopyrrolopy-based organic blue dye according to the present invention has excellent absorption rates in the red light and near-infrared regions, as will be seen below, and thus can be preferably used as a blue dye.
본 발명에 따른 화학식 (1)로 표시되는 다이케토피롤로피 기반의 유기 청색염료에서, 상기 R1 및 R2는 각각 독립적으로 치환 또는 비치환의 C1-C5 알킬, 치환 또는 비치환의 C6 아릴, 또는 치환 또는 비치환의 C4-C5 헤테로아릴로, 여기서 치환기는 C1-C5 알킬, 및 C1-C5 알콕시로 이루어진 군에서 선택되는 하나 이상일 수 있다.In the diketopyrrolopy-based organic blue dye represented by Formula (1) according to the present invention, R 1 and R 2 are each independently a substituted or unsubstituted C1-C5 alkyl, a substituted or unsubstituted C6 aryl, or A substituted or unsubstituted C4-C5 heteroaryl, wherein the substituent may be at least one selected from the group consisting of C1-C5 alkyl, and C1-C5 alkoxy.
상기 π1, π2, π'1, 및 π'2는 각각 독립적으로 C2 알킨, 치환 또는 비치환의 C6 아릴, 또는 치환 또는 비치환의 C4-C5 헤테로아릴로, 여기서 치환기는 C1-C2 알킬 및 C1-C2 알콕시로 이루어진 군에서 선택되는 하나 이상이고; 및 헤테로 원자는 N, O 및 S로 이루어진 군에서 선택된 하나 이상일 수 있다. π 1 , π 2 , π′ 1 , and π′ 2 are each independently C2 alkyne, substituted or unsubstituted C6 aryl, or substituted or unsubstituted C4-C5 heteroaryl, wherein the substituents are C1-C2 alkyl and C1 -C2 is at least one selected from the group consisting of alkoxy; And the hetero atom may be at least one selected from the group consisting of N, O and S.
상기 R3 및 R4는 각각 독립적으로, 수소, 또는 치환 또는 비치환의 C1-C10알킬로, 여기서 치환기는 C1-C5 알킬로 이루어진 군에서 선택되는 하나 이상일 수 있다. R 3 and R 4 are each independently hydrogen, or substituted or unsubstituted C1-C10 alkyl, wherein the substituent may be one or more selected from the group consisting of C1-C5 alkyl.
상기 앵커링 그룹(anchoring group)은 cyanoacrylic acid 앵커(anchors), Catechol 앵커, Pyridyl 앵커, Phosphonate 앵커, 2-Hydroxylbenzonitrile 앵커, Pyridine-N-oxide 앵커, Hydroxamate 앵커 및 Sulfonate 앵커로 이루어진 군에서 선택되는 하나 이상일 수 있다. 상기 앵커링 그룹의 구조는 당업계에 알려진 바, 예를 들어, Anchoring Groups for Dye-Sensitized Solar Cells, Lei Zhang?? and Jacqueline M. Cole, ACS Appl. Mater. Interfaces 2015, 7, 3427-3455에서 확인할 수 있다.The anchoring group may be one or more selected from the group consisting of cyanoacrylic acid anchors, Catechol anchors, Pyridyl anchors, Phosphonate anchors, 2-Hydroxylbenzonitrile anchors, Pyridine-N-oxide anchors, Hydroxamate anchors and Sulfonate anchors. have. The structure of the anchoring group is known in the art, for example, Anchoring Groups for Dye-Sensitized Solar Cells, Lei Zhang?? and Jacqueline M. Cole, ACS Appl. Mater. Interfaces 2015, 7, 3427-3455.
상세하게는, 본 발명에서 상기 앵커링 그룹은 하기 구조식 중 하나로 표현되는 cyanoacrylic acid 앵커일 수 있다.Specifically, in the present invention, the anchoring group may be a cyanoacrylic acid anchor represented by one of the following structural formulas.
본 발명에 따른 다이케토피롤로피기반의 유기 청색염료는 하기 화학식 (1-1), 화학식 (1-2), 또는 화학식 (1-1) 및 (1-2)으로 표시될 수 있다.The diketopyrrolopy-based organic blue dye according to the present invention may be represented by the following Chemical Formulas (1-1), (1-2), or (1-1) and (1-2).
화학식 (1-1) Formula (1-1)
화학식 (2-1) Formula (2-1)
이러한 유기 청색염료는 특히, 적색광 및 근적외선 영역의 흡수율이 우수하므로 청색 염료로 이용될 수 있다.This organic blue dye can be used as a blue dye, especially, because it has excellent absorption in red light and near-infrared regions.
다이케토피롤로피 기반의 유기 청색염료 제조방법Diketopyrrolopy-based organic blue dye manufacturing method
이하, 본 발명에 따른 다이케토피롤로피 기반의 유기 청색염료용 화합물의 제조방법을 살펴본다.Hereinafter, a method for preparing a diketopyrrolopy-based organic blue dye compound according to the present invention will be described.
본발명은 화학식 (1)로 표시되는 다이케토피롤로피 기반의 유기 청색염료는,The present invention is an organic blue dye based on diketopyrrolopy represented by Formula (1),
(가) D-π1과 X-π2-A-π'1-π'2-CHO의 소노가시라(Sonogashira) 커플링 반응을 통해 D-π-A-π'-CHO를 제조하는 단계; 및(A) preparing D-π-A-π'-CHO through Sonogashira coupling reaction of D-π 1 and X-π 2 -A-π' 1 -π' 2 -CHO; and
(나) 단계(가)에서 제조된 D-π-A-π'-CHO의 노베나겔(Knoevenagel) 축합반응을 통해 말단에 앵커링 그룹(anchoring group)를 결합하는 단계(상기에서, π, π1, π2, A, π', π'1, 및 π'은 제1항에서 정의한 바와 같고, X는 할로겐 원소이다);(B) coupling an anchoring group to the end through Knoevenagel condensation reaction of D-π-A-π'-CHO prepared in step (a) (in the above, π, π 1 , π 2 , A, π′, π′ 1 , and π′ are as defined in claim 1 , and X is a halogen element);
를 포함하여 제조할 수 있다.It can be prepared including
D-π-A-π'-A'화학식 (1)D-π-A-π'-A' Formula (1)
상기 단계(가)에서 촉매로, Pd(PPh3)2Cl2, Pd(PPh3)4, Pd(PPh3)2Br2, Co(PPh3)2Cl2, Co (PPh3)4, 및 Co(PPh3)2Br2로 이루어진 군에서 선택된 하나가 사용될 수 있으나 이에 제한되는 것은 아니다. 이러한 촉매는 CuI, PPh3와 함께 사용될 수 있다. As a catalyst in step (a), Pd(PPh 3 ) 2 Cl 2 , Pd(PPh 3 ) 4 , Pd(PPh 3 ) 2 Br 2 , Co(PPh 3 ) 2 Cl 2 , Co (PPh 3 ) 4 , And Co(PPh 3 ) 2 Br 2 One selected from the group consisting of may be used, but is not limited thereto. These catalysts can be used together with CuI, PPh 3 .
상기 단계(나)에서 노베나겔(Knoevenagel) 축합반응을 통해 앵커링 그룹을 D-π-A-π'-CHO의 말단에 결합시킨다. 이는 디클로로메탄, 1,2- 디클로로에탄, 아세토니트릴, 테트라히드로퓨란, 에틸에테르, 벤젠, 및 톨루엔 등의 반응 용매에서 피페리딘 등의 아민, 포름산, 초산 등의 유기산을 사용하여 수행할 수 있다.In step (b), an anchoring group is bonded to the end of D-π-A-π'-CHO through Knoevenagel condensation reaction. This can be carried out using an amine such as piperidine and an organic acid such as formic acid and acetic acid in a reaction solvent such as dichloromethane, 1,2-dichloroethane, acetonitrile, tetrahydrofuran, ethyl ether, benzene, and toluene. .
상기 단계(나)에서, 상기 앵커링 그룹은 앞서 정의한 바와 같다.In step (b), the anchoring group is as defined above.
염료감응형 태양전지Dye-sensitized solar cell
도 1은 본 발명에 따른 유기 청색염료를 포함하는 염료감응형 태양전지의 단면 모식도이다. 1 is a schematic cross-sectional view of a dye-sensitized solar cell including an organic blue dye according to the present invention.
도 1을 참고하면, 본 발명은 상기 유기 청색염료를 포함하는 염료감응형 태양전지를 제공한다. Referring to FIG. 1 , the present invention provides a dye-sensitized solar cell including the organic blue dye.
상기 염료감응형 태양전지는 제 1 전극(100), 상기 제 1 전극(100) 상에 형성된 전해질층(200), 상기 전해질층(200)에 형성되는 제 2 전극(300)의 구성을 포함한다. The dye-sensitized solar cell includes a
상기 제 1 전극(100), 및 제 2 전극(300)은 각각 투명 전극일 수 있으며, 예를 들어, 전도성 금속 산화물, 금속, 금속 합금, 또는 탄소재료일 수 있다. 상세하게는, 인듐틴옥사이드(ITO), 플루오린틴옥사이드(FTO), 인듐징크옥사이드(ISO), 안티몬틴옥사이드(ATO), 플루오르 도프 산화주석(FTO), 백금 나노입자가 형성된 FTO, SnO2, ZnO, 또는 이들의 조합; 백금, 은, 금, 요오드화구리일 수 있으나 이에 제한 되는 것은 아니다.Each of the
상기 전해질층(200)은 산화환원(redox) 전해질을 사용할 수 있다. 구체적으로는, 상기 전해질로는 할로겐 화합물 및 할로겐 분자로 구성되는 할로겐 산화 환원계 전해질, 페로시안산염-페로시안산염이나 페로센-페리시늄 이온, 코발트 착물 등의 금속착물 등의 금속산화 환원계 전해질, 알킬티올-알킬디설피드, 비올로겐 염료, 하이드로퀴논-퀴논 등의 유기산화 환원계 전해질 등을 사용할 수 있으며, 바람직하게는 할로겐 산화 환원계 전해질일 수 있다. The
또한, 상기 할로겐 분자는 요오드 분자 일수 있고, 할로겐 화합물로는 LiI, NaI, CaI2, MgI2, CuI 등의 할로겐화 금속염, 또는 테트라알킬암모늄요오드, 이미다졸리움요오드, 피리디움요오드 등의 할로겐의 유기 암모늄염, 또는 I2일 수 있다In addition, the halogen molecule may be an iodine molecule, and as the halogen compound, a metal halide salt such as LiI, NaI, CaI 2 , MgI 2 , CuI, or an organic halogen such as tetraalkylammonium iodine, imidazolium iodine, pyridium iodine, etc. It may be an ammonium salt, or I 2
또한, 산화환원 전해질은 이를 포함하는 용액의 형태로 구성될 수 있다. 이때, 상기 용액을 구성하는 용매로는 전지 화학적으로 불활성인 것을 사용할 수 있다. 예를 들어, 아세토니트릴, 프로필렌카보네이트, 에틸렌카보네이트, 3-메톡시프로피오니트릴, 메톡시아세토니트릴, 에틸렌글리콜, 프로필렌글리콜, 디에틸렌글리콜, 트리에틸렌글리콜, 부틸로락톤, 디메톡시에탄, 디메틸카보네이트, 1,3-디옥소란, 메틸포르메이트, 2-메틸테트라하이드로퓨란, 3-메톡시-옥사졸리딘-2-온, 설포란, 테트라하이드로퓨란, 물 등을 포함할 수 있다. 상세하게는, 아세토니트릴, 프로필렌카보네이트, 에틸렌카보네이트, 3-메톡시프로피오니트릴, 에틸렌글리콜, 3-메톡시-옥사졸리딘-2-온, 부틸로락톤일 수 있고, 이러한 용매들은 1종 또는 혼합해서 사용할 수 있다 In addition, the redox electrolyte may be configured in the form of a solution containing the same. In this case, as a solvent constituting the solution, a cell-chemically inactive solvent may be used. For example, acetonitrile, propylene carbonate, ethylene carbonate, 3-methoxypropionitrile, methoxyacetonitrile, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, butyrolactone, dimethoxyethane, dimethyl carbonate , 1,3-dioxolane, methyl formate, 2-methyltetrahydrofuran, 3-methoxy-oxazolidin-2-one, sulfolane, tetrahydrofuran, water, and the like. Specifically, it may be acetonitrile, propylene carbonate, ethylene carbonate, 3-methoxypropionitrile, ethylene glycol, 3-methoxy-oxazolidin-2-one, butyrolactone, and these solvents are one type or can be mixed
상기 전해질층(200)은 반도체 물질(210) 및 본 발명에 따른 유기 청색염료(220)를 포함할 수 있다. 상기 전해질층(200) 내에서 반도체 물질(210) 및 유기 청색 염료(220)는 단순 혼합 또는 어느 하나의 물질에 코팅, 흡착된 구조일 수 있으며, 상세하게는, 반도체 물질(210) 표면에는 최대 600 내지 700 nm의 근적외선 영역까지 빛을 흡수를 통해 여기 전자를 생성하여 청색을 나타내는 유기 청색 염료(220)가 흡착될 수 있다. The
상기 반도체 물질(210)은 티탄, 주석, 아연, 텅스텐, 지르코늄, 갈륨, 인듐, 이트륨, 니오브, 탄탈, 바나듐으로 이루어진 군에서 선택되는 금속 산화물을 사용할 수 있고, 상세하게는 산화티탄, 산화주석, 산화아연, 산화니오브, 산화티탄스트론튬 또는 이들의 혼합물일 수 있다. The
태양전지의 흡수 특성은 사용되는 유기 청색염료의 흡수파장에 따른 양자 효율(incident photonto-current conversion efficiency, IPCE) 또는 광포집 효율(light-harvesting efficiency, LHE)에 영향을 받는다. 따라서, 본 발명에 따른 감응형 태양전지는 광포집 효율이 높은 유기 청색염료를 담지한 광전극을 포함하여 특히, 적색광 및 적외선 영역의 흡수율이 높아 청색을 나타내며 높은 에너지 변환 효율을 나타낸다.The absorption characteristics of the solar cell are affected by the incident photonto-current conversion efficiency (IPCE) or light-harvesting efficiency (LHE) according to the absorption wavelength of the organic blue dye used. Therefore, the sensitized solar cell according to the present invention, including a photoelectrode carrying an organic blue dye with high light collection efficiency, exhibits blue color due to high absorption in red light and infrared region, and high energy conversion efficiency.
이하, 본 발명을 실시예를 통해 구체적으로 설명하나, 하기 실시예 및 실험예는 본 발명의 한 형태를 예시한 것에 불과할 뿐이며, 본 발명의 범위가 하기 실시예 및 실험예에 의해 제한되는 것은 아니다.Hereinafter, the present invention will be described in detail through Examples, but the following Examples and Experimental Examples are merely illustrative of one aspect of the present invention, and the scope of the present invention is not limited by the Examples and Experimental Examples below. .
하기에서 본 발명에 따른 다이케토피롤로피 기반의 유기 청색염료 합성 과정을 나타내었다.The synthesizing process of diketopyrrolopy-based organic blue dye according to the present invention is shown below.
실시예 1 CSD-08(화학식 1)의 합성Example 1 Synthesis of CSD-08 (Formula 1)
Compound 2Compound 2
3-neck 플라스크에 π-spacer (1.8 g, 2.54 mmol)와 TEA/toluene (30 mL/30 mL), Pd(PPh3)2Cl2(0.09 g, 0.127 mmol), PPh3(0.013 g, 0.05 mmol), CuI (0.046 g, 0.1 mmol) 그리고 4-ethynyl-N,N -dimethylaniline (0.55 g, 3.82 mmol)을 첨가하여 질소 조건하에 5 hr 동안 환류시킨다. 반응이 종결되면 상온에서 물(250 mL)과 MC(2 Х 250 mL)를 첨가하여 생성물을 유기층으로 이동 시킨 후 추출하여 MgSO4로 수분을 제거해 준 뒤 용매를 증류한다. 이렇게 얻어진 용액을 실리카겔을 이용한 컬럼 크로마토그래피를 통해 정제하여 남색 고체 (1.3 g)를 얻었다.(66.17 %) 1H NMR (300 MHz, Chloroform-d) δ 10.04 (s, 1H), 8.97 (dd, J = 12.8, 4.2 Hz, 2H), 7.94 (d, J = 8.0 Hz, 2H), 7.83 (d, J = 8.1 Hz, 2H), 7.60 (d, J = 4.1 Hz, 1H), 7.42 (d, J = 8.6 Hz, 2H), 7.31 (s, 1H), 6.67 (d, J = 8.6 Hz, 2H), 3.02 (s, 6H), 2.03 (d, J = 6.5 Hz, 2H), 1.60 (s, 4H), 1.25 (s, 16H), 0.88 (s, 12H).13C NMR (75 MHz, CDCL3)δ 217.71, 197.58, 189.16, 176.87, 169.96, 163.46, 158.31, 155.36, 149.62, 140.99, 133.73, 133.73, 129.32, 127.18, 125.96, 118.86, 112.54, 108.37, 108.00, 106.39, 103.53, 103.17, 99.12, 98.43, 95.93, 94.66, 79.20, 78.96, 78.23, 77.80, 77.38, 76.87, 76.46, 76.40, 74.03, 72.78, 69.76, 62.78, 57.51, 46.78, 40.86, 30.37, 29.08, 14.76, 12.21, 11.15, -3.74.; HRMS m/z (FAB) calc. for C47H53N3O3S2[M+]: 771.3528, found: 771.3533.In a 3-neck flask, add π-spacer (1.8 g, 2.54 mmol) with TEA/toluene (30 mL/30 mL), Pd(PPh 3 ) 2 Cl 2 (0.09 g, 0.127 mmol), PPh 3 (0.013 g, 0.05) mmol), CuI (0.046 g, 0.1 mmol) and 4-ethynyl-N,N-dimethylaniline (0.55 g, 3.82 mmol) were added and refluxed for 5 hr under nitrogen condition. When the reaction is completed, water (250 mL) and MC (2 Х 250 mL) are added at room temperature to move the product to the organic layer, and the product is extracted to remove moisture with MgSO 4 , and then the solvent is distilled off. The obtained solution was purified by column chromatography using silica gel to obtain an indigo blue solid (1.3 g). (66.17 %) 1 H NMR (300 MHz, Chloroform-d) δ 10.04 (s, 1H), 8.97 (dd, J = 12.8, 4.2 Hz, 2H), 7.94 (d, J = 8.0 Hz, 2H), 7.83 (d, J = 8.1 Hz, 2H), 7.60 (d, J = 4.1 Hz, 1H), 7.42 (d, J = 8.6 Hz, 2H), 7.31 (s, 1H), 6.67 (d, J = 8.6 Hz, 2H), 3.02 (s, 6H), 2.03 (d, J = 6.5 Hz, 2H), 1.60 (s, 4H), 1.25 (s, 16H), 0.88 (s, 12H). 13 C NMR (75 MHz, CDCL 3 )δ 217.71, 197.58, 189.16, 176.87, 169.96, 163.46, 158.31, 155.36, 149.62, 140.99, 133.73, 133.73, 129.32, 127.18, 125.96, 118.54, 108.3739, 112.54, 108.3739 , 103.53, 103.17, 99.12, 98.43, 95.93, 94.66, 79.20, 78.96, 78.23, 77.80, 77.38, 76.87, 76.46, 76.40, 74.03, 72.78, 69.76, 62.78, 57.51, 30.78, 29.08 14.86, 30.78, 40.86. , 11.15, -3.74.; HRMS m/z (FAB) calc. for C 47 H 53 N 3 O 3 S 2 [M+]: 771.3528, found: 771.3533.
CSD-08CSD-08
2-neck 플라스크에 Compound 2 (1.3 g, 1.684 mmol), 2-cyanoacetic acid (215 mg, 2.526 mmol) , ammonium acetate (1 g, 12.967 mmol) 와 acetic acid (130 mL)를 첨가하여 90 °C에 6~8 시간 반응시킨다. 반응이 종결되면 상온에서 용액을 식힌 뒤 물에 붓는다. 물 속에 침전물이 생성되면 걸러서 남색고체 1.06 g를 얻었다 (75 %). 1H NMR (300 MHz, Chloroform-d) δ 8.84 (s, 2H), 7.90 (d, J = 9.1 Hz, 2H), 7.67 (d, J = 8.1 Hz, 2H), 7.56 (s, 1H), 7.36 (d, J = 9.2 Hz, 2H), 6.67 (d, J = 9.5 Hz, 2H), 4.03 (s, 4H), 3.07 - 2.95 (m, 7H), 2.52 (d, J = 5.5 Hz, 2H), 1.36 (s, 9H), 1.26 (s, 13H), 0.94 - 0.82 (m, 16H). 13C NMR (75 MHz, CDCL3) δ 164.39, 161.32, 126.66, 126.62, 126.59, 126.53, 126.43, 112.78, 84.18, 81.73, 81.60, 81.08, 80.90, 80.86, 80.40, 80.30, 80.27, 80.17, 79.95, 79.74, 79.69, 79.56, 79.41, 79.27, 79.22, 79.21, 79.19, 79.17, 79.09, 78.01, 77.58, 77.16, 75.24, 75.19, 74.22, 73.41, 73.33, 65.12, 56.51, 40.77, 40.73, 39.74, 24.14, 23.61, 23.59, 23.54, 22.10, 16.78, 14.60, 14.53, 14.47, 11.00, 10.92.; HRMS m/z (FAB) calc. for C50H54N4O4S2[M+]: 838.3586, found: 838.3590.In a 2-neck flask, add Compound 2 (1.3 g, 1.684 mmol), 2-cyanoacetic acid (215 mg, 2.526 mmol) , ammonium acetate (1 g, 12.967 mmol) and acetic acid (130 mL) at 90 °C. React for 6-8 hours. When the reaction is complete, the solution is cooled at room temperature and poured into water. When a precipitate was formed in water, it was filtered to obtain 1.06 g of an indigo solid (75 %). 1 H NMR (300 MHz, Chloroform-d) δ 8.84 (s, 2H), 7.90 (d, J = 9.1 Hz, 2H), 7.67 (d, J = 8.1 Hz, 2H), 7.56 (s, 1H), 7.36 (d, J = 9.2 Hz, 2H), 6.67 (d, J = 9.5 Hz, 2H), 4.03 (s, 4H), 3.07 - 2.95 (m, 7H), 2.52 (d, J = 5.5 Hz, 2H) ), 1.36 (s, 9H), 1.26 (s, 13H), 0.94 - 0.82 (m, 16H). 13 C NMR (75 MHz, CDCL3) δ 164.39, 161.32, 126.66, 126.62, 126.59, 126.53, 126.43, 112.78, 84.18, 81.73, 81.60, 81.08, 80.90, 80.86, 80.40, 80.17, 80.27, 80.17, 79.95 79.69, 79.56, 79.41, 79.27, 79.22, 79.21, 79.19, 79.17, 79.09, 78.01, 77.58, 77.16, 75.24, 75.19, 74.22, 73.41, 73.33, 65.12, 56.51, 40.77, 40.73, 40.77, 40. 23.54, 22.10, 16.78, 14.60, 14.53, 14.47, 11.00, 10.92.; HRMS m/z (FAB) calc. for C 50 H 54 N 4 O 4 S 2 [M+]: 838.3586, found: 838.3590.
실시예 2 CSD-09(화학식 2)의 합성Example 2 Synthesis of CSD-09 (Formula 2)
Compound 3Compound 3
3-neck 플라스크에 π-spacer (2.1 g, 2.974 mmol), Pd(PPh3)2Cl2(0.104 g, 0.149 mmol), PPh3(0.016 g, 0.06 mmol), 그리고 4-butoxy-N-(4-butoxyphenyl)-N-(4-ethynylphenyl)benzenamine (1.845 g, 4.461 mmol)을 첨가하여 질소 조건하에 5 hr 동안 환류시킨다. 반응이 종결되면 상온에서 물(250 mL)과 MC(2Х250 mL)를 첨가하여 생성물을 유기층으로 이동 시킨 후 추출하여 MgSO4로 수분을 제거해 준 뒤 용매를 증류한다. 이렇게 얻어진 용액을 실리카겔을 이용한 컬럼 크로마토그래피를 통해 정제하여 남색 고체 (1.6 g) 를 얻었다. (51.71 %) 1H NMR (300 MHz, Chloroform-d) δ 8.95 (d, J = 2.9 Hz, 1H), 7.98 - 7.80 (m, 1H), 7.61 (s, 1H), 7.32 (s, 7H), 7.08 (d, J = 8.9 Hz, 3H), 6.91 (s, 1H), 6.85 (d, J = 9.0 Hz, 7H), 3.94 (s, 4H), 2.17 (s, 2H), 1.98 - 1.96 (m, 8H), 1.57 (s, 9H), 1.25 (s, 11H), 0.87 (s, 10H). 13C NMR (75 MHz, CDCL3) δ 221.27, 177.04, 160.45, 156.36, 150.68, 147.69, 133.49, 127.35, 123.71, 119.85, 118.84, 112.85, 93.05, 86.12, 84.09, 83.99, 82.76, 82.65, 82.52, 82.35, 82.31, 82.05, 81.77, 81.63, 81.05, 80.91, 80.84, 80.80, 80.77, 80.74, 80.52, 80.43, 80.34, 80.23, 80.14, 80.06, 79.94, 79.83, 79.79, 77.16, 76.74, 76.31, 73.73, 73.59, 73.53, 73.27, 71.42, 71.23, 70.77, 70.33, 70.21, 69.56, 69.24, 68.97, 68.64, 65.69, 61.94, 60.68, 57.36, 44.46, 41.82, 31.59, 31.35, 29.36, 29.31, 24.27, 22.34, 10.93.; HRMS m/z (FAB) calc. for C65H73N3O5S2[M+]: 1039.4992, found: 1039.4998.In a 3-neck flask, π-spacer (2.1 g, 2.974 mmol), Pd(PPh 3 ) 2 Cl 2 (0.104 g, 0.149 mmol), PPh3 (0.016 g, 0.06 mmol), and 4-butoxy-N-(4 -butoxyphenyl)-N-(4-ethynylphenyl)benzenamine (1.845 g, 4.461 mmol) was added and refluxed for 5 hr under nitrogen condition. When the reaction is completed, water (250 mL) and MC (2Х250 mL) are added at room temperature to move the product to the organic layer, and the product is extracted to remove moisture with MgSO 4 , and then the solvent is distilled off. The solution thus obtained was purified through column chromatography using silica gel to obtain an indigo blue solid (1.6 g). (51.71%) 1 H NMR (300 MHz, Chloroform-d) δ 8.95 (d, J = 2.9 Hz, 1H), 7.98 - 7.80 (m, 1H), 7.61 (s, 1H), 7.32 (s, 7H) , 7.08 (d, J = 8.9 Hz, 3H), 6.91 (s, 1H), 6.85 (d, J = 9.0 Hz, 7H), 3.94 (s, 4H), 2.17 (s, 2H), 1.98 - 1.96 ( m, 8H), 1.57 (s, 9H), 1.25 (s, 11H), 0.87 (s, 10H). 13 C NMR (75 MHz, CDCL 3 ) δ 221.27, 177.04, 160.45, 156.36, 150.68, 147.69, 133.49, 127.35, 123.71, 119.85, 118.84, 112.85, 93.05, 86.12, 843.09, 82.52, 82.65, 82.76, 82.65 , 82.31, 82.05, 81.77, 81.63, 81.05, 80.91, 80.84, 80.80, 80.77, 80.74, 80.52, 80.43, 80.34, 80.23, 80.14, 80.06, 79.94, 79.83, 79.79, 77.16, 76.73. , 73.27, 71.42, 71.23, 70.77, 70.33, 70.21, 69.56, 69.24, 68.97, 68.64, 65.69, 61.94, 60.68, 57.36, 44.46, 41.82, 31.59, 31.35, 29.36, 29.31, 24.27, 22.34, 10.93. HRMS m/z (FAB) calc. for C 65 H 73 N 3 O 5 S 2 [M+]: 1039.4992, found: 1039.4998.
CSD-09CSD-09
2-neck 플라스크에 Compound 3 (1.6 g, 1.538 mmol), 2-cyanoacetic acid (196 mg, 2.307 mmol)), ammonium acetate (912 mg, 11.843 mmol)와 acetic acid (160 mL)를 첨가하여 90 °C에 6~8 시간 반응시킨다. 반응이 종결되면 상온에서 용액을 식힌 뒤 물에 붓는다. 물 속에 침전물이 생성되면 걸러서 남색 고체 1.45 g를 얻었다 (85.18 %). 1H NMR (300 MHz, Chloroform-d) δ 8.80 (s, 1H), 8.08 (s, 1H), 7.93 (s, 2H), 7.71 (d, J = 7.3 Hz, 2H), 7.59 (s, 1H), 7.28 (s, 1H), 7.18 (s, 1H), 7.06 (d, J = 8.0 Hz, 4H), 6.83 (d, J = 8.9 Hz, 8H), 4.03 (s, 2H), 3.94 (t, J = 6.0 Hz, 5H), 2.50 (s, 1H), 1.88 (s, 2H), 1.82 - 1.69 (m, 6H), 1.34 (s, 8H), 1.27 (s, 7H), 0.97 (t, J = 7.3 Hz, 8H), 0.93 - 0.83 (m, 14H).13C NMR (75 MHz, CDCL3) δ 206.87, 204.40, 201.09, 190.24, 189.39, 174.94, 167.59, 147.57, 142.82, 140.96, 127.51, 127.49, 126.06, 119.10, 115.58, 115.55, 115.53, 112.46, 111.52, 109.03, 107.07, 100.73, 96.07, 95.49, 95.34, 94.56, 89.82, 85.68, 83.06, 81.82, 77.58, 77.16, 76.74, 74.23, 71.46, 69.46, 68.05, 63.95, 63.08, 59.69, 59.49, 58.06, 57.81, 57.28, 55.31, 54.96, 41.97, 38.01, 33.81, 32.69, 31.44, 26.86, 24.64, 23.13, 23.09, 22.38, 21.98, 20.86, 20.33, 19.66, 19.55, 19.32, 17.93, 14.82, 14.15, 13.93, 12.92, 9.62, 2.69, 0.43, 0.03.; HRMS m/z (FAB) calc. for C68H74N4O6S2[M+]: 1106.5050, found: 1106.5061. Compound 3 (1.6 g, 1.538 mmol), 2-cyanoacetic acid (196 mg, 2.307 mmol)), ammonium acetate (912 mg, 11.843 mmol) and acetic acid (160 mL) were added to a 2-neck flask at 90 °C. react for 6-8 hours. When the reaction is complete, the solution is cooled at room temperature and poured into water. When a precipitate was formed in water, it was filtered to obtain 1.45 g of an indigo blue solid (85.18 %). 1 H NMR (300 MHz, Chloroform-d) δ 8.80 (s, 1H), 8.08 (s, 1H), 7.93 (s, 2H), 7.71 (d, J = 7.3 Hz, 2H), 7.59 (s, 1H) ), 7.28 (s, 1H), 7.18 (s, 1H), 7.06 (d, J = 8.0 Hz, 4H), 6.83 (d, J = 8.9 Hz, 8H), 4.03 (s, 2H), 3.94 (t) , J = 6.0 Hz, 5H), 2.50 (s, 1H), 1.88 (s, 2H), 1.82 - 1.69 (m, 6H), 1.34 (s, 8H), 1.27 (s, 7H), 0.97 (t, J = 7.3 Hz, 8H), 0.93 - 0.83 (m, 14H). 13 C NMR (75 MHz, CDCL3) δ 206.87, 204.40, 201.09, 190.24, 189.39, 174.94, 167.59, 147.57, 142.82, 140.96, 127.51, 127.49, 126.06, 119.10, 115.58, 115.55, 111.53, 109.112. 107.07, 100.73, 96.07, 95.49, 95.34, 94.56, 89.82, 85.68, 83.06, 81.82, 77.58, 77.16, 76.74, 74.23, 71.46, 69.46, 68.05, 63.95, 63.08, 59.69, 59.81, 58.28, 55.06, 59.49, 58.06 54.96, 41.97, 38.01, 33.81, 32.69, 31.44, 26.86, 24.64, 23.13, 23.09, 22.38, 21.98, 20.86, 20.33, 19.66, 19.55, 19.32, 17.93, 14.82, 14.15, 13.93, 12.92, 9.62, 2.69, 0.43, 0.03.; HRMS m/z (FAB) calc. for C 68 H 74 N 4 O 6 S 2 [M+]: 1106.5050, found: 1106.5061.
<실험예 1><Experimental Example 1>
실시예 1의 CSD-08, 실시예 2의 CSD-09의 UV-vis 흡광스펙트럼을 측정하여 하기 도 2에 나타내었다. 구체적으로, 각각 디메틸포름아미드(DMF)에 용해시킨 후, 측정하였다.UV-vis absorption spectra of CSD-08 of Example 1 and CSD-09 of Example 2 were measured and shown in FIG. 2 below. Specifically, each was dissolved in dimethylformamide (DMF) and then measured.
CSD-08, CSD-09의 경우, 615 nm(13,708), 625 nm(14,215)에서 광흡수 극대 파장(몰 흡광 계수(M-1·cm-1))을 나타내는 것을 확인할 수 있다. CSD-09의 몰 흡광 계수가 조금 높게 나타나는 것을 확인할 수 있다. In the case of CSD-08 and CSD-09, it can be seen that the maximum light absorption wavelength (molar extinction coefficient (M -1 ·cm -1 )) is shown at 615 nm (13,708) and 625 nm (14,215). It can be seen that the molar extinction coefficient of CSD-09 is slightly higher.
<실험예 2><Experimental Example 2>
실시예 1의 CSD-08, 실시예 2의 CSD-09를 이용하여 연료 감응형 태양전지를 A fuel-sensitized solar cell was manufactured using CSD-08 of Example 1 and CSD-09 of Example 2
제1전극(광음극) 및 제2전극(대전극)을 대응시켜 봉지하며, 상기 제1전극 및 제2전극 사이에 전해질을 채워 넣어 염료감응형 태양전지를 제작하였다. A dye-sensitized solar cell was manufactured by sealing the first electrode (photocathode) and the second electrode (counter electrode) in correspondence with each other, and filling an electrolyte between the first electrode and the second electrode.
상기 각 전극은 유리 기판 상에 제조하였다. 이 때 상기 제1전극은 이산회티탄(TiO2) 나노입자가 도포된 불포가 도핑된 주석산화물(Fluorine-doped tin oxide, FTO)로 구성되며, 제2전극은 백금(Pt) 나노입자가 형성된 FTO로 구성되며, 전해질로는 아이오딘 기반의 액체 전해질(솔라로닉스 사 AN-50)을 사용하였다. Each of the electrodes was prepared on a glass substrate. At this time, the first electrode is composed of fluorine-doped tin oxide (FTO) coated with titanium dioxide (TiO2) nanoparticles, and the second electrode is FTO with platinum (Pt) nanoparticles formed thereon. , and an iodine-based liquid electrolyte (Solaronics AN-50) was used as the electrolyte.
(봉지 전) 상기 제1전극의 TiO2에 CSD-08, CSD-09 각각을 흡착시켜 준비하였다.(Before sealing) CSD-08 and CSD-09 were respectively adsorbed to TiO2 of the first electrode.
(봉지 전) 상기 제2전극의 특정부위에 전해질 주입을 위한 2개의 구멍을 형성하였다. (Before sealing) Two holes for electrolyte injection were formed in a specific portion of the second electrode.
그런 다음, 제1전극 및 제2전극 사이에 약 25 μm 두께로 격벽을 배치시키고 열과 압력을 가하여 봉지시켰다. 상기 격벽 재료로는 솔라로닉스(Solaronix) 사의 Surlyn을 사용하였다. 그런 다음, 상기 제2전극 표면에 형성된 미세구멍을 통하여 상기 두 전극 사이의 공간에 전해질 용액을 충진하고 구멍을 밀봉시켜 본 발명에 의한 염료감응형 태양전지를 제작하였다.Then, a barrier rib with a thickness of about 25 μm was placed between the first electrode and the second electrode, and heat and pressure were applied to seal it. As the barrier rib material, Surlyn manufactured by Solaronix was used. Then, an electrolyte solution was filled in the space between the two electrodes through the micropores formed on the surface of the second electrode, and the holes were sealed to prepare a dye-sensitized solar cell according to the present invention.
이렇게 CSD-08, CSD-09로 제작한 태양전지의 전류밀도-전압(J-V) 특성을 측정하고 광전지 특성을 평가하여 하기 도 3 및 표 1에 나타내었다. In this way, the current density-voltage (J-V) characteristics of the solar cells manufactured with CSD-08 and CSD-09 were measured, and the photovoltaic characteristics were evaluated, and are shown in FIG. 3 and Table 1 below.
<실험예 3><Experimental Example 3>
실험예 2에서 CSD-08, CSD-09로 제작한 태양전지의 외부양자효율(External Quantum Efficiency, EQE)을 측정하여 하기 도4에 나타내었다.In Experimental Example 2, the external quantum efficiency (External Quantum Efficiency, EQE) of the solar cells manufactured with CSD-08 and CSD-09 was measured and shown in FIG. 4 below.
도 4에 따르면, 가시광 400 내지 700 nm 파장 범위에서, 40% 이상인 것을 확인할 수 있었고, 근적외선 영역에서도 발전이 가능함을 확인할 수 있었다. According to FIG. 4 , in the wavelength range of 400 to 700 nm of visible light, it was confirmed that it was 40% or more, and it was confirmed that power generation was possible even in the near-infrared region.
Claims (8)
D-π-A-π'-A'화학식 (1)
상기 화학식 (1)에서,
D(donor)는 (R1)(R2)NC6H5-이고, 여기서 상기 R1 및 R2는 각각 독립적으로 수소, 할로겐 원소, 치환 또는 비치환의 C1-C20 알킬, 치환 또는 비치환의 C1-C20 알콕시, 치환 또는 비치환의 C4-C10 아릴, 또는 치환 또는 비치환의 C3-C10 헤테로아릴이며;
π(π spacer)는 -π1-π2-이고, 여기서 상기 π1 및 π2는 각각 독립적으로 치환 또는 비치환의 C2-C6 알켄, C2 알킨, 치환 또는 비치환의 C4-C10 아릴, 또는 치환 또는 비치환의 C3-C10 헤테로아릴이며;
A는이고, 여기서 상기 R3 및 R4는 각각 독립적으로, 수소, 할로겐 원소, 치환 또는 비치환의 C1-C20 알킬, 또는 치환 또는 비치환의 C1-C20 알콕시이며;
π'(π' spacer)는 -π'1-π'2-이고, 여기서 상기 π'1 및 π'2는 각각 독립적으로 치환 또는 비치환의 C2-C6 알켄, C2 알킨, 치환 또는 비치환의 C4-C10 아릴, 또는 치환 또는 비치환의 C3-C10 헤테로아릴이며;
A'는 앵커링 그룹(Anchoring group)이고;
치환기는 할로겐 원소, 히드록시, C1-C10 알킬, 및 C1-C10 알콕시로 이루어진 군에서 선택되는 하나 이상이며; 및
헤테로 원자는 N, O 및 S로 이루어진 군에서 선택된 하나 이상이다.Diketopyrrolopyrrole (DPP)-based organic blue dye, characterized in that represented by the following formula (1):
D-π-A-π'-A' Formula (1)
In the above formula (1),
D(donor) is (R 1 )(R 2 )NC 6 H 5 -, wherein R 1 and R 2 are each independently hydrogen, a halogen atom, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1 -C20 alkoxy, substituted or unsubstituted C4-C10 aryl, or substituted or unsubstituted C3-C10 heteroaryl;
π (π spacer) is -π 1 -π 2 -, wherein π 1 and π 2 are each independently a substituted or unsubstituted C2-C6 alkene, C2 alkyne, substituted or unsubstituted C4-C10 aryl, or substituted or unsubstituted C3-C10 heteroaryl;
A is wherein R 3 and R 4 are each independently hydrogen, a halogen atom, substituted or unsubstituted C1-C20 alkyl, or substituted or unsubstituted C1-C20 alkoxy;
π'(π' spacer) is -π' 1 -π' 2 -, wherein π' 1 and π' 2 are each independently a substituted or unsubstituted C2-C6 alkene, C2 alkyne, substituted or unsubstituted C4- C10 aryl, or substituted or unsubstituted C3-C10 heteroaryl;
A' is an anchoring group;
the substituent is at least one selected from the group consisting of a halogen atom, hydroxy, C1-C10 alkyl, and C1-C10 alkoxy; and
The hetero atom is at least one selected from the group consisting of N, O and S.
상기 R1 및 R2는 각각 독립적으로 치환 또는 비치환의 C1-C5 알킬, 치환 또는 비치환의 C6 아릴, 또는 치환 또는 비치환의 C4-C5 헤테로아릴이며; 여기서 치환기는 C1-C5 알킬, 및 C1-C5 알콕시로 이루어진 군에서 선택되는 하나 이상인 것을 특징으로 하는 다이케토피롤로피 기반의 유기 청색염료.The method of claim 1,
wherein R 1 and R 2 are each independently substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted C6 aryl, or substituted or unsubstituted C4-C5 heteroaryl; wherein the substituent is at least one selected from the group consisting of C1-C5 alkyl, and C1-C5 alkoxy.
상기 π1, π2, π'1, 및 π'2는 각각 독립적으로 C2 알킨, 치환 또는 비치환의 C6 아릴, 또는 치환 또는 비치환의 C4-C5 헤테로아릴이며; 여기서 치환기는 C1-C2 알킬 및 C1-C2 알콕시로 이루어진 군에서 선택되는 하나 이상이고; 및 헤테로 원자는 N, O 및 S로 이루어진 군에서 선택된 하나 이상인 것을 특징으로 하는 다이케토피롤로피 기반의 유기 청색염료.The method of claim 1,
π 1 , π 2 , π′ 1 , and π′ 2 are each independently C2 alkyne, substituted or unsubstituted C6 aryl, or substituted or unsubstituted C4-C5 heteroaryl; wherein the substituent is at least one selected from the group consisting of C1-C2 alkyl and C1-C2 alkoxy; And the hetero atom is a diketopyrrolopy-based organic blue dye, characterized in that at least one selected from the group consisting of N, O and S.
상기 R3 및 R4는 각각 독립적으로, 수소, 또는 치환 또는 비치환의 C1-C10알킬이며; 여기서 치환기는 C1-C5 알킬로 이루어진 군에서 선택되는 하나 이상인 것을 특징으로 하는 다이케토피롤로피 기반의 유기 청색염료.The method of claim 1,
wherein R 3 and R 4 are each independently hydrogen, or substituted or unsubstituted C1-C10 alkyl; Here, the substituent is a diketopyrrolopy-based organic blue dye, characterized in that at least one selected from the group consisting of C1-C5 alkyl.
상기 앵커링 그룹(anchoring group)은 cyanoacrylic acid 앵커(anchors), Catechol 앵커, Pyridyl 앵커, Phosphonate 앵커, 2-Hydroxylbenzonitrile 앵커, Pyridine-N-oxide 앵커, Hydroxamate 앵커 및 Sulfonate 앵커로 이루어진 군에서 선택되는 하나 이상인 것을 특징으로 하는 다이케토피롤로피 기반의 유기 청색염료.The method of claim 1,
The anchoring group is at least one selected from the group consisting of cyanoacrylic acid anchors, Catechol anchors, Pyridyl anchors, Phosphonate anchors, 2-Hydroxylbenzonitrile anchors, Pyridine-N-oxide anchors, Hydroxamate anchors and Sulfonate anchors. Diketopyrrolopy based organic blue dye.
상기 유기 청색염료는 화학식 (1-1) 및 화학식 (1-2) 중 적어도 하나 또는 둘인 것을 특징으로 하는 다이케토피롤로피 기반의 유기 청색염료:
화학식 (1-1)
화학식 (2-1)The method of claim 1,
The organic blue dye is an organic blue dye based on diketopyrrolophy, characterized in that at least one or two of Formulas (1-1) and (1-2):
Formula (1-1)
Formula (2-1)
(가) D-π1과 X-π2-A-π'1-π'2-CHO의 소노가시라(Sonogashira) 커플링 반응을 통해 D-π-A-π'-CHO를 제조하는 단계; 및
(나) 단계(가)에서 제조된 D-π-A-π'-CHO의 노베나겔(Knoevenagel) 축합반응을 통해 말단에 앵커링 그룹(anchoring group)를 결합하는 단계(상기에서, π, π1, π2, A, π', π'1, 및 π'은 제1항에서 정의한 바와 같고, X는 할로겐 원소이다);
를 포함하는 것을 특징으로 하는 다이케토피롤로피 기반의 유기 청색염료의 제조방법:
D-π-A-π'-A'화학식 (1)A method for producing an organic blue dye of formula (1) according to claim 1,
(A) preparing D-π-A-π'-CHO through Sonogashira coupling reaction of D-π 1 and X-π 2 -A-π' 1 -π' 2 -CHO; and
(B) coupling an anchoring group to the end through Knoevenagel condensation reaction of D-π-A-π'-CHO prepared in step (a) (in the above, π, π 1 , π 2 , A, π′, π′ 1 , and π′ are as defined in claim 1 , and X is a halogen element);
A method for producing a diketopyrrolophy-based organic blue dye comprising:
D-π-A-π'-A' Formula (1)
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KR20100136931A (en) | 2009-06-19 | 2010-12-29 | 주식회사 동진쎄미켐 | Novel organic dye and preparation thereof |
WO2014033582A2 (en) * | 2012-09-03 | 2014-03-06 | Ecole Polytechnique Federale De Lausanne (Epfl) | Diketopyrrolopyrole (dpp)-based sensitizers for electrochemical or optoelectronic devices |
KR20170077902A (en) * | 2015-12-28 | 2017-07-07 | (주)수양켐텍 | Novel compound and solar cell including the same |
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KR20100136931A (en) | 2009-06-19 | 2010-12-29 | 주식회사 동진쎄미켐 | Novel organic dye and preparation thereof |
WO2014033582A2 (en) * | 2012-09-03 | 2014-03-06 | Ecole Polytechnique Federale De Lausanne (Epfl) | Diketopyrrolopyrole (dpp)-based sensitizers for electrochemical or optoelectronic devices |
KR20170077902A (en) * | 2015-12-28 | 2017-07-07 | (주)수양켐텍 | Novel compound and solar cell including the same |
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