KR20110079515A - Novel organic dye and preparation thereof - Google Patents

Novel organic dye and preparation thereof Download PDF

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Publication number
KR20110079515A
KR20110079515A KR1020100131970A KR20100131970A KR20110079515A KR 20110079515 A KR20110079515 A KR 20110079515A KR 1020100131970 A KR1020100131970 A KR 1020100131970A KR 20100131970 A KR20100131970 A KR 20100131970A KR 20110079515 A KR20110079515 A KR 20110079515A
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South Korea
Prior art keywords
formula
dye
compound
photoelectric conversion
solar cell
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KR1020100131970A
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Korean (ko)
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안현철
이종찬
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주식회사 동진쎄미켐
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Priority to PCT/KR2010/009271 priority Critical patent/WO2011081357A2/en
Priority to CN2010800596062A priority patent/CN102695759A/en
Priority to CN201310476298.9A priority patent/CN103525116B/en
Priority to JP2012547000A priority patent/JP5875988B2/en
Priority to TW099146571A priority patent/TWI529221B/en
Publication of KR20110079515A publication Critical patent/KR20110079515A/en

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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
    • C09B19/00—Oxazine dyes
    • 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
    • C09B21/00—Thiazine dyes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • 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
    • 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
    • Y02E10/549—Organic PV cells

Abstract

PURPOSE: A novel organic dye with improved efficiency of a solar cell, a preparation method thereof, a dye-sensitized photoelectric conversion device using the same, and a dye-sensitized solar cell including the same are provided to ensure excellent solar extinction coefficient, Jsc(short circuit photocurrent density) and photoelectric conversion efficiency and to improve the efficiency of the solar cell. CONSTITUTION: A novel organic dye is represented by chemical formulas 1 - 4. In chemical formulas 1 - 4, Ar1 is substituted or unsubstituted C6-12 aryl; X is S or O; R1 - R4 are independently hydrogen, C1-12 alkyl or substituted or unsubstituted C6-12 aryl; and n is an integer of 1 - 5. A dye-sensitized photoelectric conversion device comprises oxide semiconductor microparticles in which the organic dye is supported. A dye-sensitized solar cell includes the dye-sensitized photoelectric conversion device.

Description

신규한 유기염료 및 이의 제조방법 {NOVEL ORGANIC DYE AND PREPARATION THEREOF}New organic dyes and preparation method thereof {NOVEL ORGANIC DYE AND PREPARATION THEREOF}

본 발명은 염료감응태양전지(dye-sensitized solar cell, DSSC)에 사용되는 신규한 염료 및 이의 제조방법에 관한 것이다.
The present invention relates to a novel dye used in dye-sensitized solar cells (DSSC) and a method for producing the same.

1991년도 스위스 국립 로잔 고등기술원(EPFL)의 마이클 그라첼(Michael Gratzel) 연구팀에 의해 염료감응 나노입자 산화티타늄 태양전지가 개발된 이후 이 분야에 관한 많은 연구가 진행되고 있다. 염료감응태양전지는 기존의 실리콘계 태양전지에 비해 효율이 높고 제조단가가 현저히 낮기 때문에 기존의 비정질 실리콘 태양전지를 대체할 수 있는 가능성을 가지고 있으며, 실리콘 태양전지와 달리 염료감응태양전지는 가시광선을 흡수하여 전자-홀(hole) 쌍을 생성할 수 있는 염료분자와, 생성된 전자를 전달하는 전이금속 산화물을 주 구성 재료로 하는 광전기화학적 태양전지이다.Since the development of the dye-sensitized nanoparticle titanium oxide solar cell by the team of Michael Gratzel of the Swiss National Lausanne Institute of Advanced Technology (EPFL) in 1991, much work has been done in this area. Dye-sensitized solar cells have the potential to replace conventional amorphous silicon solar cells because of their higher efficiency and lower manufacturing costs than conventional silicon-based solar cells. It is a photoelectrochemical solar cell whose main constituent material is a dye molecule capable of absorbing and generating electron-hole pairs, and a transition metal oxide for transferring generated electrons.

염료감응태양전지에 사용되는 염료로서 높은 광전기 전환효율을 나타내는 루테늄 금속 착체가 널리 사용되어 왔는데, 이 루테늄 금속 착체는 가격이 너무 비싸다는 단점이 있었다.As a dye used in dye-sensitized solar cells, ruthenium metal complexes having high photovoltaic conversion efficiency have been widely used, but this ruthenium metal complex has a disadvantage of being too expensive.

최근, 흡광효율, 산화환원 반응 안정성 및 분자내 전하-전달(charge-transfer, CT)계 흡수의 측면에서 우수한 물성을 나타내는, 금속을 함유하지 않은 유기염료가, 고가의 루테늄 금속 착체를 대체할 수 있는 태양전지용 염료로서 사용될 수 있음이 발견되어, 금속이 결여된 유기염료에 대한 연구가 중점적으로 이루어지고 있다.Recently, metal-free organic dyes, which exhibit excellent physical properties in terms of light absorption efficiency, redox reaction stability, and intramolecular charge-transfer (CT) absorption, can replace expensive ruthenium metal complexes. It has been found that it can be used as a dye for solar cells, and research on organic dyes lacking metals has been focused on.

유기염료는 일반적으로 π-결합 유닛에 의해 연결되는 전자 공여체(electron donor)-전자 수용체(electron acceptor) 잔기의 구조를 갖는다. 대부분의 유기염료에서, 아민 유도체가 전자 공여체의 역할을 하고, 2-시아노아크릴산 또는 로다닌 잔기가 전자 수용체의 역할을 하며, 이 두 부위는 메타인 유닛 또는 티오펜 체인과 같은 π-결합 시스템에 의해 연결된다.Organic dyes generally have a structure of electron donor-electron acceptor residues linked by π-binding units. In most organic dyes, amine derivatives act as electron donors, 2-cyanoacrylic acid or rhodanine residues act as electron acceptors, and these two sites are π-binding systems such as metaine units or thiophene chains. Is connected by.

일반적으로, 전자 공여체인 아민 유닛의 구조적 변화는 전자 특성의 변화, 예를 들어 청색 쪽으로 쉬프트(shift)된 흡광 스펙트럼을 가져오고, π-결합 길이를 변화시켜 흡광 스펙트럼과 산화환원 전위(redox potential)를 조절할 수 있다.In general, the structural change of the amine unit, which is an electron donor, results in a change in the electronic properties, for example, an absorption spectrum shifted toward blue, and by changing the π-bond length, the absorption spectrum and redox potential. Can be adjusted.

그러나, 이제까지 알려진 대부분의 유기염료는 루테늄 금속 착체 염료에 비해 낮은 변환효율과 낮은 구동 안정성을 나타내므로, 이러한 전자 공여체와 수용체의 종류 또는 π-결합 길이를 변화시킴으로써, 기존의 유기염료 화합물들에 비해 향상된 몰흡광계수를 가지며 높은 광전기 변환효율을 나타내는 새로운 염료를 개발하려는 노력이 지속되고 있는 실정이다.
However, most of the organic dyes known so far have lower conversion efficiency and lower driving stability than ruthenium metal complex dyes. Thus, by changing the type or the π-bond length of these electron donors and acceptors, Efforts have been made to develop new dyes having an improved molar absorption coefficient and showing high photoelectric conversion efficiency.

따라서, 본 발명은 종래의 염료보다 향상된 몰흡광계수 및 광전기 변환효율을 나타내어 태양전지의 효율을 크게 향상시킬 수 있는 유기염료 및 이의 제조방법을 제공하는 것을 목적으로 한다.Accordingly, an object of the present invention is to provide an organic dye and a method of manufacturing the same, which can improve the efficiency of solar cells by exhibiting an improved molar absorption coefficient and photoelectric conversion efficiency than conventional dyes.

또한 본 발명은 상기 염료를 포함하여 현저히 향상된 광전기 변환효율을 나타내며, Jsc(단회로 광전류 밀도, short circuit photocurrent density)와 몰흡광계수가 우수한 염료증감 광전변환소자, 및 효율이 현저히 향상된 태양전지를 제공하는 것을 목적으로 한다.
In addition, the present invention exhibits a significantly improved photovoltaic conversion efficiency including the dye, J sc (short circuit photocurrent density) and a dye-sensitized photoelectric conversion device excellent in the molar absorption coefficient, and a solar cell significantly improved efficiency It aims to provide.

상기 목적을 달성하기 위하여, 본 발명은 하기 화학식 1 내지 4 중 어느 하나로 표시되는 유기염료를 제공한다.In order to achieve the above object, the present invention provides an organic dye represented by any one of the following formula (1).

[화학식 1][Formula 1]

Figure pat00001
Figure pat00001

[화학식 2][Formula 2]

Figure pat00002
Figure pat00002

[화학식 3](3)

Figure pat00003
Figure pat00003

[화학식 4][Formula 4]

Figure pat00004
Figure pat00004

상기 식에서,Where

Ar1은 치환되거나 비치환된 C6-12 아릴이고;Ar 1 is substituted or unsubstituted C 6-12 aryl;

X는 S 또는 O이고;X is S or O;

A는

Figure pat00005
A is
Figure pat00005

Figure pat00006
, 또는 이들의 조합이고;
Figure pat00006
Or a combination thereof;

B는

Figure pat00007
B is
Figure pat00007

Figure pat00008
, 또는 이들의 조합이고;
Figure pat00008
Or a combination thereof;

C는 C is

Figure pat00009
Figure pat00009

Figure pat00010
Figure pat00010

Figure pat00011
이고;
Figure pat00011
ego;

R1 내지 R4는 각각 독립적으로 수소, C1-12 알킬 또는 치환되거나 비치환된 C6-12 아릴이고;R 1 to R 4 are each independently hydrogen, C 1-12 alkyl or substituted or unsubstituted C 6-12 aryl;

n은 1 내지 5의 정수이다.
n is an integer of 1-5.

또한 본 발명은 하기 화학식 5 또는 화학식 15로 표시되는 화합물과 상기 화학식 1 내지 4에서 정의한 A, B, A와 B, 또는 B와 A의 전구체 화합물을 순차 반응시킨 후 얻어진 화합물의 말단에 C를 결합하여 제조되는 화학식 1 내지 4 중 어느 하나로 표시되는 염료의 제조방법을 제공한다:In another aspect, the present invention is a compound represented by the following formula (5) or formula (15) and A, B, A and B, or a precursor compound of B and A defined in the above formulas 1 to 4 after the sequential reaction to bind C to the terminal of the compound obtained It provides a method for producing a dye represented by any one of formulas 1 to 4 prepared by:

[화학식 5][Chemical Formula 5]

Figure pat00012
Figure pat00012

[화학식 15][Formula 15]

Figure pat00013
Figure pat00013

상기 식에서, Ar1, 및 X는 상기에서 정의한 바와 같다.
Wherein Ar 1 and X are as defined above.

또한 본 발명은 상기 화학식 1 내지 4 중 어느 하나로 표시되는 화합물을 담지시킨 산화물 반도체 미립자를 포함하는 것을 특징으로 하는 염료증감 광전변환소자를 제공한다.
The present invention also provides a dye-sensitized photoelectric conversion device comprising an oxide semiconductor fine particle carrying a compound represented by any one of Formulas 1 to 4.

또한 본 발명은 상기 염료증감 광전변환소자를 포함하는 것을 특징으로 하는 염료감응태양전지를 제공한다.
In another aspect, the present invention provides a dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion device.

본 발명의 염료 화합물은 염료감응태양전지(DSSC)에 사용되어 종래의 염료보다 향상된 몰흡광계수, Jsc(단회로 광전류 밀도) 및 광전기 변환효율을 나타내어 태양전지의 효율을 크게 향상시킬 수 있고, 고가의 칼럼을 사용하지 않고도 정제가 가능하여 염료 합성단가를 획기적으로 낮출 수 있다.
The dye compound of the present invention can be used in a dye-sensitized solar cell (DSSC) to exhibit an improved molar absorption coefficient, J sc (single-circuit photocurrent density) and photoelectric conversion efficiency than conventional dyes, thereby greatly improving the efficiency of the solar cell, Purification can be performed without using an expensive column, thereby significantly lowering the cost of dye synthesis.

본 발명자들은, 특정 지방족 화합물을 전자 공여체로서 사용하고, 중간 연결부분(스페이서(spacer))에는 몰흡광계수를 증가시키고 소자의 안정성을 증가시키기 위한 티오펜계 또는 디하이드로티오펜계 유닛을 도입하되, 단일 방향으로 존재하던 스페이서 및 고정체(anchoring group)를 양 방향으로 도입하는 등 새로운 유기염료 구조를 갖는 화학식 1 내지 4 중 어느 하나로 표시되는 화합물을 산화물 반도체 미립자에 담지시켜 염료감응태양전지를 제조할 경우 광전기 변환효율, Jsc(단회로 광전류 밀도) 및 몰흡광계수가 높아 기존 염료감응태양전지보다 우수한 효율을 나타냄을 확인하고 본 발명을 완성하게 되었다.We use certain aliphatic compounds as electron donors and introduce thiophene- or dihydrothiophene-based units at the intermediate linkages (spacers) to increase the molar absorptivity and increase the stability of the device. Preparing a dye-sensitized solar cell by supporting a compound represented by any one of Formulas 1 to 4 having a new organic dye structure, such as introducing spacers and anchoring groups that existed in a single direction in both directions, on oxide semiconductor fine particles In this case, the photoelectric conversion efficiency, Jsc (short circuit photocurrent density) and the molar absorption coefficient are high, and thus, the present invention shows superior efficiency than the conventional dye-sensitized solar cell, thereby completing the present invention.

본 발명의 유기염료는 하기 화학식 1 내지 4 중 어느 하나로 표시되는 것을 특징으로 한다.The organic dyes of the present invention are characterized by being represented by any one of the following Chemical Formulas 1 to 4.

[화학식 1][Formula 1]

Figure pat00014
Figure pat00014

[화학식 2][Formula 2]

Figure pat00015
Figure pat00015

[화학식 3](3)

Figure pat00016
Figure pat00016

[화학식 4][Formula 4]

Figure pat00017
Figure pat00017

상기 식에서, Ar1, X, A, B, C, R1 내지 R4, 및 n은 상기에서 정의한 바와 같다.Wherein Ar 1 , X, A, B, C, R 1 to R 4 , and n are as defined above.

본 발명의 화학식 1의 염료 화합물은 바람직하게는 하기 구조식 중 어느 하나로 나타내어질 수 있다:The dye compound of formula 1 of the present invention may preferably be represented by any of the following structural formulas:

[화학식1-1][Formula 1-1]

Figure pat00018
Figure pat00018

[화학식1-2][Formula 1-2]

Figure pat00019
Figure pat00019

[화학식1-3][Formula 1-3]

Figure pat00020
Figure pat00020

[화학식1-4][Formula 1-4]

Figure pat00021
Figure pat00021

[화학식1-5][Formula 1-5]

Figure pat00022
Figure pat00022

[화학식1-6][Formula 1-6]

Figure pat00023
Figure pat00023

[화학식1-7][Formula 1-7]

Figure pat00024
Figure pat00024

[화학식1-8][Formula 1-8]

Figure pat00025
Figure pat00025

[화학식1-9][Formula 1-9]

Figure pat00026
Figure pat00026

[화학식1-10][Formula 1-10]

Figure pat00027
Figure pat00027

[화학식1-11][Formula 1-11]

Figure pat00028
Figure pat00028

[화학식1-12][Formula 1-12]

Figure pat00029
Figure pat00029

[화학식1-13][Formula 11-1]

Figure pat00030
Figure pat00030

상기 식에서, R은 각각 독립적으로 수소, C1-12 알킬 또는 치환되거나 비치환된 C6-12 아릴이다.Wherein each R is independently hydrogen, C 1-12 alkyl or substituted or unsubstituted C 6-12 aryl.

본 발명의 화학식 2의 염료 화합물은 바람직하게는 하기 구조식 중 어느 하나로 나타내어질 수 있다:The dye compound of formula 2 of the present invention may preferably be represented by any of the following structural formulas:

[화학식2-1][Formula 2-1]

Figure pat00031
Figure pat00031

[화학식2-2][Formula 2-2]

Figure pat00032
Figure pat00032

[화학식2-3][Formula 2-3]

Figure pat00033
Figure pat00033

[화학식2-4][Formula 2-4]

Figure pat00034
Figure pat00034

[화학식2-5][Formula 2-5]

Figure pat00035
Figure pat00035

[화학식2-6][Formula 2-6]

Figure pat00036
Figure pat00036

[화학식2-7][Formula 2-7]

Figure pat00037
Figure pat00037

상기 식에서, R은 상기에서 정의한 바와 같다.Wherein R is as defined above.

본 발명의 화학식 3의 염료 화합물은 바람직하게는 하기 구조식 중 어느 하나로 나타내어질 수 있다:The dye compound of formula 3 of the present invention may preferably be represented by any of the following structural formulas:

[화학식3-1][Formula 3-1]

Figure pat00038
Figure pat00038

[화학식3-2][Formula 3-2]

Figure pat00039
Figure pat00039

[화학식3-3][Formula 3-3]

Figure pat00040
Figure pat00040

[화학식3-4][Formula 3-4]

Figure pat00041
Figure pat00041

[화학식3-5][Formula 3-5]

Figure pat00042
Figure pat00042

상기 식에서, R은 상기에서 정의한 바와 같다.Wherein R is as defined above.

본 발명의 화학식 4의 염료 화합물은 바람직하게는 하기 구조식 중 어느 하나로 나타내어질 수 있다:The dye compound of formula 4 of the present invention may preferably be represented by any of the following structural formulas:

[화학식4-1][Formula 4-1]

Figure pat00043
Figure pat00043

[화학식4-2][Formula 4-2]

Figure pat00044
Figure pat00044

[화학식4-3][Formula 4-3]

Figure pat00045
Figure pat00045

[화학식4-4][Formula 4-4]

Figure pat00046
Figure pat00046

[화학식4-5][Formula 4-5]

Figure pat00047
Figure pat00047

상기 식에서, R은 상기에서 정의한 바와 같다.
Wherein R is as defined above.

또한 본 발명의 화학식 1 내지 4 중 어느 하나로 표시되는 염료는 하기 화학식 5 또는 화학식 15로 표시되는 화합물과 상기 화학식 1 내지 4에서 정의한 A, B, A와 B, 또는 B와 A의 전구체 화합물을 순차 반응시킨 후 얻어진 화합물의 말단에 C를 결합하여 제조할 수 있다.In addition, the dye represented by any one of formulas 1 to 4 of the present invention is a compound represented by the following formula (5) or formula (15) and A, B, A and B, or a precursor compound of B and A defined in the formulas 1 to 4 in sequence After the reaction can be prepared by bonding C to the terminal of the obtained compound.

[화학식 5][Chemical Formula 5]

Figure pat00048
Figure pat00048

[화학식 15][Formula 15]

Figure pat00049
Figure pat00049

상기 식에서, Ar1, 및 X는 상기에서 정의한 바와 같다.Wherein Ar 1 and X are as defined above.

구체적으로 본 발명에 따른 화학식 1의 화합물은 예를 들어, (1) 하기 화학식 5의 화합물을 하기 화학식 6의 화합물과 스즈끼 커플링 반응시켜 하기 화학식 7의 화합물을 제조하고, (2) 화학식 7의 화합물을 CH3CN 중에서 피페리딘 존재 하에서 시아노아세트산과 반응시킴으로써 제조될 수 있다. 그 구체적인 일례는 하기 반응식 1로서 나타낼 수 있다.Specifically, the compound of Chemical Formula 1 according to the present invention may be prepared by, for example, (1) Suzuki coupling reaction of a compound of Chemical Formula 5 with a compound of Chemical Formula 6, and (2) The compound can be prepared by reacting with cyanoacetic acid in the presence of piperidine in CH 3 CN. Specific examples thereof can be represented by the following Scheme 1.

Figure pat00050
Figure pat00050

[화학식 6][Formula 6]

Figure pat00051
Figure pat00051

[화학식 7][Formula 7]

Figure pat00052
Figure pat00052

상기 식에서, Ar1, X 및 B는 상기에서 정의한 바와 같다.Wherein Ar 1 , X and B are as defined above.

[반응식 1]Scheme 1

Figure pat00053
Figure pat00053

Figure pat00054

Figure pat00054

본 발명에 따른 화학식 2의 화합물은 예를 들어, (1) 하기 화학식 5의 화합물을 하기 화학식 8의 화합물과 스즈끼 커플링 반응시켜 하기 화학식 9의 화합물을 제조하고, (2) 화학식 9의 화합물을 테트라하이드로퓨란(THF) 중에서 트리플루오로아세트산과 반응시켜 하기 화학식 10의 화합물을 제조하고, (3) 화학식 10의 화합물을 CH3CN 중에서 피페리딘 존재 하에서 시아노아세트산과 반응시킴으로써 제조될 수 있다. 그 구체적인 일례는 하기 반응식 2로서 나타낼 수 있다.Compound of Formula 2 according to the present invention, for example, (1) Suzuki coupling reaction of a compound of Formula 5 with a compound of Formula 8 to produce a compound of Formula 9, (2) a compound of Formula 9 The compound of formula 10 may be prepared by reacting with trifluoroacetic acid in tetrahydrofuran (THF), and (3) the compound of formula 10 may be prepared by reacting with cyanoacetic acid in the presence of piperidine in CH 3 CN. . The specific example can be shown as following Reaction Scheme 2.

[화학식 5][Chemical Formula 5]

Figure pat00055
Figure pat00055

[화학식 8][Formula 8]

Figure pat00056
Figure pat00056

[화학식 9][Formula 9]

Figure pat00057
Figure pat00057

[화학식 10][Formula 10]

Figure pat00058
Figure pat00058

상기 식에서, Ar1, X, A 및 B는 상기에서 정의한 바와 같다.Wherein Ar 1 , X, A and B are as defined above.

[반응식 2]Scheme 2

Figure pat00059
Figure pat00059

Figure pat00060
Figure pat00060

본 발명에 따른 화학식 3의 화합물은 예를 들어, (1) 하기 화학식 5의 화합물을 하기 화학식 11의 화합물과 스즈끼 커플링 반응시켜 하기 화학식 12의 화합물을 제조하고, (2) 화학식 12의 화합물을 N-브로모숙신이미드와 반응시켜 하기 화학식 13의 화합물을 제조하고, (3) 화학식 13의 화합물을 하기 화학식 6의 화합물과 스즈끼 커플링 반응시켜 하기 화학식 14의 화합물을 제조하고, (4) 화학식 14의 화합물을 CH3CN 중에서 피페리딘 존재 하에서 시아노아세트산과 반응시킴으로써 제조될 수 있다. 그 구체적인 일례는 하기 반응식 3으로서 나타낼 수 있다.Compound (3) according to the present invention, for example, (1) Suzuki coupling reaction of a compound of formula (5) with a compound of formula (11) to prepare a compound of formula (12), (2) Reacting with N-bromosuccinimide to prepare a compound of formula 13, (3) to react a compound of formula 13 with a compound of formula 6 to Suzuki coupling to prepare a compound of formula 14, (4) Compounds of formula 14 can be prepared by reacting with cyanoacetic acid in the presence of piperidine in CH 3 CN. The specific example can be shown as following Reaction Scheme 3.

[화학식 5][Chemical Formula 5]

Figure pat00061
Figure pat00061

[화학식 11][Formula 11]

(HO)2B - A(HO) 2 B-A

[화학식 12][Chemical Formula 12]

Figure pat00062
Figure pat00062

[화학식 13][Formula 13]

Figure pat00063
Figure pat00063

[화학식 6][Formula 6]

Figure pat00064
Figure pat00064

[화학식 14][Formula 14]

Figure pat00065
Figure pat00065

상기 식에서, Ar1, X, A 및 B는 상기에서 정의한 바와 같다.Wherein Ar 1 , X, A and B are as defined above.

[반응식 3]Scheme 3

Figure pat00066
Figure pat00066

Figure pat00067

Figure pat00067

본 발명에 따른 화학식 4의 화합물은 예를 들어, (1) 하기 화학식 15의 화합물을 하기 화학식 16의 화합물과 테트라하이드로퓨란(THF) 중에서 칼륨 t-부톡시드 존재 하에 반응시켜 하기 화학식 17의 화합물을 제조하고, (2) 화학식 17의 화합물을 N-브로모숙신이미드와 반응시켜 하기 화학식 18의 화합물을 제조하고, (3) 화학식 18의 화합물을 하기 화학식 6의 화합물과 스즈끼 커플링 반응시켜 하기 화학식 19의 화합물을 제조하고, (4) 화학식 19의 화합물을 CH3CN 중에서 피페리딘 존재 하에서 시아노아세트산과 반응시킴으로써 제조될 수 있다. 그 구체적인 일례는 하기 반응식 4로서 나타낼 수 있다.The compound of formula 4 according to the present invention is, for example, (1) reacting a compound of formula 15 with tetrahydrofuran (THF) in the presence of potassium t-butoxide in the compound of formula (16) (2) reacting a compound of Formula 17 with N-bromosuccinimide to prepare a compound of Formula 18, and (3) reacting a compound of Formula 18 with a compound of Formula 6 to Suzuki coupling Compounds of formula 19 can be prepared and (4) compounds of formula 19 are reacted with cyanoacetic acid in the presence of piperidine in CH 3 CN. A specific example thereof can be represented by the following Scheme 4.

[화학식 15][Formula 15]

Figure pat00068
Figure pat00068

[화학식 16][Formula 16]

OHC - AOHC-A

[화학식 17][Formula 17]

Figure pat00069
Figure pat00069

[화학식 18][Formula 18]

Figure pat00070
Figure pat00070

[화학식 6][Formula 6]

Figure pat00071
Figure pat00071

[화학식 19][Formula 19]

Figure pat00072
Figure pat00072

상기 식에서, Ar1, X, A 및 B는 상기에서 정의한 바와 같다.Wherein Ar 1 , X, A and B are as defined above.

[반응식 4]Scheme 4

Figure pat00073
Figure pat00073

Figure pat00074

Figure pat00074

또한 본 발명은 염료증감 광전변환소자를 제공하는 바, 상기 염료증감 광전변환소자는 산화물 반도체 미립자에 상기 화학식 1 내지 4 중 어느 하나로 표시되는 염료를 담지시킨 것을 특징으로 한다. 본 발명은 염료증감 광전변환소자는 상기 화학식 1 내지 4 중 어느 하나로 표시되는 염료를 사용하는 것 이외에 종래 염료를 이용하여 태양전지용 염료증감 광전변환소자를 제조하는 방법들이 적용될 수 있음은 물론이며, 구체적인 일예로 대한민국공개특허공보 제10-2009-38377호(출원인 동진쎄미켐(주))에 기재된 방법들이 적용될 수 있으며, 바람직하게는 본 발명의 염료증감 광전변환소자는 산화물 반도체 미립자를 이용해서 기판상에 산화물 반도체의 박막을 제조하고, 이어서 상기 박막에 본 발명의 염료를 담지시킨 것이 좋다.
In addition, the present invention provides a dye-sensitized photoelectric conversion device, the dye-sensitized photoelectric conversion device is characterized in that the dye represented by any one of the formulas (1) to 4 in the oxide semiconductor fine particles. The present invention is a dye-sensitized photoelectric conversion device in addition to using the dye represented by any one of the formulas 1 to 4 methods of manufacturing a dye-sensitized photoelectric conversion device for solar cells using a conventional dye, of course, specific For example, the methods described in Korean Patent Publication No. 10-2009-38377 (Dongjin Semichem Co., Ltd.) may be applied. Preferably, the dye-sensitized photoelectric conversion device of the present invention is formed on a substrate using oxide semiconductor fine particles. It is good to prepare a thin film of an oxide semiconductor and then carry the dye of the present invention on the thin film.

이하에서 본 발명을 실시예에 의거하여 보다 구체적으로 설명한다. 단, 이들 실시예는 본 발명을 예시하기 위한 것일 뿐, 본 발명이 이들만으로 한정되는 것은 아니다.
Hereinafter, the present invention will be described in more detail with reference to Examples. However, these Examples are only for illustrating the present invention, the present invention is not limited to these.

실시예 1 Example 1

3,7-dibromo-10-(4-methoxyphenyl)-10H-phenothiazine 과 (E)-(5-oxothiophen-2(5H)-ylidene) methylboronic acid, Pd(PPh3)4 및 2M K2CO3 수용액을 디메틸포름아미드(DMF) 중에서 혼합한 후 12시간 동안 환류하였다. 결과로 수득된 반응 용액을 냉각시키고, 물(30ml)과 염수를 첨가한 후, 유기층을 분리 및 정제하여 중간체를 얻었다.3,7-dibromo-10- (4-methoxyphenyl) -10H-phenothiazine and (E)-(5-oxothiophen-2 (5H) -ylidene) methylboronic acid, Pd (PPh 3 ) 4 and 2M K 2 CO 3 Was mixed in dimethylformamide (DMF) and refluxed for 12 h. The resulting reaction solution was cooled, water (30 ml) and brine were added, and the organic layer was separated and purified to give an intermediate.

상기에서 제조된 중간체와 시아노아세트산을 혼합하여 제조한 혼합물을 진공건조한 후, MeCN 및 피페리딘와 혼합하고, 6시간 동안 환류하였다. 결과로 수득된 반응용액을 냉각시킨 후 유기층을 진공 하에서 제거하였다. 결과로 수득된 고형물을 실리카 겔 크로마토그래피 정제하여 하기 화합물 1을 얻었다. 얻은 화합물 1에 대해 FD-MS(Field desorption mass spectrum)을 수행한 결과 C35H21N3O5S3=660 에 대하여 m/z(측정치)=659 임을 확인했다.The mixture prepared by mixing the intermediate prepared above and cyanoacetic acid was vacuum dried, then mixed with MeCN and piperidine, and refluxed for 6 hours. After cooling the resulting reaction solution, the organic layer was removed under vacuum. The resulting solid was purified by silica gel chromatography to obtain compound 1 below. Field desorption mass spectrum (FD-MS) was performed on Compound 1 to obtain m / z (measured value) = 659 for C 35 H 21 N 3 O 5 S 3 = 660.

[화합물 1][Compound 1]

Figure pat00075
Figure pat00075

실시예 2 :Example 2:

상기 실시예 1에서 (E)-(5-oxothiophen-2(5H)-ylidene)methylboronic acid 대신에 (E)-(5-oxothieno[3,2-b]thiophen-2(5H)-ylidene)methyl- boronic acid를 사용하는 것을 제외하고는 실시예 1에서와 동일한 방법을 순차적으로 실시하여 하기 화합물 2를 얻었다. 상기 화합물 2에 대해 FD-MS(Field desorption mass spectrum)을 수행한 결과 C39H21N3O5S5=772 에 대하여 m/z(측정치)=771 임을 확인했다.(E)-(5-oxothieno [3,2-b] thiophen-2 (5H) -ylidene) methyl instead of (E)-(5-oxothiophen-2 (5H) -ylidene) methylboronic acid in Example 1 Except for using boronic acid, the same method as in Example 1 was carried out sequentially to obtain the following compound 2. Field desorption mass spectrum (FD-MS) was carried out on compound 2, and it was confirmed that m / z (measured value) = 771 with respect to C 39 H 21 N 3 O 5 S 5 = 772.

[화합물 2][Compound 2]

Figure pat00076
Figure pat00076

실시예 3 Example 3

상기 실시예 1에서 (E)-(5-oxothiophen-2(5H)-ylidene)methylboronic acid 대신에 (E)-(7-oxo-2,3-dihydrothieno[3,4-b][1,4]dioxin-5(7H) -ylidene)methylboronic acid를 사용하는 것을 제외하고는 실시예 1에서와 동일한 방법을 순차적으로 실시하여 하기 화합물 3을 얻었다. 상기 화합물에 대해 FD-MS(Field desorption mass spectrum)을 수행한 결과 C39H25N3O9S3=776 에 대하여 m/z(측정치)=775 임을 확인했다.In Example 1, (E)-(7-oxo-2,3-dihydrothieno [3,4-b] [1,4 instead of (E)-(5-oxothiophen-2 (5H) -ylidene) methylboronic acid Except for using] dioxin-5 (7H) -ylidene) methylboronic acid, the same method as in Example 1 was carried out sequentially to obtain the following compound 3. Performing a field desorption mass spectrum (FD-MS) for the compound confirmed that m / z (measured value) = 775 for C 39 H 25 N 3 O 9 S 3 = 776.

[화합물 3][Compound 3]

Figure pat00077

Figure pat00077

염료감응태양전지의 제조Fabrication of Dye-Sensitized Solar Cell

본 발명에 따른 염료의 전류-전압 특성을 평가하기 위해, 13+10 ㎛ TiO2 투명층을 이용하여 염료감응태양전지를 제조하였다. In order to evaluate the current-voltage characteristics of the dye according to the present invention, a dye-sensitized solar cell was prepared using a 13 + 10 μm TiO 2 transparent layer.

상세하게는 세척된 FTO(Pilkington, 8 Ωsq-1) 유리기판을 40 mM TiCl4 수용액 중에 함침시켰다. TiO2 페이스트(Solaronix, 13 nm 아나타제)를 스크린 프린팅하여 13 ㎛ 두께의 제1 TiO2 층을 제조하고, 광산란을 위해 다른 페이스트(CCIC, HWP-400)로 10 ㎛ 두께의 제2 TiO2 산란층을 제조하였다. 제조된 TiO2 전극을 본 발명에 따른 염료의 용액 (10mM의 3a,7a-디히드록시-5b-콜산 함유 에탄올 중에 상기 실시예 1-3에서 제조된 화합물 1-3을 각각 0.3 mM로 용해시킴)에 함침시킨 후, 실온에서 18시간 동안 방치하였다. FTO 기판 상에 H2PtCl6 용액(에탄올 1 mL 중에 Pt 2 mg 함유)을 코팅하여 대전극을 제조하였다. 이어, 아세토니트릴 중에 0.6 M 3-헥실-1,2-디메틸이미다졸리움 요오드, 0.04 M I2, 0.025 M LiI, 0.05 M 구아니디움 티오시아네이트 및 0.28 M tert-부틸피리딘을 용해시킨 전해질을 전지에 주입하여 염료감응태양전지를 제조하였다. 염료감응태양전지의 광전지 성능은 1000W 크세논 광원을 사용하여 측정하였으며, 그 결과를 하기 표 1에 나타내었다.Specifically, the washed FTO (Pilkington, 8 μsq-1) glass substrate was impregnated in an aqueous 40 mM TiCl 4 solution. TiO 2 paste (Solaronix, 13 nm anatase) was screen printed to produce a 13 μm thick first TiO 2 layer, and another 10 μm thick TiO 2 scattering layer with another paste (CCIC, HWP-400) for light scattering Was prepared. The prepared TiO 2 electrode was dissolved in 0.3 mM of the compound 1-3 prepared in Example 1-3 above in a solution of dye according to the present invention (10 mM 3a, 7a-dihydroxy-5b-cholic acid containing ethanol). ), And left at room temperature for 18 hours. The counter electrode was prepared by coating a solution of H 2 PtCl 6 (containing 2 mg of Pt in 1 mL of ethanol) on an FTO substrate. Then, an electrolyte in which 0.6 M 3-hexyl-1,2-dimethylimidazolium iodine, 0.04 MI 2 , 0.025 M LiI, 0.05 M guanidium thiocyanate and 0.28 M tert -butylpyridine was dissolved in acetonitrile was obtained. Was injected into a dye-sensitized solar cell. The photovoltaic performance of the dye-sensitized solar cell was measured using a 1000W xenon light source, and the results are shown in Table 1 below.

구분division 효율(η)(%)Efficiency (η) (%) 화합물 1Compound 1 4.84.8 화합물 2Compound 2 5.25.2 화합물 3Compound 3 4.94.9

상기 표 1에서 나타난 바와 같이 본 발명의 신규 염료는 우수한 광전기 변환효율을 나타내었다. 따라서 본 발명의 신규한 염료화합물은 태양전지의 효율을 크게 향상시킬 수 있고, 고가의 칼럼을 사용하지 않고도 정제가 가능하여 염료 합성단가를 획기적으로 낮출 수 있다.As shown in Table 1, the novel dye of the present invention showed excellent photoelectric conversion efficiency. Therefore, the novel dye compound of the present invention can greatly improve the efficiency of the solar cell, and can be purified without using expensive columns, thereby significantly lowering the cost of dye synthesis.

Claims (5)

하기 화학식 1 내지 4 중 어느 하나로 표시되는 유기염료:
[화학식 1]
Figure pat00078

[화학식 2]
Figure pat00079

[화학식 3]
Figure pat00080

[화학식 4]
Figure pat00081

상기 식에서,
Ar1은 치환되거나 비치환된 C6-12 아릴이고;
X는 S 또는 O이고;
A는
Figure pat00082

Figure pat00083
, 또는 이들의 조합이고;
B는
Figure pat00084

Figure pat00085
, 또는 이들의 조합이고;
C는
Figure pat00086

Figure pat00087

Figure pat00088
이고;
R1 내지 R4는 각각 독립적으로 수소, C1-12 알킬 또는 치환되거나 비치환된 C6-12 아릴이고;
n은 1 내지 5의 정수이다.An organic dye represented by one of the following Chemical Formulas 1 to 4:
[Formula 1]
Figure pat00078

(2)
Figure pat00079

(3)
Figure pat00080

[Chemical Formula 4]
Figure pat00081

Where
Ar 1 is substituted or unsubstituted C 6-12 aryl;
X is S or O;
A is
Figure pat00082

Figure pat00083
Or a combination thereof;
B is
Figure pat00084

Figure pat00085
Or a combination thereof;
C is
Figure pat00086

Figure pat00087

Figure pat00088
ego;
R 1 to R 4 are each independently hydrogen, C 1-12 alkyl or substituted or unsubstituted C 6-12 aryl;
n is an integer of 1-5. 제1항에 있어서,
상기 염료가 하기 구조식들 중 어느 하나인 것을 특징으로 하는 유기염료:
[화학식1-1]
Figure pat00089

[화학식1-2]
Figure pat00090

[화학식1-3]
Figure pat00091

[화학식1-4]
Figure pat00092

[화학식1-5]
Figure pat00093

[화학식1-6]
Figure pat00094

[화학식1-7]
Figure pat00095

[화학식1-8]
Figure pat00096

[화학식1-9]
Figure pat00097

[화학식1-10]
Figure pat00098

[화학식1-11]
Figure pat00099

[화학식1-12]
Figure pat00100

[화학식1-13]
Figure pat00101


[화학식2-1]
Figure pat00102

[화학식2-2]
Figure pat00103

[화학식2-3]
Figure pat00104

[화학식2-4]
Figure pat00105

[화학식2-5]
Figure pat00106

[화학식2-6]
Figure pat00107

[화학식2-7]
Figure pat00108

[화학식3-1]
Figure pat00109

[화학식3-2]
Figure pat00110

[화학식3-3]
Figure pat00111

[화학식3-4]
Figure pat00112

[화학식3-5]
Figure pat00113

[화학식4-1]
Figure pat00114

[화학식4-2]
Figure pat00115

[화학식4-3]
Figure pat00116

[화학식4-4]
Figure pat00117

[화학식4-5]
Figure pat00118

상기 식에서, R은 각각 독립적으로 수소, C1-12 알킬 또는 치환되거나 비치환된 C6-12 아릴이다.The method of claim 1,
Organic dyes, wherein the dye is any one of the following structural formulas:
[Formula 1-1]
Figure pat00089

[Formula 1-2]
Figure pat00090

[Formula 1-3]
Figure pat00091

[Formula 1-4]
Figure pat00092

[Formula 1-5]
Figure pat00093

[Formula 1-6]
Figure pat00094

[Formula 1-7]
Figure pat00095

[Formula 1-8]
Figure pat00096

[Formula 1-9]
Figure pat00097

[Formula 1-10]
Figure pat00098

[Formula 1-11]
Figure pat00099

[Formula 1-12]
Figure pat00100

[Formula 11-1]
Figure pat00101


[Formula 2-1]
Figure pat00102

[Formula 2-2]
Figure pat00103

[Formula 2-3]
Figure pat00104

[Formula 2-4]
Figure pat00105

[Formula 2-5]
Figure pat00106

[Formula 2-6]
Figure pat00107

[Formula 2-7]
Figure pat00108

[Formula 3-1]
Figure pat00109

[Formula 3-2]
Figure pat00110

[Formula 3-3]
Figure pat00111

[Formula 3-4]
Figure pat00112

[Formula 3-5]
Figure pat00113

[Formula 4-1]
Figure pat00114

[Formula 4-2]
Figure pat00115

[Formula 4-3]
Figure pat00116

[Formula 4-4]
Figure pat00117

[Formula 4-5]
Figure pat00118

Wherein each R is independently hydrogen, C 1-12 alkyl or substituted or unsubstituted C 6-12 aryl. 화학식 5 또는 화학식 15로 표시되는 화합물과 청구항 1에서 정의한 A, B, A와 B, 또는 B와 A의 전구체 화합물을 순차 반응시킨 후 얻어진 화합물의 말단에 C를 결합하여 제조되는 화학식 1 내지 4 중 어느 하나로 표시되는 염료의 제조방법:
[화학식 5]
Figure pat00119

[화학식 15]
Figure pat00120

상기 식에서, Ar1, 및 X는 제1항에서 정의한 바와 같다.In the formulas 1 to 4 prepared by binding C to the terminal of the compound obtained after sequentially reacting the compound represented by the formula (5) or (15) and the precursor compound of A, B, A and B, or B and A as defined in claim 1 Preparation method of the dye represented by either:
[Chemical Formula 5]
Figure pat00119

[Formula 15]
Figure pat00120

Wherein Ar 1 and X are as defined in claim 1. 제1항의 유기염료를 담지시킨 산화물 반도체 미립자를 포함하는 것을 특징으로 하는 염료증감 광전변환소자.A dye-sensitized photoelectric conversion element comprising oxide semiconductor fine particles carrying the organic dye of claim 1. 제4항의 염료증감 광전변환소자를 포함하는 것을 특징으로 하는 염료감응태양전지.A dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion device of claim 4.
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CN201310476298.9A CN103525116B (en) 2009-12-30 2010-12-23 Organic dye and its preparing process
JP2012547000A JP5875988B2 (en) 2009-12-30 2010-12-23 Novel organic dye and method for producing the same
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